Photosensitive resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device

Abstract

A photosensitive resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device. The photosensitive resin composition contains: at least one resin selected from the group consisting of a heterocyclic ring-containing polymer and a precursor thereof; and a compound A-a as a photochromic compound.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition, a cured product, a laminate, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device, and a semiconductor device. Background Technology

[0002] Today, the technology of using resin materials made from photosensitive resin compositions containing resins is being utilized in various fields.

[0003] For example, heterocyclic polymers such as polyimide have excellent heat resistance and insulation properties, and are therefore used in a variety of applications. These applications are not particularly limited, but taking semiconductor devices for mounting as an example, they can be used as insulating films, sealing materials, or protective films. Furthermore, they can also be used as base films and cover layers for flexible substrates.

[0004] For example, in the above-described applications, heterocyclic polymers such as polyimide are used in the form of photosensitive resin compositions containing heterocyclic polymers or their precursors.

[0005] For example, this photosensitive resin composition can be applied to a substrate by coating to form a photosensitive film, and then exposed, developed, heated, etc., as needed, thereby forming a cured product on the substrate.

[0006] Photosensitive resin compositions can be applied using known coating methods, thus offering excellent manufacturing adaptability, such as a high degree of design freedom in the shape, size, and application location of the applied resin composition. From the perspective of this excellent manufacturing adaptability, in addition to the high performance of heterocyclic polymers such as polyimide, the industrial applications of the aforementioned photosensitive resin compositions are increasingly promising.

[0007] For example, Patent Document 1 describes a negative photosensitive resin composition containing: (A) a polyamic acid, polyamic acid ester, or polyamic acid salt as a precursor of a polyimide with a specific structure; and (B) a photosensitizer.

[0008] Previous technical documents

[0009] Patent documents

[0010] Patent Document 1: International Publication No. 2017 / 170600 Summary of the Invention

[0011] The technical problem to be solved by the invention

[0012] When exposing and developing a photosensitive resin composition containing heterocyclic polymers to create a pattern of cured material, a large focus margin is required for the photosensitive resin composition.

[0013] The present invention aims to provide a photosensitive resin composition with high focus margin when forming a pattern of a cured material, a cured material formed by curing the photosensitive resin composition, a laminate containing the cured material, a method for manufacturing the cured material, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured material, and a semiconductor device containing the cured material.

[0014] means for solving technical problems

[0015] The following are examples of representative embodiments of the present invention.

[0016] <1> A photosensitive resin composition comprising:

[0017] At least one resin selected from the group consisting of heterocyclic polymers and their precursors; and

[0018] Compound Aa is a photochromic compound.

[0019] <2> The photosensitive resin composition according to <1>, wherein,

[0020] The above compound Aa satisfies conditions 1 and 2 below.

[0021] Condition 1: The structure changes to compound A when exposed to light with a wavelength of 365 nm. ex .

[0022] Condition 2: When the absorbance of compound Aa at 365 nm is set to abs365-A1, and compound A... ex The absorbance at 365nm was set to abs365-A ex1 When abs365-A1 exceeds abs365-A ex1 .

[0023] <3> The photosensitive resin composition according to <1> or <2>, wherein,

[0024] The membrane containing the above-mentioned resin and the above-mentioned compound Aa satisfies the following conditions 3 and 4.

[0025] Condition 3: When the membrane is illuminated with light of wavelength 365 nm, the structure of compound Aa in the membrane changes to that of compound A. ex .

[0026] Condition 4: When the content of compound Aa in the membrane is compared with that of compound Aa and compound A... ex The absorbance at 365 nm of a membrane containing a total content of 1% or more is defined as abs365-A2. Compound A contained in the membrane...ex The content of [a] relative to compound Aa and compound A ex The absorbance at 365 nm of a film with a total content of less than 0.5% by mass is defined as abs365-A. ex2 When abs365-A2 exceeds abs365-A ex2 .

[0027] <4> The photosensitive resin composition according to any one of <1> to <3>, wherein,

[0028] The film formed from the above-mentioned photosensitive resin composition satisfies the following conditions 5 and 6.

[0029] Condition 5: When the membrane is exposed to light with a wavelength of 365 nm, the structure of compound Aa in the membrane changes to that of compound A. ex .

[0030] Condition 6: When the content of compound Aa in the membrane is compared with that of compound Aa and compound A... ex The absorbance at 365 nm of a membrane containing a total content of 1% or more is defined as abs365-A3. Compound A contained in the membrane... ex The content of [a] relative to compound Aa and compound A ex The absorbance at 365 nm of a film with a total content of less than 0.5% by mass is defined as abs365-A. ex3 When, abs365-A3 exceeds abs365-A ex3 .

[0031] <5> The resin composition according to <4>, wherein,

[0032] The maximum absorption wavelength of compound Aa in the wavelength range of 300–700 nm is similar to that of compound A. ex The difference in maximum absorption wavelength between 300 and 700 nm is 10–400 nm.

[0033] <6> The photosensitive resin composition according to any one of <1> to <5>, wherein,

[0034] Compound Aa is a compound represented by any one of the following formulas: (Ab-1) to (Ab-6), (Ac-1), (Ac-2), (Ad-1), (Ad-2), (Ae-1), and (Ae-2).

[0035] [Chemical Formula 1]

[0036]

[0037] [Chemical Formula 2]

[0038]

[0039] [Chemical Formula 3]

[0040]

[0041] [Chemical Formula 4]

[0042]

[0043] In equation (Ab-1), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, R 4 R can be a hydrogen atom or any organic group. 5 R can be a hydrogen atom or any organic group. 4 With R 5 They can bond together to form a ring structure, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - Z 1 -O-, -S-, -NR 6 any one of - R 6 The dashed part represents a hydrogen atom or any organic group. The dashed part indicates a single bond or a double bond. When the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist.

[0044] In formula (Ab-2) or formula (Ab-3), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - R 6 Z can be a hydrogen atom or any organic group. 3 =C(R) Z )- or =N-, R Z L can be a hydrogen atom or any organic group. 2 Z can be any divalent linking group that can have substituents. 1 -O, -S, or -NR 6 When the dashed part is a double bond or R2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist.

[0045] In equation (Ab-4), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - R 6 L can be a hydrogen atom or any organic group. 2 Z can be any divalent linking group that can have substituents. 2 =O, =S, or =NR 7 R 7 It can be a hydrogen atom or any organic group, when the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist.

[0046] In formula (Ab-5) or formula (Ab-6), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - R 6 Z can be a hydrogen atom or any organic group. 3 =C(R) Z )- or =N-, R Z L can be a hydrogen atom or any organic group. 2 Z can be any divalent linking group that can have substituents. 4 -OH, -SH, -N(R) 6 Any one of H, R 6 An is a hydrogen atom or any organic group, where An is a counter anion. When the dashed part is a double bond or R... 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist.

[0047] In equation (Ac-1), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 Ar is any divalent linking group that can have substituents. 1 Each is an independent aromatic group. The dashed part represents a single bond or a double bond. When the dashed part represents a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist.

[0048] In equation (Ac-2), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R is a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 Ar is any divalent linking group that can have substituents. 1 Each can be an aromatic group that has substituents. The dashed part represents a single bond or a double bond. When the dashed part represents a double bond, R 3 It does not exist.

[0049] In equation (Ad-1), R 7 R can be independently a hydrogen atom, a halogen atom, or any organic group. 7 They can bond together to form a ring structure, and Ar can be an aromatic ring structure that can have substituents.

[0050] In equation (Ad-2), R 7 R can be independently a hydrogen atom, a halogen atom, or any organic group. 7 They can bond together to form a ring structure, R 8 Each R is independently a hydrogen atom, a halogen atom, or any organic group, and each R is independently a ring structure that may have substituents.

[0051] In equation (Ae-1), R 9 ~R 16 R can be independently a hydrogen atom, a halogen atom, or any organic group. 9 ~R 16 At least two of them can bond together to form a ring structure, where X is -O-, -S-, or -NR. 6 any one of - R 6 It can be a hydrogen atom or any organic group.

[0052] In equation (Ae-2), R 9 ~R 16 R can be independently a hydrogen atom, a halogen atom, or any organic group. 9 ~R16 At least two of them can bond together to form a ring structure, where X is -O-, -S-, or -NR. 6 any one of - R 6 It can be a hydrogen atom or any organic group.

[0053] <7> The photosensitive resin composition according to any one of <1> to <6>, wherein,

[0054] The content of the above compound Aa is 0.001 to 30% by mass relative to the total solids content of the photosensitive resin composition.

[0055] <8> A photosensitive resin composition comprising:

[0056] At least one resin selected from the group consisting of heterocyclic polymers and their precursors; and

[0057] Compound Ab is represented by any one of formulas (Ab-1) to (Ab-6).

[0058] [Chemical Formula 5]

[0059]

[0060] In equation (Ab-1), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, R 4 R can be a hydrogen atom or any organic group. 5 R can be a hydrogen atom or any organic group. 4 With R 5 They can bond together to form a ring structure, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - Z 1 -O-, -S-, -NR 6 any one of - R 6 The dashed part represents a hydrogen atom or any organic group. The dashed part indicates a single bond or a double bond. When the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist.

[0061] In formula (Ab-2) or formula (Ab-3), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group.2 They can bond with each other to form alicyclic or aromatic rings, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - R 6 Z can be a hydrogen atom or any organic group. 3 =C(R) Z )- or =N-, R Z L can be a hydrogen atom or any organic group. 2 Z can be any divalent linking group that can have substituents. 1 -O, -S, or -NR 6 When the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist.

[0062] In equation (Ab-4), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - R 6 L can be a hydrogen atom or any organic group. 2 Z can be any divalent linking group that can have substituents. 2 =O, =S, or =NR 6 - When the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist.

[0063] In formula (Ab-5) or formula (Ab-6), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - R 6 Z can be a hydrogen atom or any organic group. 3 =C(R) Z )- or =N-, R Z L can be a hydrogen atom or any organic group. 2Z can be any divalent linking group that can have substituents. 4 -OH, -SH, -N(R) 6 Any one of H, R 6 An is a hydrogen atom or any organic group, where An is a counter anion. When the dashed part is a double bond or R... 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist.

[0064] <9> A photosensitive resin composition comprising:

[0065] At least one resin selected from the group consisting of heterocyclic polymers and their precursors; and

[0066] Compound Ac is represented by formula (Ac-1) or formula (Ac-2).

[0067] [Chemical Formula 6]

[0068]

[0069] In equation (Ac-1), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 Ar is any divalent linking group that can have substituents. 1 Each is an independent aromatic group. The dashed part represents a single bond or a double bond. When the dashed part represents a double bond or R 2 When two R bonds are bonded to form an aromatic ring, the two R bonds... 3 It does not exist.

[0070] In equation (Ac-2), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R is a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 Ar is any divalent linking group that can have substituents. 1 Each can be an aromatic group that has substituents. The dashed part represents a single bond or a double bond. When the dashed part represents a double bond, R 3 It does not exist.

[0071] <10> A photosensitive resin composition comprising:

[0072] At least one resin selected from the group consisting of heterocyclic polymers and their precursors; and

[0073] Compound Ad is represented by formula (Ad-1) or formula (Ad-2).

[0074] [Chemical Formula 7]

[0075]

[0076] In equation (Ad-1), R 7 R can be independently a hydrogen atom, a halogen atom, or any organic group. 7 They can bond together to form a ring structure, and Ar can be an aromatic ring structure that can have substituents.

[0077] In equation (Ad-2), R 7 R can be independently a hydrogen atom, a halogen atom, or any organic group. 7 They can bond together to form a ring structure, R 8 Each R is independently a hydrogen atom, a halogen atom, or any organic group, and each R is independently a ring structure that may have substituents.

[0078] <11> A photosensitive resin composition comprising:

[0079] At least one resin selected from the group consisting of heterocyclic polymers and their precursors; and

[0080] Compound Ae is represented by formula (Ae-1) or formula (Ae-2).

[0081] [Chemical Formula 8]

[0082]

[0083] In equation (Ae-1), R 9 ~R 16 R can be independently a hydrogen atom, a halogen atom, or any organic group. 9 ~R 16 At least two of them can bond together to form a ring structure, where X is -O-, -S-, or -NR. 6 any one of - R 6 It can be a hydrogen atom or any organic group.

[0084] In equation (Ae-2), R 9 ~R 16 R can be independently a hydrogen atom, a halogen atom, or any organic group. 9 ~R 16 At least two of them can bond together to form a ring structure, where X is -O-, -S-, or -NR. 6 any one of - R 6 It can be a hydrogen atom or any organic group.

[0085] <12> The photosensitive resin composition according to any one of <1> to <11>, wherein,

[0086] The above-mentioned resin is a polyimide or a polyimide precursor.

[0087] <13> The resin composition according to <12>, wherein,

[0088] The imidization rate of the above polyimide precursors is 3-40%.

[0089] <14> The resin composition according to <13>, wherein,

[0090] The imidization rate is above 10% and below 30%.

[0091] <15> The photosensitive resin composition according to any one of <12> to <14>, wherein,

[0092] The above-mentioned polyimide precursor contains a structure represented by the following formula (1-5).

[0093] [Chemical Formula 9]

[0094]

[0095] R 51 Each is an independent organic group, and * indicates a bonding site with the resin structure.

[0096] <16> The photosensitive resin composition according to any one of <12> to <15>, wherein,

[0097] The resin described above has at least one repeating unit selected from the group consisting of the following repeating units: repeating unit represented by the following formula (1-1), repeating unit represented by the following formula (1-2), repeating unit represented by the following formula (1-3), and repeating unit represented by the following formula (1-4).

[0098] [Chemical Formula 10]

[0099]

[0100] [Chemical Formula 11]

[0101]

[0102] In equation (1-1), X 1 Y is a tetravalent organic group. 1 It is a divalent organic group.

[0103] In equation (1-2), A 2 For -O- or -NRZ-, RZ R is a hydrogen atom or a monovalent organic group. 2 X is a hydrogen atom or a monovalent organic group. 2 Y is a tetravalent organic group. 2 It is a divalent organic group.

[0104] In equation (1-3), A 3 For -O- or -NRZ-, R Z R is a hydrogen atom or a monovalent organic group. 3 X is a hydrogen atom or a monovalent organic group. 3 Y is a tetravalent organic group. 3 It is a divalent organic group.

[0105] In equation (1-4), A 41 and A 42 Each can be independently -O- or -NR. Z -, R Z R is a hydrogen atom or a monovalent organic group. 41 and R 42 Each can be independently a hydrogen atom or a monovalent organic group, X 4 Y is a tetravalent organic group. 4 It is a divalent organic group.

[0106] <17> The photosensitive resin composition according to <16>, wherein,

[0107] The resin described above contains at least one repeating unit selected from the group consisting of repeating unit A-1, repeating unit A-2, repeating unit A-3 and repeating unit A-4.

[0108] Repeating unit A-1: ​​It is a repeating unit represented by the above formula (1-1), and X1 is a repeating unit of any one of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure formed by removing two or more hydrogen atoms from the structure represented by the following formula (V-4).

[0109] Repeating unit A-2: It is a repeating unit represented by the above formula (1-2), and X2 is a repeating unit of any one of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure formed by removing two or more hydrogen atoms from the structure represented by the following formula (V-4).

[0110] Repeating unit A-3: It is a repeating unit represented by the above formula (1-3), and X3 is a repeating unit of any one of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure formed by removing two or more hydrogen atoms from the structure represented by the following formula (V-4).

[0111] Repeating unit A-4: It is a repeating unit represented by the above formula (1-4), and X4 is a repeating unit of any one of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure formed by removing two or more hydrogen atoms from the structure represented by the following formula (V-4).

[0112] [Chemical Formula 12]

[0113]

[0114] In equations (2a) to (2e), L 1 and L 2 Each is an independent divalent group or single bond that is not conjugated with the benzene ring to which it is bonded. 1 ~* 4 These represent the bonding sites with the carbonyl groups described in formulas (1-1), (1-2), (1-3), or (1-4), respectively, in which hydrogen atoms can be replaced by substituents.

[0115] In equation (V-4), n1 represents an integer greater than or equal to 1.

[0116] <18> The photosensitive resin composition according to <16> or <17>, wherein,

[0117] The resin further contains at least one repeating unit selected from the group consisting of repeating unit B-1, repeating unit B-2, repeating unit B-3 and repeating unit B-4.

[0118] Repeating unit B-1: It is a repeating unit represented by the above formula (1-1), and X1 contains a repeating unit with a structure formed by removing two or more hydrogen atoms from the structure represented by any one of the following formulas (V-1), (V-2), (V-3) and (V-5).

[0119] Repeating unit B-2: It is a repeating unit represented by the above formula (1-2), and X2 contains a repeating unit with a structure formed by removing two or more hydrogen atoms from the structure represented by any one of the following formulas (V-1), (V-2), (V-3) and (V-5).

[0120] Repeating unit B-3: It is a repeating unit represented by the above formula (1-3), and X3 contains a repeating unit with a structure formed by removing two or more hydrogen atoms from the structure represented by any one of the following formulas (V-1), (V-2), (V-3) and (V-5).

[0121] Repeating unit B-4: It is a repeating unit represented by the above formula (1-4), and X4 contains a repeating unit with a structure formed by removing two or more hydrogen atoms from the structure represented by any one of the following formulas (V-1), (V-2), (V-3) and (V-5).

[0122] [Chemical Formula 13]

[0123]

[0124] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0125] In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

[0126] <19> The photosensitive resin composition according to any one of <16> to <18>, wherein,

[0127] The resin described above contains at least one repeating unit selected from the group consisting of the following repeating units: a repeating unit represented by the above formula (1-1) where Y1 is a structure containing the structure represented by the following formulas (C-1) to (C-3); a repeating unit represented by the above formula (1-2) where Y2 is a structure containing the structure represented by the following formulas (C-1) to (C-3); a repeating unit represented by the above formula (1-3) where Y3 is a structure containing the structure represented by the following formulas (C-1) to (C-3); and a repeating unit represented by the above formula (1-4) where Y4 is a structure containing the structure represented by the following formulas (C-1) to (C-3).

[0128] [Chemical Formula 14]

[0129]

[0130] In equation (C-1), R 1 Each can independently represent a hydrogen atom or a monovalent organic group, n1 represents an integer from 0 to 3, n2 represents an integer from 0 to 3, and * indicates a bonding site with other structures.

[0131] In equation (C-2), R 1 Each can independently represent a hydrogen atom or a monovalent organic group, where n1 represents an integer from 0 to 3, n2 represents an integer from 0 to 3, and R 2 Alkyl or fluoroalkyl groups are indicated independently, and * indicates a bonding site with other structures.

[0132] In equation (C-3), R1 Each can be used to independently represent a hydrogen atom or a monovalent organic group, n1 represents an integer from 0 to 3, and * represents a bonding site with other structures.

[0133] <20> The photosensitive resin composition according to any one of <1> to <19> further comprises a photopolymerization initiator and a polymerizable compound.

[0134] <21> The photosensitive resin composition according to any one of <1> to <20> further contains an alkali-generating agent.

[0135] <22> The photosensitive resin composition according to any one of <1> to <21> further contains an organometallic complex.

[0136] <23> The photosensitive resin composition according to any one of <1> to <22> further contains a urea compound.

[0137] <24> The photosensitive resin composition according to any one of <1> to <23>, wherein,

[0138] The polystyrene equivalent weight-average molecular weight (Mw) of the resin is less than 20,000.

[0139] <25> The photosensitive resin composition according to any one of <1> to <23>, wherein,

[0140] The polystyrene resin has a converted weight-average molecular weight of 5,000 or more and 40,000 or less.

[0141] <26> A cured product formed by curing any one of the photosensitive resin compositions <1> to <25>.

[0142] <27> A laminate comprising two or more layers formed of the cured material described in <26>, wherein a metal layer is included between any of the layers formed of the cured material.

[0143] <28> A method for manufacturing a cured material, comprising:

[0144] The film forming process involves applying the photosensitive resin composition described in any one of <1> to <25> onto a substrate to form a film.

[0145] <29> The method for manufacturing the cured product according to <28> includes:

[0146] The exposure process selectively exposes the aforementioned film; and

[0147] In the developing process, the above film is developed using a developing solution to form a pattern.

[0148] <30> The method for manufacturing the cured product according to <28> or <29> includes:

[0149] The heating process involves heating the membrane at 50–450°C.

[0150] <31> A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in any one of <28> to <30>.

[0151] <32> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in any one of <28> to <30>.

[0152] <33> A semiconductor device comprising the cured material described in <26>.

[0153] Invention Effects

[0154] According to the present invention, a photosensitive resin composition with high focus margin when forming a pattern of a cured material is provided, a cured material formed by curing the photosensitive resin composition, a laminate containing the cured material, a method for manufacturing the cured material, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured material, and a semiconductor device containing the cured material are provided. Detailed Implementation

[0155] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

[0156] In this specification, the numerical range represented by the symbol “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower limit and upper limit, respectively.

[0157] In this specification, the term "process" means not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as they can achieve the intended function of the process.

[0158] In the designation of groups (atomic groups) in this specification, the designations without indicating whether they are substituted or unsubstituted include not only groups (atomic groups) without substituents, but also groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups).

[0159] In this specification, unless otherwise specified, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and photochemical rays or radiation such as electron beams.

[0160] In this specification, “(meth)acrylate” means “acrylate” and “methacrylate” or either of them, “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid” or either of them, and “(meth)acryloyl” means “acryloyl” and “methacryloyl” or either of them.

[0161] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0162] In this specification, total solids content refers to the total mass of the components after removing the solvent from all components of the composition. Furthermore, in this specification, solids concentration refers to the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0163] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​determined by gel permeation chromatography (GPC) and are defined as polystyrene conversion values. In this specification, for example, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series as a column, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined. Unless otherwise specified, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. In cases where THF has low solubility, or where THF is unsuitable as the eluent, NMP (N-methyl-2-pyrrolidone) can be used. Furthermore, unless otherwise specified, detection in GPC measurements uses a UV (ultraviolet) detector with a wavelength of 254 nm.

[0164] In this specification, when referring to the positional relationship of the layers constituting the laminate as "upper" or "lower," other layers may be located above or below the reference layer among the layers of interest. That is, a third layer or element may also be sandwiched between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction of the substrate stacked layers will be referred to as "upper," or, when a resin composition layer is present, the direction from the substrate toward the resin composition layer will be referred to as "upper," and the opposite direction will be referred to as "lower." Furthermore, this vertical orientation is for ease of explanation of this specification; in practice, the "upper" direction in this specification may differ from the vertically upward direction.

[0165] In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to that component as each component in the composition. Unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to that component.

[0166] In this manual, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50%RH.

[0167] In this specification, the preferred combination of methods is a more preferred method.

[0168] (Photosensitive resin composition)

[0169] The photosensitive resin composition of the first aspect of the present invention (hereinafter also simply referred to as the "first photosensitive resin composition") comprises: at least one resin selected from the group consisting of heterocyclic polymers and their precursors; and compound Aa as a photochromic compound.

[0170] The photosensitive resin composition of the second aspect of the present invention (hereinafter also simply referred to as the "second photosensitive resin composition") comprises: at least one resin selected from the group consisting of heterocyclic polymers and their precursors; and a compound Ab represented by any one of formulas (Ab-1) to (Ab-6).

[0171] The third-order photosensitive resin composition of the present invention (hereinafter also simply referred to as the "third photosensitive resin composition") comprises: at least one resin selected from the group consisting of heterocyclic polymers and their precursors; and a compound Ac represented by formula (Ac-1) or formula (Ac-2).

[0172] The photosensitive resin composition of the fourth aspect of the present invention (hereinafter also simply referred to as the "fourth photosensitive resin composition") comprises: at least one resin selected from the group consisting of heterocyclic polymers and their precursors; and compound Ad represented by formula (Ad-1) or formula (Ad-2).

[0173] The photosensitive resin composition of the fifth aspect of the present invention (hereinafter also simply referred to as the "fifth photosensitive resin composition") comprises: at least one resin selected from the group consisting of heterocyclic polymers and their precursors; and a compound Ae represented by formula (Ae-1) or formula (Ae-2).

[0174] Hereinafter, the first photosensitive resin composition, the second photosensitive resin composition, the third photosensitive resin composition, the fourth photosensitive resin composition and the fifth photosensitive resin composition will also be referred to as "photosensitive resin compositions".

[0175] Hereinafter, at least one resin selected from the group consisting of heterocyclic polymers and their precursors will also be referred to as "specific resin".

[0176] Hereinafter, compounds Aa, Ab, Ac, Ad, and Ae will be referred to as "compound A".

[0177] The photosensitive resin composition of the present invention is preferably used to form a photosensitive film (for exposure and development), and more preferably to form a film (for exposure and development using a developer containing an organic solvent).

[0178] The photosensitive resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for rewiring layers.

[0179] Furthermore, the photosensitive resin composition of the present invention is preferably used to form a photosensitive film for negative development.

[0180] In this invention, during exposure and development, negative development refers to development that removes non-exposed areas, while positive development refers to development that removes exposed areas.

[0181] As the above-described exposure method, developer, and developing method, for example, the exposure method described in the exposure step of the description of the method for manufacturing cured material described later, and the developer and developing method described in the developing step can be used.

[0182] The photosensitive resin composition of the present invention has a large focusing margin when forming patterns in cured products.

[0183] The mechanism by which these effects are achieved is not yet clear, but the following is a hypothesis.

[0184] In recent years, with the increase in signal speed, the pattern refinement is being carried out in cured photosensitive resin compositions used for forming patterns for purposes such as rewiring and insulation.

[0185] Here, especially when forming fine patterns, the focal point of the exposure light in the depth direction of the photosensitive layer is very important. If this focal point is significantly off, the amount of exposure to the unexposed areas will increase due to light leakage, thus reducing the resolution of the pattern obtained after development. Light leakage refers to the exposure light that shines into the photosensitive layer outside the area intended to be exposed.

[0186] Therefore, in the past, schemes to precisely control the focal position of the exposure light through improvements in the device have been studied. However, as mentioned above, with the progress of pattern miniaturization, the pattern width, pattern thickness, etc. tend to decrease, making it increasingly difficult to cope with the problem solely through device improvements.

[0187] Therefore, in this invention, the design of a photosensitive resin composition with high tolerance for focal position, i.e., capable of forming a pattern even if the focal position is slightly off, was studied. In this invention, high tolerance for focal position is also referred to as "large focus margin".

[0188] Specifically, the resin composition of the first aspect of the present invention contains compound Aa as a photochromic compound.

[0189] The resin composition of the second aspect of the present invention contains compound Ab.

[0190] The third-party resin composition of the present invention contains compound Ac.

[0191] The resin composition of the fourth embodiment of the present invention contains compound Ad.

[0192] The resin composition of the fifth embodiment of the present invention contains the compound Ae.

[0193] The compounds Aa to Ae are all compounds whose molecular geometry changes due to light absorption, thereby altering their absorption spectra.

[0194] Therefore, if a photosensitive film obtained from a photosensitive resin composition containing such a compound is exposed, in areas of low exposure, the exposure light is absorbed by compounds Aa to Ae or compounds generated from these compounds, thereby reducing the actual exposure of other photosensitive components. Furthermore, in areas of high exposure, the photosensitive components are sufficiently exposed due to the aforementioned changes in the absorption spectrum.

[0195] Therefore, in areas with low exposure, the photosensitivity reaction is difficult to occur, while in areas with high exposure, the photosensitivity reaction is fully carried out.

[0196] Therefore, it is believed that even if the focal position of the exposed light is slightly off and the area with low exposure becomes larger, the difference in actual exposure of the photosensitive components between the area with low exposure and the area with high exposure is also large, thereby increasing the contrast of the dissolution rate relative to the exposure, that is, increasing the focus margin.

[0197] Furthermore, as mentioned above, it is believed that due to the large difference in the actual exposure of the photosensitive components between areas with low exposure and areas with high exposure, fine patterns can be formed, that is, the resolution is also excellent.

[0198] Furthermore, because compound A contains highly polar structures or aromatic ring structures, its compatibility with the film is improved when used in combination with heterocyclic polymers or their precursors. Therefore, it is believed that the aggregation of compound A in the film can be easily suppressed, and the focusing margin and resolution can be further improved.

[0199] Here, patent document 1 does not describe a photosensitive resin composition containing compound A.

[0200] The components contained in the photosensitive resin composition of the present invention will be described in detail below.

[0201] <Specific Resins>

[0202] The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of heterocyclic polymers and their precursors.

[0203] The heterocyclic polymer is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.

[0204] In this invention, "main chain" refers to the longest bonded chain in the resin molecule, and "side chain" refers to the bonded chain other than the main chain.

[0205] Examples of heterocyclic polymers include polyimide, polybenzoxazole, and polyamide-imide.

[0206] The precursor of a heterocyclic polymer refers to a resin that becomes a heterocyclic polymer by undergoing a change in its chemical structure through external stimulation. Preferably, it is a resin that becomes a heterocyclic polymer by undergoing a change in its chemical structure through heat. More preferably, it is a resin that becomes a heterocyclic polymer by forming a ring structure through a ring-closing reaction through heat.

[0207] Examples of precursors for heterocyclic polymers include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors.

[0208] That is, the photosensitive resin composition preferably contains at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide imide and polyamide imide precursor as a specific resin.

[0209] The photosensitive resin composition preferably contains polyimide or a polyimide precursor as a specific resin.

[0210] The resin preferably has polymerizable groups, and more preferably contains free radical polymerizable groups.

[0211] When a particular resin has free radical polymerizable groups, the photosensitive resin composition of the present invention preferably contains a free radical polymerization initiator, more preferably a free radical polymerization initiator and a free radical crosslinking agent. Furthermore, a sensitizer may be included as needed. For example, a negative photosensitive film can be formed from such a resin composition.

[0212] Furthermore, certain resins may have polar conversion groups such as acid-decomposing groups.

[0213] When a particular resin has acid-decomposing groups, the photosensitive resin composition preferably contains a photoacid-generating agent. Such a photosensitive resin composition can, for example, form a positive or negative photosensitive film that is chemically amplified.

[0214] Setting the weight-average molecular weight of the polystyrene from a specific resin to less than 20,000 is also a preferred embodiment of the present invention. In this case, the lower limit of the weight-average molecular weight is preferably 5,000 or more, and more preferably 8,000 or more.

[0215] [Polyimide precursor]

[0216] The type of polyimide precursor used in this invention is not particularly limited, but preferably contains repeating units represented by the following formula (2).

[0217] [Chemical Formula 15]

[0218]

[0219] In equation (2), A 1 and A 2 Each independently represents an oxygen atom or -NR. z -, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group, R z It represents a hydrogen atom or a monovalent organic group.

[0220] A in equation (2) 1 and A2 Each independently represents an oxygen atom or -NR. z - Preferably, it contains oxygen atoms.

[0221] R z It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.

[0222] R in equation (2) 111 This indicates a divalent organic group. Examples of divalent organic groups include groups containing straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, these are straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof. More preferably, these are groups containing aromatic groups with 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the cyclic hydrocarbon groups in the aforementioned cyclic aliphatic groups and aromatic groups can be replaced by groups containing heteroatoms. R in formula (2) 111 Examples include groups represented by -Ar- and -Ar-L-Ar-, with a preference for groups represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. Their preferred ranges are as described above.

[0223] R 111 The preferred diamine is derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

[0224] Specifically, R 111 Preferably, the diamine contains a straight-chain or branched aliphatic group with 2 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 3 to 20 carbon atoms, or a combination thereof; more preferably, it is a diamine containing an aromatic group with 6 to 20 carbon atoms. The hydrocarbon group in the chain of the aforementioned straight-chain or branched aliphatic group can be replaced by a group containing heteroatoms, and the cyclic hydrocarbon group of the aforementioned cyclic aliphatic group and aromatic group can be replaced by a group containing heteroatoms. Examples of groups containing aromatic groups include the following groups.

[0225] [Chemical Formula 16]

[0226]

[0227] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO- or combinations thereof, more preferably a single bond or a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S- or -SO2-, and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-.

[0228] In the formula, * indicates the bonding site with other structures.

[0229] As diamines, examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane.

[0230] 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine;

[0231] m-Phenylenediamine or p-Phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2, 2-Bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfone, bis[4-(3-aminophenoxy)phenyl] sulfone, bis[4-(2-aminophenoxy)phenyl] sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4' -Dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, At least one diamine selected from the following: 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobitoluidine, or 4,4'-diaminotetraphenyl.

[0232] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0233] Furthermore, the diamine having two or more alkylene glycol units on the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 may also be preferred.

[0234] From the perspective of the flexibility of the obtained organic membrane, R 111 Preferably represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. Ar is preferably phenylene, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group here is preferably alkylene.

[0235] Furthermore, from the perspective of i-ray transmittance, R 111 Preferably, it is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, it is more preferably a divalent organic group represented by formula (61).

[0236] Equation (51)

[0237] [Chemical Formula 17]

[0238]

[0239] In equation (51), R 50 ~R 57 Each can be independently a hydrogen atom, a fluorine atom, or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * represents the bonding site with the nitrogen atom in formula (2) independently.

[0240] As R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0241] [Chemical Formula 18]

[0242]

[0243] In equation (61), R 58 and R 59 Each of the above can be independently represented by a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2).

[0244] Examples of diamines that impart the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One or more of these may be used.

[0245] Furthermore, R 111 It is also preferable to use a group represented by the following formula (71). In the above manner, R 111 More preferably, it is a group represented by the following formula (72).

[0246] [Chemical Formula 19]

[0247]

[0248] In equation (71), A 1 ~A 3 Each is a single bond or a divalent linker, and * indicates the bonding site with the nitrogen atom in formula (2). The hydrogen atoms of the four benzene rings recorded in formula (71) can be replaced by substituents.

[0249] In this specification, a bond that intersects the edge of a ring structure refers to a bond that replaces any one of the hydrogen atoms in the ring structure.

[0250] In equation (72), * represents the bonding site with the nitrogen atom in equation (2).

[0251] In equation (71), A 1 ~A 3 Preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a combination of two or more thereof. More preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -C(=O)-, or a combination of two or more thereof. Even more preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms or -O- that can be replaced by a fluorine atom.

[0252] In particular, A 1 and A 3 The preferred option is -O-.

[0253] In particular, A 2 Preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by fluorine atoms.

[0254] Among these, A 1 and A 3 For -O- and A 2 The -C(CH3)2- configuration is also one of the preferred embodiments of the present invention.

[0255] The number of carbon atoms in the aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by fluorine atoms is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 4.

[0256] Specific examples of aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms include -CH2-, -C(CH3)2-, and -C(CF3)2-, among which -C(CH3)2- is preferred.

[0257] Examples of substituents in the four benzene rings described in formula (71) include fluorine atoms, hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms.

[0258] Furthermore, the fact that all four benzene rings described in formula (71) are unsubstituted is also one of the preferred embodiments of the present invention.

[0259] Furthermore, R 111 It is also preferable to use a group represented by the following formula (81). In the above manner, R 111 More preferably, it is a group represented by the following formula (82).

[0260] [Chemical Formula 20]

[0261]

[0262] In equation (81), A 1 and A 2 Each is a single bond or a divalent linker, and * indicates the bonding site with the nitrogen atom in formula (2). The hydrogen atoms in the three benzene rings recorded in formula (81) can be replaced by substituents.

[0263] In equation (82), * represents the bonding site with the nitrogen atom in equation (2).

[0264] In equation (81), A 1 and A 2 Each group is preferably an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a combination of two or more thereof. More preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, -O-, -C(=O)-, or a combination of two or more thereof. Even more preferably, it is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom or -O-. Particularly preferred is -C(CH3)2-.

[0265] R in equation (2) 115 It represents a tetravalent organic group. As a tetravalent organic group, it is preferred to be a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

[0266] In equation (5) or equation (6), * independently represents the bonding site with other structures.

[0267] [Chemical Formula 21]

[0268]

[0269] In equation (5), R 112 It is a single bond or a divalent linker, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and combinations thereof, more preferably a single bond or a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S- and -SO2-, and even more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0270] Furthermore, R 115 It is also preferable to use a group represented by the following formula (7). In the above manner, R 115More preferably, it is a group represented by the following formula (7-2).

[0271] [Chemical Formula 22]

[0272]

[0273] In equation (7), A 1 ~A 3 Each is a single bond or a divalent linker, and * indicates the bonding site with the carbonyl group in formula (2). The hydrogen atoms of the four benzene rings recorded in formula (7) can be replaced by substituents.

[0274] In equation (7-2), * indicates the bonding site with the carbonyl group in equation (2).

[0275] In equation (7), A 1 ~A 3 The preferred method for the substituents in the benzene ring is the same as that for A in formula (7-1) above. 1 ~A 3 The preferred method is the same as that for substituents in the benzene ring.

[0276] Specifically, R 115 Examples include the tetracarboxylic acid residue remaining after removing the anhydride group from a tetracarboxylic dianhydride. As a counterpart to R... 115 The structure of the polyimide precursor can contain only one tetracarboxylic dianhydride residue or more than two tetracarboxylic dianhydride residues.

[0277] Tetracarboxylic dianhydride is preferably represented by the following formula (O).

[0278] [Chemical Formula 23]

[0279]

[0280] In equation (O), R 115 This indicates a tetravalent organic group. R 115 The meaning of R in equation (2) 115 The meanings are the same, and the preferred ranges are also the same.

[0281] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride. 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0282] Furthermore, tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can be cited as preferred examples.

[0283] In equation (2), R 111 and R 115 At least one of them can also have an OH group. More specifically, as R 111 Examples of residues from diaminophenol derivatives can be cited.

[0284] R in equation (2) 113 and R 114 Each can be independently represented by a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferred to contain a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkoxide group. Furthermore, R is preferred. 113 and R 114 At least one of them contains a polymeric group, more preferably both contain polymeric groups. R is also preferred. 113 and R 114At least one of them contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a cross-linking reaction through the action of heat, free radicals, etc., and is preferably a free radical polymerizable group. Specific examples of polymerizable groups include groups having olefinic unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetyl, benzoxazolyl, terminal isocyanate, and amino groups. As for the free radical polymerizable group in the polyimide precursor, a group having an olefinic unsaturated bond is preferred.

[0285] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, groups represented by formula (III) below, and preferably groups represented by formula (III) below.

[0286] [Chemical Formula 24]

[0287]

[0288] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0289] In equation (III), * indicates the bonding site with other structures.

[0290] In equation (III), R 201 It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0291] R 201 Preferred examples include alkylene compounds such as ethylene, propyleneene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH2CH(OH)CH2-, and polyalkoxide compounds; more preferably, alkylene compounds such as ethylene and propyleneene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkoxide compounds; and even more preferably, alkylene compounds such as ethylene and propyleneene or polyalkoxide compounds.

[0292] In this invention, polyalkoxide refers to a group consisting of two or more alkoxide groups directly bonded together. The alkylene groups within the multiple alkoxide groups in a polyalkoxide group may be the same or different.

[0293] When polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0294] The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.

[0295] Furthermore, the aforementioned alkylene group may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0296] Furthermore, the number of alkoxides contained in the polyalkoxide (the number of repetitions of the polyalkoxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0297] From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or groups bonded to multiple ethoxy groups and multiple propoxy groups are preferred as polyvinyloxy groups, more preferably polyvinyloxy or polypropyleneoxy, and even more preferably polyvinyloxy. Among the aforementioned groups bonded to multiple ethoxy and propoxy groups, the ethoxy groups and propoxy groups can be arranged randomly, form blocks, or be arranged in alternating patterns. The preferred manner for the number of repetitions of the ethoxy groups, etc., is as described above.

[0298] In equation (2), when R 113 When it is a hydrogen atom or R 114 When the hydrogen atom is present, the polyimide precursor can form a salt pair with a tertiary amine compound having an olefinically unsaturated bond. N,N-dimethylaminopropyl methacrylate is an example of such a tertiary amine compound having an olefinically unsaturated bond.

[0299] Furthermore, R in equation (2) is preferred. 113 A 2 and carbonyl group, and R 114 A 1 At least one of the carbonyl groups constitutes the structure represented by the formulas (1-5) described later.

[0300] In equation (2), R 113 and R 114 At least one of them can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it decomposes through the action of acid to produce a base-soluble group such as a phenolic hydroxyl group or a carboxyl group. Acetal, ketal, silyl, silyl ether, tert-alkyl ester, etc. are preferred. From the viewpoint of exposure sensitivity, acetal or ketal is more preferred.

[0301] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0302] The polyimide precursor also preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0303] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0304] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in this invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the range of exposure latitude can be further increased.

[0305] Equation (2-A)

[0306] [Chemical Formula 25]

[0307]

[0308] In equation (2-A), A 1 and A 2 R represents an oxygen atom. 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, preferably both of them are groups containing polymerizable groups.

[0309] A 1 A 2 R 111 R 113 and R 114 The meanings are independently related to A in equation (2). 1 A 2 R 111 R 113 and R 114 The meanings are the same, and the preferred ranges are also the same. R112 The meaning of R in equation (5) 112 The meanings are the same, and the preferred ranges are also the same.

[0310] The polyimide precursor may contain one repeating unit represented by formula (2), or two or more repeating units represented by formula (2). Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit represented by formula (2) above, the polyimide precursor may also contain other types of repeating units.

[0311] As one embodiment of the polyimide precursor in this invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide except for the end units can be repeating units represented by formula (2).

[0312] The polyimide precursor preferably has at least one repeating unit selected from the group consisting of the following repeating units: repeating unit represented by formula (1-1), repeating unit represented by formula (1-2), repeating unit represented by formula (1-3), and repeating unit represented by formula (1-4).

[0313] In these, the polyimide precursor preferably has at least a repeating unit represented by formula (1-4), more preferably a repeating unit represented by formula (1-4) and at least one repeating unit selected from the group consisting of repeating units represented by formula (1-1), repeating units represented by formula (1-2) and repeating units represented by formula (1-3).

[0314] [Chemical Formula 26]

[0315]

[0316] [Chemical Formula 27]

[0317]

[0318] In equation (1-1), X 1 Y is a tetravalent organic group. 1 It is a divalent organic group.

[0319] In equation (1-2), A 2 -O- or -NR Z -, R Z R is a hydrogen atom or a monovalent organic group. 2 X is a hydrogen atom or a monovalent organic group. 2Y is a tetravalent organic group. 2 It is a divalent organic group.

[0320] In equation (1-3), A 3 -O- or -NR Z -, R Z R is a hydrogen atom or a monovalent organic group. 3 X is a hydrogen atom or a monovalent organic group. 3 Y is a tetravalent organic group. 3 It is a divalent organic group.

[0321] In equation (1-4), A 41 and A 42 Each can be independently -O- or -NR. Z -, R Z R is a hydrogen atom or a monovalent organic group. 41 and R 42 Each can be independently a hydrogen atom or a monovalent organic group, X 4 Y is a tetravalent organic group. 4 It is a divalent organic group.

[0322] [X] 1 ]

[0323] In equation (1-1), X 1 The number of carbon atoms is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40.

[0324] In equation (1-1), X 1 Preferably, it is any one of the structures represented by formulas (2a) to (2e) below, or contains a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4) below.

[0325] [Chemical Formula 28]

[0326]

[0327] In equations (2a) to (2e), L 1 and L 2 Each of the above represents a divalent group or single bond that is not conjugated with the benzene ring to which it is bonded. *1 to *4 represent the bonding sites with the carbonyl groups described in formulas (1-1), (1-2), (1-3), or (1-4), respectively. The hydrogen atoms in these structures can be replaced by substituents.

[0328] In equation (V-4), n1 represents an integer greater than or equal to 1.

[0329] In equation (2c), L 1 and L 2 Each is preferably -CH2- or -O-, independently.

[0330] In formulas (2a) to (2e), the hydrogen atoms can be replaced by substituents. Examples of substituents include alkyl groups and haloalkyl groups, preferably alkyl groups with 1 to 4 carbon atoms or haloalkyl groups with 1 to 4 carbon atoms, and more preferably methyl or trifluoromethyl groups. A haloalkyl group refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom. As a halogen atom, F or Cl is preferred, and more preferably F.

[0331] In formula (V-4), n1 is preferably an integer from 1 to 5, more preferably 1 or 2, and even more preferably 1.

[0332] When X 1 When X contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-4), 2 Preferably, it is a group represented by the following formula (V-4-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the definition and preferred configuration of n1 are as described above. The hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0333] [Chemical Formula 29]

[0334]

[0335] Furthermore, in equation (1-1), X 1 It is also preferred to contain a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1), (V-2), (V-3) and (V-5).

[0336] [Chemical Formula 30]

[0337]

[0338] In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group.

[0339] In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can bond together to form a ring structure.

[0340] In equation (V-2), R X1Each of the components is preferably an alkyl or haloalkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, and even more preferably methyl or trifluoromethyl. A haloalkyl group refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom. The halogen atom is preferably F or Cl, more preferably F.

[0341] In equation (V-3), R X2 and R X3 Each atom is preferably a hydrogen atom.

[0342] When R X2 With R X3 When bonded to form a ring structure, R X2 With R X3 The structure formed by bonding is preferably a single bond, -O- or -C(R)2-, more preferably -O- or -C(R)2-, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, alkyl or aryl, and even more preferably a hydrogen atom.

[0343] When X 1 When X contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-1), 1 Preferably, it is a group represented by the following formula (V-1-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0344] [Chemical Formula 31]

[0345]

[0346] When X 1 When X contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-2), 1 Preferably, the group is represented by the following formula (V-2-1). In this specification, a bond intersecting the edge of the ring structure refers to a bond that substitutes for any one of the hydrogen atoms in the ring structure. In the following formulas, * indicates a group corresponding to X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, R X1 The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0347] [Chemical Formula 32]

[0348]

[0349] When X 1When X contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-3), 1 Preferably, the group is represented by formula (V-3-1) or formula (V-3-2) below. From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (V-3-2) is preferred. In the following formulas, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, R X2 and R X3 The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0350] [Chemical Formula 33]

[0351]

[0352] When X 1 When X contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (V-5), 1 Preferably, it is a group represented by the following formula (V-5-1). In the following formula, * represents X in formula (1-1). 1 The bonding sites of the four carbonyl groups. Furthermore, the hydrogen atoms in the following structure can be further replaced by known substituents such as hydrocarbon groups.

[0353] [Chemical Formula 34]

[0354]

[0355] In addition, X 1 It can be the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic acid dianhydride as described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0356] And, X 1 Preferably, the structure does not contain imide bonds.

[0357] And, X 1 Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds.

[0358] In this invention, the carbamate bond refers to the bond formed by *-OC(=O)-NR. N -* indicates the key, R N Represents a hydrogen atom or a monovalent organic group, with * indicating the bonding site with a carbon atom. R N Preferably, it is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.

[0359] In this invention, the urea bond refers to the bond formed by *-NR. N-C(=O)-NR N -* indicates the key, R N Each symbol represents a hydrogen atom or a monovalent organic group independently, and * indicates the bonding site with a carbon atom. R N The preferred method is as described above.

[0360] In addition, X 1 Preferably, the structure does not contain ester bonds.

[0361] In this invention, an ester bond refers to a bond represented by *-OC (=O)-*.

[0362] Among these, X 1 Preferably, it is free of imide bonds, carbamate bonds, urea bonds and amide bonds, and more preferably, it is free of imide bonds, carbamate bonds, urea bonds, amide bonds and ester bonds.

[0363] [Y] 1 ]

[0364] In equation (1-1), Y 1 The number of carbon atoms is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40.

[0365] In equation (1-1), Y 1 Preferably, the structure contains the structure represented by formulas (C-1) to (C-3).

[0366] [Chemical Formula 35]

[0367]

[0368] In equation (C-1), R 1 Each can independently represent a hydrogen atom or a monovalent organic group, n1 represents an integer from 0 to 3, n2 represents an integer from 0 to 3, and * indicates a bonding site with other structures.

[0369] In equation (C-2), R 1 Each can independently represent a hydrogen atom or a monovalent organic group, where n1 represents an integer from 0 to 3, n2 represents an integer from 0 to 3, and R 2 Alkyl or fluoroalkyl groups are indicated independently, and * indicates a bonding site with other structures.

[0370] In equation (C-3), R 1 Each can be used to independently represent a hydrogen atom or a monovalent organic group, n1 represents an integer from 0 to 3, and * represents a bonding site with other structures.

[0371] In equation (C-1), R 1Each of the components is preferably an alkyl or haloalkyl group, more preferably an alkyl or haloalkyl group having 1 to 4 carbon atoms, and even more preferably methyl or trifluoromethyl. The halogen atom in the haloalkyl group is preferably F or Cl, more preferably F.

[0372] In formula (C-1), n1 is preferably 0 or 1, and more preferably 1.

[0373] In formula (C-1), n2 is preferably 0 or 1, and more preferably 1.

[0374] In equation (C-2), R 1 The preferred methods for n1 and n2 are respectively related to R in equation (C-1). 1 The preferred methods for n1 and n2 are the same.

[0375] In equation (C-2), R 2 Each of the components is preferably an alkyl group having 1 to 4 carbon atoms or a fluoroalkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or a trifluoromethyl group.

[0376] In equation (C-3), R 1 The preferred methods for n1 are respectively related to R in equation (C-1). 1 The preferred method is the same as that for n1.

[0377] In formulas (C-1) to (C-3), each * is preferably a bonding site with a nitrogen atom.

[0378] And, when Y 1 When Y contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (C-1), 1 Preferably, the group is represented by the following formula (C-1-2) or formula (C-1-3). In the following formulas, * indicates the bonding site with the nitrogen atom, and n1 represents an integer from 0 to 5. Furthermore, an n1 of 0 is also one of the preferred embodiments of the present invention. Furthermore, the hydrogen atom in the following structure can be further replaced by a known substituent such as a hydrocarbon group. Examples of known substituents include alkyl groups, haloalkyl groups, and halogen atoms.

[0379] [Chemical Formula 36]

[0380]

[0381] And, when Y 1 When Y contains a group that is formed by removing two or more hydrogen atoms from the structure represented by formula (C-2), 1 Preferably, the group is represented by the following formula (C-2-3) or formula (C-2-4). From the viewpoint of reducing the dielectric constant of the cured product, the group represented by formula (C-2-4) is preferred. In the following formula, LX1 * indicates a single bond or -O-, and * indicates the bonding site with a nitrogen atom. Furthermore, R 2 The definitions and preferred methods are as described above. Furthermore, the hydrogen atoms in these structures can be further replaced by known substituents such as hydrocarbon groups.

[0382] [Chemical Formula 37]

[0383]

[0384] [X] 2 Y 2 ]

[0385] X in equation (1-2) 2 and Y 2 The preferred method is the same as X in equation (1-1) 1 and Y 1 The preferred method is the same. Among them, X... 1 and Y 1 The description of “Equation (1-1)” should be replaced with “Equation (1-2)”.

[0386] [A] 2 ]

[0387] A in equation (1-2) 2 Indicates -O- or -NR z -, Preferred -O-.

[0388] R z It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.

[0389] [R] 2 ]

[0390] R in equation (1-2) 2 This represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group contains a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkoxide group.

[0391] Furthermore, R 2 Preferably, it contains a polymerizable group. The polymerizable group is a group capable of cross-linking through the action of heat, free radicals, etc., and is preferably a free radical polymerizable group. Specific examples of polymerizable groups include groups having an olefinic unsaturated bond, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetyl, benzoxazolyl, terminal isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having an olefinic unsaturated bond is preferred.

[0392] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, groups represented by formula (III) below, and preferably groups represented by formula (III) below.

[0393] [Chemical Formula 38]

[0394]

[0395] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0396] In equation (III), * indicates the bonding site with other structures.

[0397] In equation (III), R 201 It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0398] R 201 Preferred examples include alkylene compounds such as ethylene, propyleneene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butadiene, 1,3-butadiene, -CH2CH(OH)CH2-, and polyalkoxide compounds; more preferably, alkylene compounds such as ethylene and propyleneene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkoxide compounds; and even more preferably, alkylene compounds such as ethylene and propyleneene or polyalkoxide compounds.

[0399] In this invention, polyalkoxide refers to a group consisting of two or more alkoxide groups directly bonded together. The alkylene groups within the multiple alkoxide groups in a polyalkoxide group may be the same or different.

[0400] When polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0401] The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.

[0402] Furthermore, the aforementioned alkylene group may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0403] Furthermore, the number of alkoxides contained in the polyalkoxide (the number of repetitions of the polyalkoxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0404] From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or groups bonded to multiple ethoxy groups and multiple propoxy groups are preferred as polyvinyloxy groups, more preferably polyvinyloxy or polypropyleneoxy, and even more preferably polyvinyloxy. Among the aforementioned groups bonded to multiple ethoxy and propoxy groups, the ethoxy groups and propoxy groups can be arranged randomly, form blocks, or be arranged in alternating patterns. The preferred manner for the number of repetitions of the ethoxy groups, etc., is as described above.

[0405] In equation (1-2), when R 2 When the hydrogen atom is present, the polyimide precursor can form a salt pair with a tertiary amine compound having an olefinically unsaturated bond. N,N-dimethylaminopropyl methacrylate is an example of such a tertiary amine compound having an olefinically unsaturated bond.

[0406] Furthermore, R in (1-2) 2 A 2 The carbonyl group is also preferably configured as the structure represented by formula (1-5) described later.

[0407] In equation (1-2), R 2 It can be a polarity-converting group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it decomposes through the action of acid to produce a base-soluble group such as a phenolic hydroxyl group or a carboxyl group. It is preferred to use acetal, ketal, silyl, silyl ether, tert-alkyl ester, etc. From the point of view of exposure sensitivity, acetal or ketal is more preferred.

[0408] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0409] [X] 3 Y 3 A 3 R 3 ]

[0410] X in equation (1-3) 3 and Y 3 The preferred method is the same as X in equation (1-1) 1 and Y 1 The preferred method is the same. Among them, X...1 and Y 1 The description of “Equation (1-1)” should be replaced with “Equation (1-3)”.

[0411] A in equation (1-3) 3 and R 3 The preferred method is the same as A in equation (1-2). 2 and R 2 The preferred method is the same. Among them, A... 2 and R 2 The description of “Equation (1-2)” should be replaced with “Equation (1-3)”.

[0412] Furthermore, R in (1-3) 3 A 3 The carbonyl group is also preferably configured as the structure represented by formula (1-5) described later.

[0413] [X] 4 Y 4 A 41 A 42 R 41 R 42 ]

[0414] X in equation (1-4) 4 and Y 4 The preferred method is the same as X in equation (1-1) 1 and Y 1 The preferred method is the same. Among them, X... 1 and Y 1 The description of “Equation (1-1)” should be replaced with “Equation (1-4)”.

[0415] A in equation (1-4) 41 and A 42 The preferred methods are respectively related to A in equation (1-2) 2 The preferred method is the same. Among them, A... 2 The description of “Equation (1-2)” should be replaced with “Equation (1-4)”.

[0416] R in equation (1-4) 41 and R 42 The preferred methods are respectively related to R in equation (1-2) 2 The preferred method is the same. Among them, R... 2 The description of “Equation (1-2)” should be replaced with “Equation (1-4)”.

[0417] Furthermore, R in (1-4) 41 A 41 and carbonyl group, and R 42 A 42At least one of the carbonyl groups also preferably forms the structure represented by formulas (1-5) described later.

[0418] Here, in all the repeating units represented by formula (1-2), formula (1-3), and formula (1-4) contained in the polyimide precursor, R 2 and R 3 R 41 and R 42 Those that are monovalent organic groups relative to R 2 and R 3 R 41 and R 42 The total molar content of the ingredients is preferably 50.0-100%, more preferably 85.0-100%, and even more preferably 92.0-100%.

[0419] Furthermore, the molar ratio of the content of the amyl ester structure to the total molar ratio of the amyl acid structure and the amyl ester structure in the polyimide precursor (esterification rate) is preferably 90% or more, more preferably 95% or more, and even more preferably 97% or more.

[0420] Furthermore, the upper limit of the above ratio is not specifically limited; it can be below 100%.

[0421] The esterification rate mentioned above can be estimated based on the acid value and structure of the resin.

[0422] The polyimide precursor preferably contains at least one repeating unit selected from the group consisting of repeating unit A-1, repeating unit A-2, repeating unit A-3 and repeating unit A-4.

[0423] Repeating unit A-1: ​​It is a repeating unit represented by the above equation (1-1), and is X. 1 A repeating unit of any one of the structures represented by equations (2a) to (2e), or a repeating unit containing a structure formed by removing two or more hydrogen atoms from the structure represented by equation (V-4).

[0424] Repeating unit A-2: It is a repeating unit represented by the above equation (1-2), and is X. 2 A repeating unit of any one of the structures represented by equations (2a) to (2e), or a repeating unit containing a structure formed by removing two or more hydrogen atoms from the structure represented by equation (V-4).

[0425] Repeating unit A-3: It is a repeating unit represented by the above equation (1-3), and is X. 3A repeating unit of any one of the structures represented by equations (2a) to (2e), or a repeating unit containing a structure formed by removing two or more hydrogen atoms from the structure represented by equation (V-4).

[0426] Repeating unit A-4: It is a repeating unit represented by the above equation (1-4), and is X. 4 A repeating unit of any one of the structures represented by equations (2a) to (2e), or a repeating unit containing a structure formed by removing two or more hydrogen atoms from the structure represented by equation (V-4).

[0427] In these, the polyimide precursor preferably contains repeating unit A-4, more preferably has repeating unit A-4 and at least one repeating unit selected from the group consisting of repeating unit A-1, repeating unit A-2 and repeating unit A-3.

[0428] The polyimide precursor preferably contains at least one repeating unit selected from the group consisting of repeating unit B-1, repeating unit B-2, repeating unit B-3 and repeating unit B-4.

[0429] In particular, the polyimide precursor preferably contains at least one repeating unit selected from the group consisting of repeating unit A-1, repeating unit A-2, repeating unit A-3 and repeating unit A-4, and at least one repeating unit selected from the group consisting of repeating unit B-1, repeating unit B-2, repeating unit B-3 and repeating unit B-4.

[0430] The polyimide precursor preferably contains repeating unit A-4 and repeating unit B-4.

[0431] Repeating unit B-1: It is a repeating unit represented by the above equation (1-1), and is X. 1 A repeating unit containing a structure formed by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1), (V-2), (V-3), and (V-5).

[0432] Repeating unit B-2: It is a repeating unit represented by the above equation (1-2), and is X. 2 A repeating unit containing a structure formed by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1), (V-2), (V-3), and (V-5).

[0433] Repeating unit B-3: It is a repeating unit represented by the above equation (1-3), and is X. 3 A repeating unit containing a structure formed by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1), (V-2), (V-3), and (V-5).

[0434] Repeating unit B-4: It is a repeating unit represented by the above equation (1-4), and is X. 4 A repeating unit containing a structure formed by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1), (V-2), (V-3), and (V-5).

[0435] The polyimide precursor preferably contains at least one repeating unit selected from the group consisting of repeating units represented by the above formula (1-2) and being R. 2 It is a repeating unit with a monovalent organic group having an olefinic unsaturated bond, represented by the above formula (1-3) and being R. 3 A repeating unit having a monovalent organic group with an olefinic unsaturated bond, and represented by the above formula (1-4) and R 41 and R 42 At least one of them is a repeating unit having a monovalent organic group with an olefinic unsaturated bond, and the polyimide precursor is more preferably a unit containing the expression represented by the above formula (1-4) and R 41 and R 42 At least one of them is a repeating unit with a monovalent organic group having an olefinic unsaturated bond.

[0436] The polyimide precursor preferably contains at least one repeating unit selected from the group consisting of the following repeating units: represented by the above formula (1-1) and Y 1 For a repeating unit of a structure containing the structure represented by equations (C-1) to (C-3), and represented by the above equation (1-2) and Y 2 For repeating units of a structure containing the structure represented by equations (C-1) to (C-3) below, and represented by equation (1-3) above, and Y 3 The repeating unit of the structure containing the structure represented by equations (C-1) to (C-3) and the repeating unit represented by equation (1-4) above, and Y 4 A repeating unit of a structure containing the structure represented by equations (C-1) to (C-3).

[0437] Here, Y is represented by equation (1-1) and 1 The repeating unit of the structure containing the structure represented by formulas (C-1) to (C-3) is preferably a repeating unit corresponding to the repeating unit A-1 or repeating unit B-1 mentioned above.

[0438] Here, Y is represented by equation (1-2) and 2 The repeating unit of the structure containing the structure represented by formulas (C-1) to (C-3) is preferably a repeating unit corresponding to the repeating unit A-2 or repeating unit B-2 mentioned above.

[0439] Here, Y is represented by equation (1-3) and 3The repeating unit of the structure containing the structure represented by formulas (C-1) to (C-3) is preferably a repeating unit corresponding to the repeating unit A-3 or repeating unit B-3 mentioned above.

[0440] Here, Y is represented by equation (1-4) and 4 The repeating unit of the structure containing the structure represented by formulas (C-1) to (C-3) is preferably a repeating unit corresponding to the repeating unit A-4 or repeating unit B-4 mentioned above.

[0441] As one embodiment of the polyimide precursor of the present invention, the total content of repeating units represented by formula (1-1), formula (1-2), formula (1-3), or formula (1-4) is 50 mol% or more of all repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor, except for the terminal units, can be repeating units represented by formula (1-1), formula (1-2), formula (1-3), or formula (1-4).

[0442] Furthermore, as another embodiment of the polyimide precursor in this invention, an example is provided where the total content of the repeating units represented by formulas (1-4) is 50 mol% or more of all repeating units. More preferably, the total content is 60 mol% or more, further preferably 70 mol% or more, and particularly preferably 80 mol% or more. The upper limit of the total content is preferably 97 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, and particularly preferably 85 mol% or less.

[0443] Furthermore, in the polyimide precursor of the present invention, the total content of repeating units (also referred to as "repeating unit A") corresponding to repeating unit A-1, repeating unit A-2, repeating unit A-3, or repeating unit A-4 is preferably 20 mol% or more of all repeating units. More preferably, the total content is 30 mol% or more, further preferably 40 mol% or more, and particularly preferably 50 mol% or more. The upper limit of the above total content is not particularly limited; all repeating units in the polyimide precursor except for the end units can be repeating unit A.

[0444] Furthermore, in the polyimide precursor of the present invention, the total content of repeating units (also referred to as "repeating unit B") corresponding to repeating unit B-1, repeating unit B-2, repeating unit B-3 or repeating unit B-4 is preferably 0 to 80 mol% of all repeating units. The above total content is more preferably 5 to 70 mol%, further preferably 10 to 60 mol%, and particularly preferably 15 to 50 mol%.

[0445] Furthermore, the total content of repeating unit A and repeating unit B in the polyimide precursor of the present invention is preferably 50 mol% or more of all repeating units. More preferably, the total content is 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor, except for the terminal units, can be repeating unit A or repeating unit B.

[0446] Furthermore, from the viewpoint of adhesion, the polyimide precursor is preferably substantially free of fluorine atoms. Here, "substantially free" means that the amount of fluorine atoms relative to the total mass of the polyimide precursor is less than 5% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass. The lower limit of the above-mentioned amount of fluorine atoms is not particularly limited and can be 0% by mass.

[0447] Furthermore, the polyimide precursor preferably contains a structure represented by the following formulas (1-5).

[0448] [Chemical Formula 39]

[0449]

[0450] R 51 Each is an independent organic group, R 52 It represents a hydrogen atom or an organic group; * indicates a bonding site with the resin structure.

[0451] In equation (1-5), R 51 Each group is preferably an aliphatic group or an aromatic group, more preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and even more preferably an aliphatic hydrocarbon group.

[0452] The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group with 1 to 20 carbon atoms, more preferably a saturated aliphatic hydrocarbon group with 3 to 10 carbon atoms, even more preferably a saturated aliphatic hydrocarbon group with 3 to 6 carbon atoms, and more preferably isopropyl or cyclohexyl.

[0453] Furthermore, 2 Rs 51 The groups can be the same or different, but having the same groups is also one of the preferred embodiments of the present invention.

[0454] The aforementioned aliphatic hydrocarbon groups may have known substituents, but the absence of substituents is also one of the preferred embodiments of the present invention.

[0455] The aromatic hydrocarbon group mentioned above is preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, more preferably a phenyl or naphthyl group, and even more preferably a phenyl group.

[0456] The aforementioned aromatic hydrocarbon group may have known substituents, and alkyl groups are examples of such substituents. Preferably, the alkyl group is an alkyl group with 1 to 10 carbon atoms, more preferably a branched alkyl group with 3 to 10 carbon atoms or a cyclic alkyl group with 5 to 10 carbon atoms, even more preferably a branched alkyl group with 3 to 6 carbon atoms, and particularly preferably isopropyl.

[0457] The number of the above-mentioned substituents is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2.

[0458] Furthermore, R 51 The carbon atoms or hydrocarbon groups of aliphatic or aromatic groups can be replaced by heteroatoms. Examples of heteroatoms include oxygen, nitrogen, and sulfur atoms. Specifically, -O- or -NR- can be present within the aliphatic or aromatic groups. N Structures such as -, -N=, -S-, etc. The above R N It represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, even more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0459] In equation (1-5), R 52 Preferably, it contains hydrogen atoms. R 52 Preferred method when it is a monovalent organic group and R 51 The preferred method is the same.

[0460] The structure represented by formula (1-5) can exist at the end of the main chain of the resin or in the side chain.

[0461] For example, R in equation (2) can be cited. 113 A 2 and carbonyl, R 114 A 1 and carbonyl group, R of formula (1-2) 2 A 2 and carbonyl group, R of formula (1-3) 3 A 3 and carbonyl group, R of formula (1-4) 41 A 41 and carbonyl and R 42 A 42 And the way in which at least one of the carbonyl groups constitutes the structure represented by formula (1-5), etc.

[0462] Furthermore, as a structure represented by formula (1-5), for example, the resin also preferably has a structure represented by formula (1-5-1) or formula (1-5-2).

[0463] [Chemical Formula 40]

[0464]

[0465] In equation (1-5-1), A 2 -O- or -NR Z -, R Z R is a hydrogen atom or a monovalent organic group. 2 X is a hydrogen atom or a monovalent organic group. 2 It is a tetravalent organic group, R A The group is represented by the above formula (1-5), and * represents the bonding site with other structures.

[0466] In equation (1-5-2), A 41 and A 42 Each can be independently -O- or -NR. Z -, R Z R is a hydrogen atom or a monovalent organic group. 41 and R 42 Each can be independently a hydrogen atom or a monovalent organic group, X 4 It is a tetravalent organic group, R A The group is represented by the above formula (1-5), and * represents the bonding site with other structures.

[0467] In equation (1-5-1), A 2 R Z R 2 and X 2 The preferred method is the same as A in the above formula (1-2). 2 R Z R 2 and X 2 The preferred method is the same.

[0468] In equation (1-5-1), R A The preferred method is the same as the preferred method of equation (1-5) above.

[0469] In equation (1-5-2), A 41 A 42 R Z R 41 R 42 and X 4 The preferred method is the same as A in the above formula (1-4). 41 A 42 R Z R 41 R 42 and X 4 The preferred method is the same.

[0470] In equation (1-5-2), R A The preferred method is the same as the preferred method of equation (1-5) above.

[0471] The content of the structure represented by formula (1-5) in the polyimide precursor is preferably 0.01 to 1.0 mmol / g, more preferably 0.01 to 0.85 mmol / g.

[0472] - Cyclation rate (imide ratio) -

[0473] From the viewpoint of the obtained organic membrane's strength and insulation properties, the cyclization rate (imidization rate) of the polyimide precursor is preferably less than 70%, more preferably less than 60%, further preferably less than 50%, even more preferably less than 40%, and particularly preferably less than 30%.

[0474] Furthermore, the imidization rate of 3 to 40% is also one of the preferred embodiments of the present invention.

[0475] From the viewpoint of elongation at break, the imidization rate is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more.

[0476] Furthermore, from the viewpoint of resolution, the imidization rate is preferably 35% or less, more preferably 30% or less, and even more preferably 25% or less.

[0477] The lower limit of the cyclization rate mentioned above is not specifically limited; 0% is sufficient.

[0478] The cyclization rate described above can be determined, for example, by the following method.

[0479] The infrared absorption spectrum of the polyimide precursor was measured, and the absorption peak at 1377 cm⁻¹, which is derived from the imide structure, was determined. -1 The peak intensity P1 is located nearby. Next, after heat-treating the polyimide precursor at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P1 at 1377 cm⁻¹ was determined. -1 The peak intensity P2 is nearby. Using the obtained peak intensities P1 and P2, the cyclization rate of the polyimide precursor can be calculated according to the following formula.

[0480] Cycloning rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0481] In the determination of imidization rate, for example, a resin for which the imidization rate can be determined can be obtained from the composition by the following method: A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water and allowed to crystallize, causing the resin to precipitate, and then filtered. The residue is recovered, dissolved in 3.0 g of THF (tetrahydrofuran), added to 50 g of methanol or water and allowed to crystallize, then filtered, and dried at 45°C for 20 hours to obtain the resin.

[0482] The polystyrene equivalent weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0483] Furthermore, in another preferred embodiment, the polystyrene of the polyimide precursor is preferably 120,000 or less, more preferably 50,000 or less, and even more preferably 40,000 or less.

[0484] Furthermore, the aforementioned Mw is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more.

[0485] The number average molecular weight (Mn) of the specific resin is preferably 40,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less.

[0486] Furthermore, the Mn is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.

[0487] The molecular weight dispersion of the aforementioned polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not specifically defined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0488] In this specification, the molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight.

[0489] Furthermore, when the photosensitive resin composition contains multiple polyimide precursors as a specific resin, the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are preferably within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple polyimide precursors are used as a single resin are each within the aforementioned ranges.

[0490] [Polyimide]

[0491] The polyimide used in this invention can be an alkali-soluble polyimide or a polyimide soluble in a developer solution with organic solvent as the main component.

[0492] In this specification, alkali-soluble polyimide refers to polyimide in which 0.1 g or more is dissolved in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, it is preferable to dissolve 0.5 g or more of polyimide, and more preferably 1.0 g or more of polyimide. The upper limit of the above-mentioned dissolution amount is not particularly limited, but it is preferably 100 g or less.

[0493] From the viewpoint of the strength and insulation of the obtained organic membrane, polyimide is preferably a polyimide having multiple imide structures on the main chain.

[0494] -Fluorine atom-

[0495] From the viewpoint of the membrane strength of the obtained organic membrane, polyimide is also preferably provided with fluorine atoms.

[0496] Fluorine atoms are preferably included, for example, in the repeating unit represented by equation (4) described later. 132 Or, as will be discussed later, R in the repeating unit represented by equation (4). 131 More preferably, R is included in the repeating unit represented by equation (4) described later. 132 Or, as will be discussed later, R in the repeating unit represented by equation (4). 131 It is used as a fluorinated alkyl group.

[0497] The amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0498] Furthermore, from the viewpoint of adhesion or mechanical strength, polyimide is preferably substantially free of fluorine atoms. Here, "substantially free" means that the amount of fluorine atoms relative to the total mass of the polyimide is less than 5% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass. The lower limit of the above-mentioned amount of fluorine atoms is not particularly limited and can be 0% by mass.

[0499] -Silicon atom-

[0500] From the viewpoint of the strength of the obtained organic membrane, polyimide is also preferably composed of silicon atoms.

[0501] Silicon atoms are preferably included, for example, in the repeating unit represented by equation (4) described later. 131 More preferably, R is included in the repeating unit represented by equation (4) described later. 131 The structure is referred to later as an organically modified (poly)siloxane.

[0502] The aforementioned silicon atoms or the aforementioned organically modified (poly)siloxane structure may also be included in the side chain of the polyimide, but preferably in the main chain of the polyimide.

[0503] The amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0504] -ene unsaturated bond-

[0505] From the viewpoint of the strength of the obtained organic membrane, polyimide preferably has olefinic unsaturated bonds.

[0506] Polyimide can have olefinic unsaturated bonds at the end of the main chain or on the side chain, but it is preferred to have olefinic unsaturated bonds on the side chain.

[0507] The aforementioned olefinic unsaturated bonds preferably possess free radical polymerization properties.

[0508] The olefinic unsaturated bond is preferably contained in the repeating unit represented by formula (4) described later. 132 or R 131 More preferably, it is included in R 132 or R 131 It is a group with an olefinic unsaturated bond.

[0509] In these, the olefinic unsaturated bond is preferably contained in the repeating unit represented by formula (4) described later. 131 More preferably, it is included in R 131 It is a group with an olefinic unsaturated bond.

[0510] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, vinylphenyl, and other vinyl groups that are directly bonded to the aromatic ring and can be substituted, as well as (meth)acrylamido, (meth)acryloyloxy, and groups represented by the following formula (IV).

[0511] [Chemical Formula 41]

[0512]

[0513] In equation (IV), R 20 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0514] In equation (IV), R 21 The group refers to an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkoxide group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and particularly preferably 2 or 3. The number of repetitions of the alkoxide group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3) or a group formed by combining two or more of these groups.

[0515] As the aforementioned alkylene groups having 2 to 12 carbon atoms, they can be any of the following: linear, branched, cyclic, or a combination thereof.

[0516] As the aforementioned alkylene groups having 2 to 12 carbon atoms, alkylene groups having 2 to 8 carbon atoms are preferred, and alkylene groups having 2 to 4 carbon atoms are more preferred.

[0517] Among these, R 21 Preferably, it is a group represented by any one of the following formulas (R1) to (R3), and more preferably, it is a group represented by formula (R1).

[0518] [Chemical Formula 42]

[0519]

[0520] In formulas (R1) to (R3), L represents a single bond or an alkylene group with 2 to 12 carbon atoms, a (poly)alkoxide group with 2 to 30 carbon atoms, or a group formed by bonding two or more of them; X represents an oxygen atom or a sulfur atom; * represents a bonding site with other structures; and ● represents a group with R in formula (IV). 21 The bonding sites of the bonded oxygen atoms.

[0521] In formulas (R1) to (R3), the preferred form of L is an alkylene group having 2 to 12 carbon atoms or a (poly)alkene group having 2 to 30 carbon atoms, and is also R in formula (IV). 21 The preferred configurations are the same for alkylene groups with 2 to 12 carbon atoms or (poly)alkoxide groups with 2 to 30 carbon atoms.

[0522] In formula (R1), X is preferably an oxygen atom.

[0523] In equations (R1) to (R3), the meaning of * is the same as that of * in equation (IV), and the preferred method is also the same.

[0524] The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having hydroxyl groups such as phenolic hydroxyl groups with a compound having isocyanate groups and olefinic unsaturated bonds (e.g., ethyl 2-isocyanate methacrylate).

[0525] The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having hydroxyl and olefinic unsaturated bonds (e.g., 2-hydroxyethyl methacrylate, etc.).

[0526] The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having hydroxyl groups such as phenolic hydroxyl groups with a compound having glycidyl groups and olefinic unsaturated bonds (e.g., glycidyl methacrylate, etc.).

[0527] In formula (IV), * represents the bonding site with other structures, and * is preferably the bonding site with the main chain of polyimide.

[0528] The amount of olefinic unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g.

[0529] - Polymerizable groups other than those with olefinic unsaturated bonds-

[0530] Polyimides can have polymerizable groups other than those with olefinic unsaturated bonds.

[0531] Examples of polymerizable groups other than those with olefinic unsaturated bonds include cyclic ether groups such as epoxy and oxobutyl groups, alkoxymethyl groups such as methoxymethyl, and hydroxymethyl groups.

[0532] Polymerizable groups other than those with olefinic unsaturated bonds, preferably R in the repeating unit represented by formula (4) described later. 131 middle.

[0533] The amount of polymerizable groups other than those having olefinic unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0534] -Polar switching group-

[0535] Polyimides can possess polar conversion groups such as acid-degradable groups. The acid-degradable groups in polyimides are analogous to the R groups in formula (2) above. 113 and R 114 The acid-decomposing groups described herein are the same, and the preferred methods are also the same.

[0536] Polar conversion groups, such as R contained in the repeating unit represented by formula (4) described later, are examples of such groups. 131 R 132 In the end of polyimide, etc.

[0537] -Acid Value-

[0538] When polyimide is used for alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more.

[0539] The acid value is preferably below 500 mg KOH / g, more preferably below 400 mg KOH / g, and even more preferably below 200 mg KOH / g.

[0540] When polyimide is supplied to a developing solution that uses an organic solvent as the main component (e.g., "solvent developing"), the acid value of the polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g.

[0541] The acid value is determined by a known method, for example by the method described in JIS K 0070:1992.

[0542] From the viewpoint of balancing storage stability and developability, acid groups containing acid groups with a pKa of 0 to 10 are preferred as part of polyimide, and more preferably acid groups with a pKa of 3 to 8.

[0543] pKa is the value of the equilibrium constant Ka, expressed as its negative common logarithm, pKa, taking into account the dissociation reaction that releases hydrogen ions from an acid. In this specification, unless otherwise specified, pKa is set as a calculated value based on ACD / ChemSketch (registered trademark). pKa can also be referenced to the value published in the "Fifth Revised Edition of the Chemical Handbook: Basic Edition" edited by the Chemical Society of Japan.

[0544] When the acid group is a polybasic acid such as phosphoric acid, the above pKa is the first dissociation constant.

[0545] As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0546] -Phenolic hydroxyl-

[0547] From the viewpoint of achieving an appropriate development speed using alkaline developing solution, polyimide preferably has phenolic hydroxyl groups.

[0548] Polyimide can have phenolic hydroxyl groups at the end of the main chain or on the side chain.

[0549] Phenolic hydroxyl groups are preferably included, for example, in the repeating unit represented by formula (4) described later. 132 or R 131 middle.

[0550] The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0551] The polyimide used in this invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferred to contain repeating units represented by the following formula (4).

[0552] [Chemical Formula 43]

[0553]

[0554] In equation (4), R 131 R represents a divalent organic group. 132 It represents a tetravalent organic group.

[0555] When it has polymerizable groups, the polymerizable groups can be located at R. 131 and R 132 At least one of them, as shown in formula (4-1) or formula (4-2) below, may also be located at the end of the polyimide.

[0556] Equation (4-1)

[0557] [Chemical Formula 44]

[0558]

[0559] In equation (4-1), R 133 The group is a polymerizable group, and the meanings of the other groups are the same as those in formula (4).

[0560] Equation (4-2)

[0561] [Chemical Formula 45]

[0562]

[0563] In equation (4-2), R 134 and R 135 At least one of them is a polymeric group, and when it is not a polymeric group, it is an organic group. The meanings of the other groups are the same as those in formula (4).

[0564] Examples of polymerizable groups include groups containing the aforementioned olefinic unsaturated bonds or crosslinking groups other than those containing the aforementioned olefinic unsaturated bonds.

[0565] R 131 This represents a divalent organic group. As a divalent organic group, it can be exemplified by R in formula (2). 111 The same organic groups have the same preferred range.

[0566] As R 131 Examples of diamines include the diamine residue remaining after the amino group of the diamine is removed. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. As a specific example, R in formula (2) of a polyimide precursor can be cited. 111 Examples.

[0567] From the perspective of more effectively suppressing warping during calcination, R 131Preferably, it is a diamine residue having at least two alkylene glycol units on the main chain. More preferably, it is a diamine residue containing a total of two or more ethylene glycol chains, propylene glycol chains, or both in one molecule. Even more preferably, it is a diamine residue that does not contain an aromatic ring.

[0568] Examples of diamines containing a total of two or more ethylene glycol chains or propylene glycol chains in one molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc., but not limited to these.

[0569] Furthermore, R 131 Preferably, it is a group containing a group represented by formula (2-1), and more preferably a group represented by formula (2-1).

[0570] [Chemical Formula 46]

[0571]

[0572] In equation (2-1), R 1 and R 2 Each group independently represents a group with an olefinic unsaturated bond, L represents a single bond or a divalent linker without an imide bond, and * represents a bonding site with other structures.

[0573] In equation (2-1), R 1 and R 2 Each group is preferably represented by the following formula (R1-1).

[0574] [Chemical Formula 47]

[0575]

[0576] In equation (R1-1), L R1 R represents an n+1 valence linker. R1 Each of the following groups independently represents an aromatic group, maleimide group, (meth)acryloyloxy group, or (meth)acrylamide group that is directly bonded to a vinyl group, where n represents an integer from 1 to 10, and * represents the bonding site with the oxygen atom in formula (2-1).

[0577] R R1Each of the aromatic groups or maleimide groups, which are directly bonded to the vinyl group, is preferred to be a vinylphenyl group.

[0578] L R1 Preferably, it is a hydrocarbon group or a hydrocarbon group combined with -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N - The group represented by at least one group in the group, preferably a hydrocarbon group or * 1 -C (=O) -L R2 -* 2 or* 1 -C(=O)NR N -L R2 -* 2 The group to be represented.

[0579] As mentioned above L R1 The hydrocarbon group in the form is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0580] The above L R2 The group represents a hydrocarbon group, preferably an alkylene group, more preferably an alkylene group having 2 to 10 carbon atoms, and even more preferably an alkylene group having 2 to 6 carbon atoms.

[0581] The above R N The preferred method is as described above.

[0582] The above* 1 The meaning of * is the same as the meaning of * in equation (R1-1). 2 R represents the expression (R1-1) R1 The bonding sites.

[0583] And, when R R1 When it is vinylphenyl, L R1 Preferably, it is an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group.

[0584] When R R1 When it is maleimide, L R1 Preferably, it is an alkylene group having 1 to 4 carbon atoms or composed of * 1 -C (=O) -L R2 -* 2 The group indicated.

[0585] When R R1 When it is (meth)acryloyloxy or (meth)acrylamide, L R1 Preferred to be made of * 1 -C(=O)NR N -L R2 -* 2 The group indicated.

[0586] n is preferably an integer from 1 to 4, more preferably 1 or 2, and more preferably 1.

[0587] In formula (2-1), L is preferably a single bond, -C(CH3)2-, -C(CF3)2-, -S(=O)2-, or 9,9-fluorene dimethyl. Furthermore, L being a single bond, -C(CH3)2-, or -C(CF3)2- is also one of the preferred embodiments of the present invention.

[0588] R 132 This represents a tetravalent organic group. As a tetravalent organic group, it can be exemplified by R in formula (2). 115 The same organic groups have the same preferred range.

[0589] For example, as R 115 The four connectors of the exemplified tetravalent organic group are bonded to the four -C (=O)- portions in the above formula (4) to form a fused ring.

[0590] R 132 Examples include the tetracarboxylic acid residue remaining after removing the anhydride group from a tetracarboxylic dianhydride. As a specific example, R in formula (2) of a polyimide precursor can be cited. 115 Examples. From the perspective of the strength of organic membranes, R 132 Preferably, it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0591] R is also preferred 131 and R 132 At least one of them has an OH group. More specifically, as R 131 Examples of preferred embodiments include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the aforementioned (DA-1) to (DA-18). 132 Examples of better choices can be found in (DAA-1) to (DAA-5).

[0592] The polyimide preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, more preferably 20% by mass or less.

[0593] To improve adhesion to the substrate, polyimide can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0594] To improve the storage stability of the photosensitive resin composition, the main chain of the polyimide is preferably capped with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds. Among these, monoamines are more preferred. Examples of preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl-5-aminonaphthalene. -Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, or multiple different end groups can be introduced by reacting various end-capping agents.

[0595] -Imidization rate (ring-closure rate)-

[0596] From the viewpoint of the obtained organic film's strength and insulation properties, the imidization rate (also known as "ring-closing rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0597] The upper limit of the imidization rate is not particularly limited; it can be below 100%.

[0598] The imidization rate described above was determined using the method described above.

[0599] Polyimide can contain R consisting of all repeating units 131 and R 132 The repeating units represented by the above equation (4) with the same combination can also contain R consisting of two or more types. 131 and R 132 The repeating units represented by the above formula (4) can be different combinations. In addition to the repeating units represented by the above formula (4), polyimide may also contain other types of repeating units. For example, the repeating units represented by the above formula (2) can be cited as other types of repeating units.

[0600] Polyimides can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine (with a portion replaced as a capping agent for a monoamine) at low temperature; by reacting a tetracarboxylic dianhydride (with a portion replaced as a capping agent for an anhydride, a monoacyl chloride, or a monoactive ester compound) with a diamine at low temperature; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine (with a portion replaced as a capping agent for a monoamine) in the presence of a condensing agent; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acyl-chlorinating the remaining dicarboxylic acid and reacting it with a diamine (with a portion replaced as a capping agent for a monoamine), and then fully imidizing it using a known imidization reaction method; or by stopping the imidization reaction midway and introducing a partial imide structure; and by introducing a partial imide structure by mixing a fully imidized polymer with the polyimide precursor. Furthermore, other known methods for synthesizing polyimides can also be applied.

[0601] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural strength of the cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or more is particularly preferred.

[0602] The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0603] The molecular weight dispersion of the aforementioned polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0604] When the photosensitive resin composition contains multiple polyimides as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated when the multiple polyimides are considered as a single resin are each within the above-mentioned ranges.

[0605] [Polybenzoxazole precursor]

[0606] Compounds described in paragraphs 0073 to 0095 of International Publication No. 2022 / 145355 as precursors of polybenzoxazole can be cited as examples. These descriptions are incorporated herein by reference.

[0607] [Polybenzoxazole]

[0608] As polybenzoxazoles, examples include compounds described in paragraphs 0101 to 0108 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0609] [Polyamide-imide precursor]

[0610] Compounds described in paragraphs 0104 to 0119 of International Publication No. 2022 / 145355 can be cited as precursors for polyamide-imide. These descriptions are incorporated herein by reference.

[0611] [Polyamide-imide]

[0612] As polyamide-imides, examples include compounds described in paragraphs 0125 to 0138 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0613] [Methods for manufacturing polyimide precursors, etc.]

[0614] Polyimide precursors, etc., are manufactured, for example, by the methods described in paragraphs 0134 to 0136 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0615] 〔content〕

[0616] Relative to the total solids content of the photosensitive resin composition, the content of a specific resin in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, relative to the total solids content of the photosensitive resin composition, the content of the resin in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and still even more preferably 95% by mass or less.

[0617] The photosensitive resin composition of the present invention may contain only one specific resin or two or more specific resins. When containing two or more specific resins, the total amount is preferably within the above-mentioned range.

[0618] The photosensitive resin composition of the present invention preferably contains at least two resins.

[0619] Specifically, the photosensitive resin composition of the present invention may contain a total of two or more specific resins and other resins described below, or may contain two or more specific resins, but preferably contains two or more specific resins.

[0620] When the photosensitive resin composition of the present invention contains two or more specific resins, for example, it is preferable to contain a structure derived from dianhydride (R in formula (2) above) as a polyimide precursor. 115 Two or more different polyimide precursors.

[0621] <Other Resins>

[0622] The photosensitive resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins").

[0623] Other resins that can be cited include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins.

[0624] For example, by further adding (meth)acrylic resins, a photosensitive resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.

[0625] For example, by adding a (meth)acrylic resin to the photosensitive resin composition in place of the polymerizable compound described later, or by adding a (meth)acrylic resin in addition to the polymerizable compound described later, the coatability of the photosensitive resin composition, the solvent resistance of the pattern (cured product), etc., can be improved. This (meth)acrylic resin has a weight-average molecular weight of 20,000 or less and a high value of polymerizable groups (e.g., the molar content of polymerizable groups in 1g of resin is 1×10⁻⁶). -3 (more than moles / g).

[0626] When the photosensitive resin composition of the present invention contains other resins, the content of other resins relative to the total solid content of the photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0627] When the photosensitive resin composition of the present invention contains other resins, the content of other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0628] As a preferred embodiment of the photosensitive resin composition of the present invention, it is also possible to set the content of other resins to be low. In the above embodiment, the content of other resins relative to the total solids content of the photosensitive resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, and 0% by mass or more is acceptable.

[0629] The photosensitive resin composition of the present invention may contain only one other resin or may contain two or more other resins. When containing two or more specific resins, the total amount is preferably within the above-mentioned range.

[0630] <Compound A>

[0631] [Compound Aa]

[0632] The first photosensitive resin composition of the present invention contains compound Aa as a photochromic compound.

[0633] Photochromic compounds are compounds whose molecular geometry changes due to light absorption, thereby altering their absorption spectrum.

[0634] Compound Aa is preferably transformed into compound A through exposure. ex The compound, compound A ex This refers to a compound whose absorption of a certain wavelength of light contained in the exposure light is less than that of compound Aa. Hereinafter, this method will also be referred to as Method 1.

[0635] In method 1, the above compound A ex Preferably, the compound whose structure is changed back to compound Aa by exposure to other wavelengths (e.g., exposure to visible light), heating, or shading. Here, in Method 1, the wavelength of the exposure light that changes the structure of compound Aa is preferably the wavelength that sensitizes the photosensitizer (e.g., photopolymerization initiator or photoacid generator) contained in the photosensitive resin composition.

[0636] Furthermore, compound Aa can also be transformed into compound A through exposure, heating, or light shielding. ex The compound, compound A ex The compound whose absorption of light at a wavelength of 365 nm is greater than that of compound Aa. Hereinafter, this method will also be referred to as Method 2.

[0637] In method 2, the above compound A ex Preferably, the compound whose structure changes back to Aa through exposure, heating, or shading at other wavelengths. Here, in method 2, compound A is... exThe wavelength of the exposure light for structural changes is preferably the wavelength that sensitizes the photosensitizer (e.g., photopolymerization initiator or photoacid generator) contained in the photosensitive resin composition.

[0638] For example, in a photosensitive resin composition or photosensitive film containing compound Aa of method 2, the structure is changed to that of compound A of method 2 by means of exposure, heating or shading. ex Thus, in the film obtained from the above-described photosensitive resin composition or in the above-described photosensitive film, as described above, in areas with low exposure, the exposure light is absorbed by compound A. ex It absorbs, thus reducing the actual exposure to other photosensitive components.

[0639] Or, corresponding to compound A ex Sometimes, compounds in photosensitive resin compositions are protonated or otherwise transformed into compounds Aa through their relationship with other components.

[0640] Compound Aa preferably satisfies conditions 1 and 2 below.

[0641] Condition 1: The structure changes to compound A when exposed to light with a wavelength of 365 nm. ex ,

[0642] Condition 2: When the absorbance of compound Aa at 365 nm is set to abs365-A1, and compound A... ex The absorbance at 365nm was set to abs365-A ex1 When abs365-A1 exceeds abs365-A ex1 .

[0643] In this invention, the above-mentioned abs365-A1 is determined by the following method.

[0644] Compound Aa was dissolved in NMP to prepare a concentration of 10 mg / L, which was then used as the sample for determination. The determination was performed using a UV-1800 UV-Vis spectrophotometer (manufactured by SHIMADZU CORPORATION) with a 1 cm cuvette. The absorbance at 365 nm (abs365-A1) of the sample was measured.

[0645] Then, the aforementioned colorimetric cell was exposed using a LightningCure LC8 UV spot exposure machine (manufactured by Hamamatsu Photonics KK) to achieve an exposure dose of 1000 mJ / cm. 2The absorbance at 365 nm of the exposed sample was measured using a UV-1800 UV-Vis spectrophotometer (manufactured by SHIMADZU CORPORATION) and a 1 cm cuvette. Similar to the abs365-A1 measurement, this absorbance was designated as abs365-A. ex1 .

[0646] When compound Aa satisfies conditions 1 and 2 above, abs365-A1 and abs365-A ex1 The difference is preferably 0.00001 to 3.00000, more preferably 0.00010 to 2.00000.

[0647] When compound Aa satisfies conditions 1 and 2 above, the maximum absorption wavelength of compound Aa in the wavelength range of 300–700 nm is similar to that of compound A. ex The difference in maximum absorption wavelengths between 300 and 700 nm is preferably 50 to 400 nm, more preferably 75 to 400 nm, and even more preferably 100 to 400 nm.

[0648] Furthermore, when compound Aa satisfies conditions 1 and 2 above, compound A ex The maximum absorption wavelength at 365 nm is related to that of compound A. ex The difference in the maximum absorption wavelength at wavelengths of 300–700 nm is preferably 10–335 nm, more preferably 20–335 nm, and even more preferably 30–335 nm.

[0649] Membranes containing a specific resin and compound Aa preferably satisfy conditions 3 and 4 below.

[0650] Condition 3: When the membrane is illuminated with light of wavelength 365 nm, the structure of compound Aa in the membrane changes to that of compound A. ex ,

[0651] Condition 4: When the content of compound Aa in the membrane is compared with that of compound Aa and compound A... ex The absorbance at 365 nm of a membrane containing a total content of 1% or more is defined as abs365-A2. Compound A contained in the membrane... ex The content of [a] relative to compound Aa and compound A ex The absorbance at 365 nm of a film with a total content of less than 0.5% by mass is defined as abs365-A. ex2 When abs365-A2 exceeds abs365-A ex2 .

[0652] Used to determine abs365-A2 and abs365-A ex2The aforementioned membrane can be obtained, for example, by preparing a mixture of a specific resin, compound Aa, and compound A. ex A solution dissolved in a solvent is applied to a substrate such as a quartz substrate with a thickness of 2 mm, and then dried as needed. During drying, the film thickness after drying becomes 6 μm.

[0653] As a specific resin, compound Aa, and compound A used to dissolve the above solution ex For solvents that are difficult to implement, γ-butyrolactone can be used. However, if it is difficult to implement a solution where γ-butyrolactone is insoluble in a particular resin, compound Aa, or compound A... ex If so, the solvent can be appropriately changed to N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc.

[0654] The content of a specific resin in the above solution can be set as the content in each photosensitive resin composition. However, if it is difficult to form a 6 μm film with the above content, or if the solubility of the specific resin is low and it cannot be prepared, the above content can be appropriately set between 10 and 60% by mass. Furthermore, if a 6 μm film cannot be obtained, it can be determined by measuring the film thickness that can be formed and converting it to the case of a film thickness of 6 μm.

[0655] The absorbance of the obtained membrane can be measured using a UV-Vis spectrophotometer UH-4150 (manufactured by Hitachi High-Tech Corporation).

[0656] Furthermore, for compounds Aa and A ex The total content in the above solution is equal to that in the photosensitive resin composition of compound Aa and compound A. ex After the total amount is the same, the relative amounts of compound Aa and compound A can be adjusted by exposure to light with a wavelength of 365nm, heating, exposure to visible light, and shading. ex The total content of compound Aa or compound A ex The content of.

[0657] For example, it can be adjusted as follows: In order to determine abs365-A2, relative to compound Aa and compound A ex The total content of compound Aa is set to 1% by mass or more, or for the purpose of determining abs365-A. ex2 The relative compounds Aa and A ex The total content of compound Aa is set to less than 0.5% by mass.

[0658] Here, in compounds Aa and A exWhen it is difficult to strictly adjust the content of one or both of them, for example, the content of compound Aa can be adjusted relative to that of compound Aa and compound A. ex The total content change was measured after approximately 5 points, and, for example, by HPLC, compounds Aa and A were determined. ex The content of abs365-A2 and abs365-A was determined, and a calibration curve was constructed based on the content and absorbance to calculate the abs365-A2 and abs365-A2 content. ex2 .

[0659] Quartz substrates can be used as the substrate. If it is difficult to form a film with a thickness of 10 μm on a quartz substrate, other substrates with different properties such as surface wettability can be used. Furthermore, transparent substrates such as glass substrates can also be used when considering the convenience of measuring absorbance.

[0660] The method for applying the above solution to the substrate is not particularly limited, as long as the film thickness is 10 μm, spin coating can be used. When it is difficult to form a film with a thickness of 10 μm by spin coating, a suitable method can be selected from known methods such as dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, slot coating, and inkjet coating.

[0661] Drying is preferably carried out until the amount of solvent in the membrane is less than 0.1% by mass.

[0662] The drying conditions are not particularly limited and can be achieved by heating. Furthermore, when heating alone is insufficient for thorough drying, reduced pressure can be applied.

[0663] Drying can be carried out under atmospheric conditions. However, when the resin composition contains components that are easily modified by oxygen, it can also be carried out under conditions such as displacement by inert gases like nitrogen or under vacuum.

[0664] The drying method is not particularly limited, but examples include heating plates. However, when the aforementioned pressure reduction or inert gas replacement is required, ovens with pressure reduction functions or ovens with gas replacement functions can also be used.

[0665] When drying is performed using heat, drying can be carried out at a heating temperature of, for example, 110°C. However, if it is difficult to dry at 110°C, the drying temperature can be appropriately changed between 70°C and 130°C, preferably between 90°C and 120°C, depending on the type of solvent contained in the resin composition.

[0666] When drying is performed using heat, the drying time (the time exposed to the aforementioned heating temperature) can be, for example, 5 minutes. However, if it is difficult to dry within 5 minutes, the drying time can be appropriately changed between 30 seconds and 20 minutes, preferably between 1 minute and 10 minutes, depending on the type of solvent contained in the solution.

[0667] When drying is performed using heating, the heating rate is not particularly limited; for example, it can be set to 5°C / minute. When drying is difficult to perform at the above heating rate, the heating rate can be appropriately changed between 1 and 12°C / minute or 2 and 10°C / minute, depending on the type of solvent contained in the solution.

[0668] When compound Aa satisfies conditions 3 and 4 above, abs365-A2 and abs365-A ex2 The difference is preferably 0.0001 to 3.0000, more preferably 0.0005 to 2.0000.

[0669] When compound Aa satisfies conditions 3 and 4 above, the maximum absorption wavelength of compound Aa in the wavelength range of 300–700 nm is similar to that of compound A. ex The difference in maximum absorption wavelengths between 300 and 700 nm is preferably 50 to 400 nm, more preferably 75 to 400 nm, and even more preferably 100 to 400 nm.

[0670] Furthermore, when compound Aa satisfies conditions 3 and 4 above, compound A ex The maximum absorption wavelength at 365 nm is related to that of compound A. ex The difference in the maximum absorption wavelength at wavelengths of 300–700 nm is preferably 10–335 nm, more preferably 20–335 nm, and even more preferably 30–335 nm.

[0671] The film formed from the photosensitive resin composition preferably satisfies conditions 5 and 6 below.

[0672] Condition 5: When the membrane is exposed to light with a wavelength of 365 nm, the structure of compound Aa in the membrane changes to that of compound A. ex ,

[0673] Condition 6: When the content of compound Aa in the membrane is compared with that of compound Aa and compound A... ex The absorbance at 365 nm of a membrane containing a total content of 1% or more is defined as abs365-A3. Compound A contained in the membrane... ex The content of [a] relative to compound Aa and compound A exThe absorbance at 365 nm of a film with a total content of less than 0.5% by mass is defined as abs365-A. ex3 When, abs365-A3 exceeds abs365-A ex3 .

[0674] Used to determine abs365-A3 and abs365-A ex3 The aforementioned film can be obtained, for example, by preparing a photosensitive resin composition, applying the solution to a substrate such as a quartz substrate, and drying it as needed. During drying, the film thickness after drying is 6 μm. Furthermore, regarding abs365-A3 and abs365-A... ex3 The determination method is the same as that for abs365-A2 and abs365-A. ex2 The determination method is the same.

[0675] When compound Aa satisfies conditions 5 and 6 above, abs365-A3 and abs365-A ex3 The difference is preferably 0.0001 to 3.0000, more preferably 0.0005 to 2.0000.

[0676] When compound Aa satisfies conditions 5 and 6 above, the maximum absorption wavelength of compound Aa in the wavelength range of 300–700 nm is similar to that of compound A. ex The difference in maximum absorption wavelengths between 300 and 700 nm is preferably 50 to 400 nm, more preferably 75 to 400 nm, and even more preferably 100 to 400 nm.

[0677] Furthermore, when compound Aa satisfies conditions 5 and 6 above, compound A ex The maximum absorption wavelength at 365 nm is related to that of compound A. ex The difference in the maximum absorption wavelength at wavelengths of 300–700 nm is preferably 10–335 nm, more preferably 20–335 nm, and even more preferably 30–335 nm.

[0678] Compound Aa is preferably a compound represented by any one of the following formulas: (Ab-1) to (Ab-6), (Ac-1), (Ac-2), (Ad-1), (Ad-2), (Ae-1), and (Ae-2).

[0679] The compound represented by formula (Ab-1) is preferably compound Aa from the above-described method 1.

[0680] The compounds represented by formulas (Ab-2) to (Ab-6) are preferably compounds Aa in the above-described method 2.

[0681] The compound represented by formula (Ac-1) is preferably compound Aa from the above-described method 1.

[0682] The compound represented by formula (Ac-2) is preferably compound Aa from the above-described method 2.

[0683] The compound represented by formula (Ad-1) is preferably compound Aa from the above-described method 1.

[0684] The compound represented by formula (Ad-2) is preferably compound Aa from the above-described method 2.

[0685] The compound represented by formula (Ae-1) is preferably compound Aa from the above-described method 1.

[0686] The compound represented by formula (Ae-2) is preferably compound Aa from the above-described method 2.

[0687] [Chemical Formula 48]

[0688]

[0689] [Chemical Formula 49]

[0690]

[0691] [Chemical Formula 50]

[0692]

[0693] [Chemical Formula 51]

[0694]

[0695] In equation (Ab-1), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, R 4 R can be a hydrogen atom or any organic group. 5 R can be a hydrogen atom or any organic group. 4 With R 5 They can bond together to form a ring structure, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - Z 1 -O-, -S-, -NR 6 any one of - R 6The dashed part represents a hydrogen atom or any organic group. The dashed part indicates a single bond or a double bond. When the dashed part is a double bond or R 2 When they bond together to form an aromatic ring, there are no two Rs. 3 ,

[0696] In formula (Ab-2) or formula (Ab-3), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - R 6 Z can be a hydrogen atom or any organic group. 3 =C(R) Z )- or =N-, R Z L can be a hydrogen atom or any organic group. 2 Z can be any divalent linking group that can have substituents. 1 -O, -S, or -NR 6 When the dashed part is a double bond or R 2 When they bond together to form an aromatic ring, there are no two Rs. 3 ,

[0697] In equation (Ab-4), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - R 6 L can be a hydrogen atom or any organic group. 2 Z can be any divalent linking group that can have substituents. 2 =O, =S, or =NR 7 R 7 It can be a hydrogen atom or any organic group, when the dashed part is a double bond or R 2 When they bond together to form an aromatic ring, there are no two Rs. 3 ,

[0698] In formula (Ab-5) or formula (Ab-6), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 X is any divalent linker that can have substituents, where X is -O-, -S-, or -NR. 6 any one of - R 6 Z can be a hydrogen atom or any organic group. 3 =C(R) Z )- or =N-, R Z L can be a hydrogen atom or any organic group. 2 Z can be any divalent linking group that can have substituents. 4 -OH, -SH, -N(R) 6 Any one of H, R 6 An is a hydrogen atom or any organic group, where An is a counter anion. When the dashed part is a double bond or R... 2 When they bond together to form an aromatic ring, there are no two Rs. 3 ,

[0699] In equation (Ac-1), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 Ar is any divalent linking group that can have substituents. 1 Each is an independent aromatic group. The dashed part represents a single bond or a double bond. When the dashed part represents a double bond or R 2 When they bond together to form an aromatic ring, there are no two Rs. 3 ,

[0700] In equation (Ac-2), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can bond with each other to form alicyclic or aromatic rings, L 1 Ar is any divalent linking group that can have substituents. 1 Each can be an aromatic group that has substituents. The dashed part represents a single bond or a double bond. When the dashed part is a double bond, R does not exist. 3 .

[0701] In equation (Ad-1), R 7 R can be independently a hydrogen atom, a halogen atom, or any organic group. 7They can bond together to form ring structures, and Ar can be independently aromatic ring structures that can have substituents.

[0702] In equation (Ad-2), R 7 R can be independently a hydrogen atom, a halogen atom, or any organic group. 7 They can bond together to form a ring structure, R 8 Each of the R groups can be a hydrogen atom, a halogen atom, or any organic group, and each of the R groups can be a ring structure that may have substituents.

[0703] In equation (Ae-1), R 9 ~R 16 R can be independently a hydrogen atom, a halogen atom, or any organic group. 9 ~R 16 At least two of them can bond together to form a ring structure, where X is -O-, -S-, or -NR. 6 any one of - R 6 It can be a hydrogen atom or any organic group.

[0704] In equation (Ae-2), R 9 ~R 16 R can be independently a hydrogen atom, a halogen atom, or any organic group. 9 ~R 16 At least two of them can bond together to form a ring structure, where X is -O-, -S-, or -NR. 6 any one of - R 6 It can be a hydrogen atom or any organic group.

[0705] In equation (Ab-1), R 2 Each of the following can be independently a hydrogen atom, a halogen atom, or any organic group, preferably any organic group. As R 2 Any of the organic groups mentioned above can be exemplified by hydrocarbon groups, alkoxy groups, aryloxy groups, etc.

[0706] In equation (Ab-1), R 3 Each of the following is an independent hydrogen atom, halogen atom, or any organic group, preferably a hydrogen atom. As R 3 Any of the organic groups mentioned above can be exemplified by hydrocarbon groups, alkoxy groups, aryloxy groups, etc.

[0707] Furthermore, in equation (Ab-1), R 2 Preferably, the rings are bonded together to form alicyclic or aromatic rings, more preferably aromatic rings. Examples of aromatic rings include fused polycyclic hydrocarbon rings such as benzene rings or naphthalene rings. The aforementioned alicyclic or aromatic rings may further contain substituents, provided that the effects of the present invention are achieved.

[0708] In equation (Ab-1), R 4 It can be a hydrogen atom or any organic group, preferably any organic group. As an arbitrary organic group, it is preferably a hydrocarbon group, and more preferably an alkyl group.

[0709] In equation (Ab-1), Z 1 The preferred option is -O-.

[0710] In equation (Ab-1), R 5 It can be a hydrogen atom or any organic group, preferably any organic group. As an arbitrary organic group, a hydrocarbon group is preferred.

[0711] In equation (Ab-1), R 4 With R 5 Preferably, a ring structure is formed by bonding. The formed ring structure preferably contains Z. 1 The heteroatom can be a 5-membered or 6-membered ring, more preferably a 6-membered ring. Furthermore, the ring structure is preferably unsaturated aliphatic. Moreover, the ring structure can be further fused with other ring structures. Other ring structures include aromatic hydrocarbon ring structures that can have substituents, preferably benzene ring structures or naphthalene ring structures that can have substituents. Examples of substituents include halogen atoms, nitro groups, alkoxy groups, etc.

[0712] Among these, as R 4 With R 5 The ring structure formed by bonding is preferably a pyran ring structure fused with the other ring structures mentioned above.

[0713] The following shows R 4 With R 5 Examples of ring structures formed by bonding are given, but the invention is not limited to these. In the following structures, Z... 1 The meaning of Z in equation (Ab-1) 1 The meaning is the same as L, * indicates the same as L. 1 The bonding site, # indicates the bonding site with X.

[0714] [Chemical Formula 52]

[0715]

[0716] In formula (Ab-1), L 1 It can be any divalent linking group that has substituents, preferably alkylene, more preferably -C(CH3)2-.

[0717] In formula (Ab-1), X is preferably -NR. 6 -. R 6 Preferably, it is an alkyl group that can have substituents. Examples of substituents include hydroxyl groups. Regarding the R in other symbols...6 The preferred method is also the same.

[0718] Furthermore, equation (Ab-1) contains X and L. 1 The ring structure is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring.

[0719] In equation (Ab-2), R 2 R 3 L 1 The preferred method for X is the same as R in equation (Ab-1). 2 R 3 L 1 The preferred methods for X are the same.

[0720] In formula (Ab-2), L 2 Preferably, the substituent is a hydrocarbon group, more preferably an aromatic hydrocarbon group. Examples of substituents include alkoxy groups, nitro groups, and halogen atoms. Hereinafter, L... 2 Specific examples of preferred methods. In the following structures, * respectively represent L in equation (Ab-2). 2 The bonding sites of the carbon atoms are shown, with # indicating the bonding sites with Z. 1 The bonding sites. Furthermore, in the following structures, geometric heterogeneity is not particularly limited.

[0721] [Chemical Formula 53]

[0722]

[0723] In equation (Ab-2), Z 1 -O is preferred.

[0724] In equation (Ab-2), Z 3 Preferably =C(R) Z )- or =N-, =C(R) Z )-。 R Z It can be a hydrogen atom or any organic group, preferably a hydrogen atom. When R z When the organic group is any organic group, examples include hydrocarbon groups, but alkyl groups are preferred.

[0725] In equation (Ab-3), R 2 R 3 L 1 X and Z 3 The preferred method is the same as R in equation (Ab-1) 2 R 3 L 1 X and Z 3 The preferred method is the same.

[0726] In formula (Ab-3), L2 The preferred method is the same as L in equation (Ab-2) 2 The preferred method is the same.

[0727] In equation (Ab-3), Z 1 -O is preferred.

[0728] In equation (Ab-4), R 2 R 3 L 1 The preferred method for X is the same as R in equation (Ab-1). 2 R 3 L 1 The preferred methods for X are the same.

[0729] In formula (Ab-4), L 2 Preferably, it is a hydrocarbon group that can have substituents, and more preferably, it is a hydrocarbon cyclic group that can have substituents. Examples of substituents include alkoxy groups, nitro groups, and halogen atoms.

[0730] The following shows L 2 Specific examples of preferred methods. In the following structures, * respectively represent L in equation (Ab-4) 2 The bonding sites of the carbon atoms are shown, with # indicating the bonding sites with Z. 2 The bonding sites.

[0731] [Chemical Formula 54]

[0732]

[0733] In equation (Ab-4), Z 2 The preferred value is =O.

[0734] In formula (Ab-5) or formula (Ab-6), R 2 R 3 L 1 X, Z 3 L 2 The preferred method is the same as R in formula (Ab-2) or formula (Ab-3). 2 R 3 L 1 X, Z 3 L 2 The preferred method is the same.

[0735] In formula (Ab-5) or formula (Ab-6), Z 4 The preferred option is -OH.

[0736] An is a counter anion, and its structure is not particularly limited; it can be any other component in the composition. For example, examples include the way that the terminal carboxyl group of a particular resin can be a counter anion.

[0737] The compound represented by formula (Ab-1) is preferably a compound that has a maximum absorption wavelength in the range of 340 to 380 nm.

[0738] The compound represented by any one of formulas (Ab-2) to (Ab-6) is preferably a compound that has a maximum absorption wavelength at a wavelength of 400 to 700 nm.

[0739] The compound represented by formula (Ab-1) is preferably a compound whose structure is changed to that represented by any one of formulas (Ab-2) to (Ab-6) by irradiation with light of any wavelength in the range of 340 to 380 nm.

[0740] The compound represented by any one of formulas (Ab-2) to (Ab-6) is preferably transformed into the compound represented by formula (Ab-1) by irradiation with light of any wavelength between 400 and 700 nm, shading, or heating.

[0741] When the photosensitive resin composition contains a compound represented by any one of formulas (Ab-2) to (Ab-6), a compound represented by formula (Ab-1) can be generated by irradiating the composition or a film formed from the composition with light of any wavelength between 400 and 700 nm, by blocking light, or by heating. It is believed that in this manner, when the compound represented by formula (Ab-1) has a maximum absorption wavelength between 340 and 380 nm, the focusing margin increases through the aforementioned mechanism.

[0742] In equation (Ac-1), R 2 Each of the following can be independently a hydrogen atom, a halogen atom, or any organic group, preferably any organic group. As R 2 Any of the organic groups mentioned above can be exemplified by hydrocarbon groups, alkoxy groups, aryloxy groups, etc.

[0743] In equation (Ac-1), R 3 Each of the following is an independent hydrogen atom, halogen atom, or any organic group, preferably a hydrogen atom. As R 3 Any of the organic groups mentioned above can be exemplified by hydrocarbon groups, alkoxy groups, aryloxy groups, etc.

[0744] Furthermore, in equation (Ac-1), R 2Preferably, the rings are bonded together to form alicyclic or aromatic rings, more preferably aromatic rings. Naphthalene rings are an example of aromatic rings. The aforementioned alicyclic or aromatic rings may further contain substituents, provided that the effects of the present invention are achieved.

[0745] In equation (Ac-1), L 1 It can be any divalent linking group that may have substituents, preferably a hydrocarbon group that may have substituents, more preferably an alkenyl group that may have substituents, and even more preferably an vinylidene group (-CH=CH-).

[0746] In equation (Ac-1), Ar 1 Phenyl is preferred independently.

[0747] In equation (Ac-2), R 2 Each of the following can be independently a hydrogen atom, a halogen atom, or any organic group, preferably any organic group. As R 2 Any of the organic groups mentioned above can be exemplified by hydrocarbon groups, alkoxy groups, aryloxy groups, etc.

[0748] In equation (Ac-2), R 3 Each of the following is an independent hydrogen atom, halogen atom, or any organic group, preferably a hydrogen atom. As R 3 Any of the organic groups mentioned above can be exemplified by hydrocarbon groups, alkoxy groups, aryloxy groups, etc.

[0749] Furthermore, in equation (Ac-2), R 2 Preferably, they are bonded together to form a ring structure. As an example of the formed ring structure, a structure represented by the following formula (Cy-1) can be cited.

[0750] [Chemical Formula 55]

[0751]

[0752] In equation (Cy-1), R c1 Each of the two Rs can independently represent a hydrogen atom or an organic group. c1 They can bond together to form a ring structure, R c2 Each of the two Rs can independently represent a hydrogen atom or an organic group. c2 They can bond together to form a ring structure, * indicating a connection with L. 1 The bonding site, # indicates the bonding with R 3 The bonding site is indicated by a dashed line, which represents a single bond or a double bond. When the dashed line represents a double bond, there is no bonding site recorded as #.

[0753] In equation (Cy-1), two R values ​​are preferred. c1 Bonded to form a ring structure or 2 R c2They bond together to form a ring structure. The formed ring structure is preferably an aromatic ring structure, and more preferably a benzene ring structure.

[0754] In formula (Cy-1), the dashed part preferably represents a double bond.

[0755] In equation (Ac-2), L 1 The preferred group is a hydrocarbon group. In particular, when the dashed part is a double bond, -CH= is preferred.

[0756] In equation (Ac-2), Ar 1 The preferred method is the Ar in formula (Ac-1) 1 The preferred method is the same.

[0757] The compound represented by formula (Ac-1) is preferably a compound that has a maximum absorption wavelength in the range of 340 to 380 nm.

[0758] The compound represented by formula (Ac-2) is preferably a compound that has a maximum absorption wavelength in the range of 400 to 700 nm.

[0759] The compound represented by formula (Ac-1) is preferably a compound whose structure is changed to that represented by formula (Ac-2) by irradiation with light of any wavelength in the range of 340 to 380 nm.

[0760] The compound represented by formula (Ac-2) is preferably a compound whose structure is changed to that represented by formula (Ac-1) by irradiation with light of any wavelength in the range of 400 to 700 nm.

[0761] When a photosensitive resin composition contains a compound represented by formula (Ac-2), a compound represented by formula (Ac-1) can be generated by irradiating the composition or a film formed from the composition with light of any wavelength between 400 and 700 nm. It is believed that in this manner, when the compound represented by formula (Ac-1) has a maximum absorption wavelength between 340 and 380 nm, the focusing margin increases through the aforementioned mechanism.

[0762] In equation (Ad-1), R 7 Each of the following is independently a hydrogen atom, a halogen atom, or any organic group, preferably any organic group, more preferably a hydrocarbon group or a cyano group.

[0763] In equation (Ad-1), R 7 Preferably, they are bonded together to form a ring structure. As R 7 The structure formed by mutual bonding is preferably -C(=O)-NR N -C(=O)-, -C(=O)-OC(=O)- or -(CF2)3-. R NIt represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

[0764] In formula (Ad-1), Ar is preferably an aromatic ring heterocyclic structure that can have substituents, and more preferably a thiophene ring structure that can have substituents. As substituents, alkyl or aryl groups are preferred, and more preferably alkyl or phenyl groups having 1 to 4 carbon atoms.

[0765] In equation (Ad-2), R 7 The preferred method is the same as R in equation (Ad-1) 7 The preferred method is the same.

[0766] In equation (Ad-2), R 8 Preferably, it is an alkyl or aryl group, more preferably an alkyl or phenyl group having 1 to 4 carbon atoms.

[0767] In formula (Ad-2), R is preferably a heterocyclic structure, more preferably a hetero 5-membered ring structure, and even more preferably a structure represented by the following formula (Cy-2).

[0768] [Chemical Formula 56]

[0769]

[0770] In equation (Cy-2), R cy Each can be represented independently by a hydrogen atom or a substituent, Z cy The dashed part represents the ethylene bonded to R as described in formula (Ad-2), which represents an oxygen or sulfur atom.

[0771] In equation (Cy-2), R cy Each of the following is preferably a hydrogen atom or a hydrocarbon group, more preferably an alkyl or aromatic hydrocarbon group, and even more preferably a methyl or phenyl group.

[0772] In equation (Cy-2), Z cy The preferred atom is sulfur.

[0773] The compound represented by formula (Ad-1) is preferably a compound that has a maximum absorption wavelength at a wavelength of 340 to 380 nm.

[0774] The compound represented by formula (Ad-2) is preferably a compound that has a maximum absorption wavelength in the range of 400 to 700 nm.

[0775] The compound represented by formula (Ad-1) is preferably a compound whose structure is changed to that represented by formula (Ad-2) by irradiation with light of any wavelength in the range of 340 to 380 nm.

[0776] The compound represented by formula (Ad-2) is preferably a compound whose structure is changed to that represented by formula (Ad-1) by irradiation with light of any wavelength in the range of 400 to 700 nm.

[0777] When the photosensitive resin composition contains a compound represented by formula (Ad-2), a compound represented by formula (Ad-1) can be generated by irradiating the composition or a film formed from the composition with light of any wavelength between 400 and 700 nm. It is believed that in this manner, when the compound represented by formula (Ad-1) has a maximum absorption wavelength between 340 and 380 nm, the focusing margin increases through the aforementioned mechanism.

[0778] In equation (Ae-1), R 9 ~R 16 Each of the following is independently a hydrogen atom, a halogen atom, or any organic group, preferably a hydrogen atom or an alkyl group.

[0779] R is also preferred 9 ~R 16 At least two bonds in the ring are bonded to form a ring structure. In particular, R is preferred. 13 and R 14 They bond together to form a ring structure. Furthermore, the formed ring structure can be an aliphatic ring structure or an aromatic ring structure, but an aliphatic ring structure is preferred.

[0780] Furthermore, R is preferred. 10 and R 11 The bonds form a ring structure. The formed ring structure can be an aromatic ring structure, but is preferably an aromatic ring structure.

[0781] X is preferably -O-.

[0782] In equation (Ae-2), R 9 ~R 16 The preferred method of X is related to R in equation (Ae-1). 9 ~R 16 The preferred method for X is the same.

[0783] The compound represented by formula (Ae-1) is preferably a compound that has a maximum absorption wavelength at a wavelength of 340 to 380 nm.

[0784] The compound represented by formula (Ae-2) is preferably a compound that has a maximum absorption wavelength in the range of 400 to 700 nm.

[0785] The compound represented by formula (Ae-1) is preferably a compound whose structure is changed to that represented by formula (Ae-2) by irradiation with light of any wavelength in the range of 340 to 380 nm.

[0786] The compound represented by formula (Ae-2) is preferably a compound whose structure is changed to that represented by formula (Ae-1) by irradiation with light of any wavelength in the range of 400 to 700 nm.

[0787] When a photosensitive resin composition contains a compound represented by formula (Ae-2), a compound represented by formula (Ae-1) can be generated by irradiating the composition or a film formed from the composition with light of any wavelength between 400 and 700 nm. It is believed that in this manner, when the compound represented by formula (Ae-1) has a maximum absorption wavelength between 340 and 380 nm, the focusing margin increases through the aforementioned mechanism.

[0788] [Compound Ab]

[0789] The second photosensitive resin composition contains a compound Ab represented by any one of formulas (Ab-1) to (Ab-6).

[0790] The preferred embodiments of each symbol in formulas (Ab-1) to (Ab-6) and the preferred embodiments of these compounds are as described above.

[0791] [Compound Ac]

[0792] The third photosensitive resin composition contains a compound Ac represented by any one of formulas (Ac-1) to (Ac-2).

[0793] The preferred embodiments of each symbol in formulas (Ac-1) to (Ac-2) and the preferred embodiments of these compounds are as described above.

[0794] [Compound Ad]

[0795] The fourth photosensitive resin composition contains a compound Ad represented by any one of formulas (Ad-1) to (Ad-2).

[0796] The preferred embodiments of the symbols in formulas (Ad-1) to (Ad-2) and the preferred embodiments of these compounds are as described above.

[0797] [Compound Ae]

[0798] The fifth photosensitive resin composition contains a compound Ae represented by any one of formulas (Ae-1) to (Ae-2).

[0799] The preferred embodiments of each symbol in formulas (Ae-1) to (Ae-2) and the preferred embodiments of these compounds are as described above.

[0800] [Molecular weight]

[0801] The molecular weight of compound A is preferably 200 to 1500, more preferably 220 to 1000, and even more preferably 250 to 800.

[0802] [Synthesis Method]

[0803] Compound A can be synthesized, for example, by the methods described in the examples below. It can also be synthesized by other known synthetic methods, and the synthetic methods are not particularly limited. Furthermore, commercially available compounds from companies such as Tokyo Chemical Industry Co., Ltd. can also be used.

[0804] [Specific example]

[0805] As a specific example of compound A, and not particularly limited thereto, examples of compounds used in the following examples may be cited.

[0806] 〔content〕

[0807] The content of compound A relative to the total solids content of the photosensitive resin composition of the present invention is preferably 0.005 to 30% by mass. The lower limit is more preferably 0.010% by mass or more, and even more preferably 0.012% by mass or more. The upper limit is more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0808] Furthermore, when the content of the heterocyclic polymer is set to 100 parts by mass, the content of compound A is preferably 0.10 to 30 parts by mass, more preferably 0.010 to 30 parts by mass, even more preferably 0.020 to 20 parts by mass, and particularly preferably 0.024 to 15 parts by mass.

[0809] Compound A can be used alone or in combination with two or more compounds. When two or more compounds are used in combination, it is preferable that their total amount is within the above-mentioned range. For example, when the photosensitive resin composition contains compound Ab, the photosensitive resin composition may sometimes contain multiple compounds represented by any one of formulas (Ab-1) to (Ab-6). Furthermore, in the photosensitive resin composition, compounds Ab and Ac, etc., can be used in combination.

[0810] <Organometallic complexes>

[0811] The photosensitive resin composition of the present invention preferably contains an organometallic complex. Preferably, the organometallic complex contains a group IV element.

[0812] The compound containing a Group IV element is preferably a compound containing titanium, zirconium or hafnium, and more preferably a compound containing titanium.

[0813] Furthermore, compounds containing Group IV elements are preferably organometallic complexes, and more preferably organotitanium complexes.

[0814] Specific examples of compounds containing titanium are shown in I) to VII) below:

[0815] I) Titanium chelate compounds: From the viewpoint of obtaining the storage stability and good pattern of the negative photosensitive resin composition, titanium chelates having two or more alkoxy groups are more preferred, such as bis(triethanolamine) diisopropoxide titanium, bis(n-butanol) bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, diisopropoxide bis(tetramethylheptanedione) titanium, diisopropoxide bis(ethyl acetoacetate) titanium, etc.

[0816] II) Tetraalkoxy titanium compounds: such as tetra(n-butanol)titanium, tetraethanol titanium, tetra(2-ethylhexanol)titanium, tetraisobutanol titanium, tetraisopropanol titanium, tetramethanol titanium, tetramethoxypropanol titanium, tetramethylphenol titanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, etc.

[0817] III) Titanium eccentricity compounds: for example, pentamethylcyclopentadienyltrimethyltitanium, bis(η) 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-Cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium, etc.

[0818] IV) Monoalkoxy titanium compounds: such as titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzene sulfonate) isopropoxide, etc.

[0819] V) Titanium oxide compounds: such as bis(pentanedione) titanium oxide, bis(tetramethylheptanedione) titanium oxide, phthalocyanine titanium oxide, etc.

[0820] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0821] VII) Titanate coupling agents: such as isopropyltris(dodecyl)benzenesulfonyl titanate, etc.

[0822] In the above I) to VII), from the viewpoint of exhibiting better chemical resistance, the titanium-containing compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) titanium dicene compounds. In particular, diisopropanol bis(ethyl acetoacetate) titanium, tetra(n-butanol) titanium, and bis(n-butanol) titanium are preferred. 5-2,4-Cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium.

[0823] Furthermore, the aforementioned organometallic complex is preferably a metal complex having one or more π-conjugated sites containing nitrogen atoms (hereinafter also referred to as "specific metal complex").

[0824] Here, the nitrogen atom is preferably directly bonded to a metal atom in a specific metal complex. The bond is not particularly limited, but coordinate bonds are preferred.

[0825] Furthermore, the aforementioned π-conjugated site may have only one nitrogen atom or more than two nitrogen atoms. When it has more than two nitrogen atoms, it is preferable that one of them is directly bonded to a metal atom in a specific metal complex.

[0826] Here, a particular metal complex may have only one of the above-mentioned π-conjugated sites containing nitrogen atoms, or it may have two or more of the above-mentioned π-conjugated sites containing nitrogen atoms, preferably one or two.

[0827] The π-conjugated site containing nitrogen atoms is preferably represented by the following formula (Co-1).

[0828] [Chemical Formula 57]

[0829]

[0830] In formula (Co-1), X 1 ~X 3 -C(-*)= or -N= can be represented independently, with * indicating the bonding site with other structures and # indicating the bonding site with metal atoms.

[0831] In formula (Co-1), X 1 ~X 3 -C(-*)= or -N= can be represented independently, preferably at least one of them is -C(-*)=, more preferably at least two of them are -C(-*)=.

[0832] In formula (Co-1), structures bonded to at least two asterisks can also bond to form a ring structure. The ring structure can be an aliphatic ring structure or an aromatic ring structure, but an aromatic ring structure is preferred.

[0833] Furthermore, it is also preferred to contain a compound represented by the following formula (T-1) as a specific metal complex.

[0834] [Chemical Formula 58]

[0835]

[0836] In equation (T-1), M represents titanium, zirconium, or hafnium; l1 is an integer from 0 to 2; l2 is 0 or 1; l1 + l2 × 2 is an integer from 0 to 2; m is an integer from 0 to 4; n is an integer from 0 to 2; l1 + l2 + m + n × 2 = 4; R 11 R is independently substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted phenoxy. 12 R is a substituted or unsubstituted hydrocarbon group. 2 Each is independently a group containing a structure represented by the following formula (T-2), R 3 Each of the following groups independently contains a structure represented by the following formula (T-2), X A Each can be an oxygen atom or a sulfur atom, independently.

[0837] [Chemical Formula 59]

[0838]

[0839] In equation (T-2), X 1 ~X 3 -C(-*)= or -N= can be represented independently, with * indicating the bonding site with other structures and # indicating the bonding site with metal atoms.

[0840] In formula (T-1), from the viewpoint of the preservation stability of the composition, M is preferably titanium.

[0841] In formula (T-1), the method in which l1 and l2 are 0 is also one of the preferred methods of the present invention.

[0842] In formula (T-1), m is preferably 2 or 4, and more preferably 2.

[0843] In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1.

[0844] In this case, it is also preferable that l1 and l2 are 0 and m is 0, 2 or 4 in equation (T-1).

[0845] In equation (T-1), from the perspective of the stability of a specific metal complex, R 11 Preferably, it is a substituted or unsubstituted cyclopentadienyl ligand.

[0846] Furthermore, R 11 The cyclopentadienyl, alkoxy, and phenoxy groups in the present invention can be substituted, but the unsubstituted form is also one of the preferred forms of the present invention.

[0847] In equation (T-1), R 12 Preferably, it is a hydrocarbon group with 1 to 20 carbon atoms, and more preferably a hydrocarbon group with 2 to 10 carbon atoms.

[0848] As R 12 The hydrocarbon group in the form can be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with aromatic hydrocarbon groups being preferred.

[0849] As an aliphatic hydrocarbon group, it can be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.

[0850] As an aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 20 carbon atoms is preferred, an aromatic hydrocarbon group with 6 to 10 carbon atoms is more preferred, and phenylene oxide is even more preferred.

[0851] As R 12 The substituents in [the group] are preferably monovalent substituents, such as halogen atoms. Furthermore, when R [is present]... 12 When it is an aromatic hydrocarbon group, it can have alkyl groups as substituents.

[0852] In these, in equation (T-1), R 12 Preferably, it is an unsubstituted phenylene oxide. Furthermore, R 12 The phenylene oxide in the sample is preferably 1,2-phenylene oxide.

[0853] In equation (T-1), m is 2 or more, when there are 2 or more R. 2 At that time, there are more than 2 Rs 2 The structures can be the same or different.

[0854] In equation (T-1), n ​​is 2 or more, and when there are more than 2 R... 3 At that time, there are more than 2 Rs 3 The structures can be the same or different.

[0855] In equation (T-2), X 1 ~X 3 -C(-*)= or -N= can be represented independently, preferably at least one of them is -C(-*)=, more preferably at least two of them are -C(-*)=.

[0856] When the photosensitive resin composition contains an organometallic complex, the content is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the heterocyclic polymer. When the above content is 0.05 parts by weight or more, the heat resistance and chemical resistance are improved, and when it is 10 parts by weight or less, the storage stability is improved.

[0857] The resin composition of the present invention preferably further contains a polymerizable compound and a photopolymerization initiator.

[0858] The following sections will explain each point.

[0859] <Polymerizing compounds>

[0860] The photosensitive resin composition of the present invention preferably contains a polymerizable compound.

[0861] Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0862] [Free radical cross-linking agent]

[0863] The photosensitive resin composition of the present invention preferably contains a free radical crosslinking agent.

[0864] Free radical crosslinking agents are compounds having free radical polymerizable groups. Preferably, these groups contain olefinically unsaturated bonds. Examples of such olefinically unsaturated groups include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido.

[0865] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred, and (meth)acryloyl is more preferred from a reactivity point of view.

[0866] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may have three or more olefinic unsaturated bonds.

[0867] As compounds having two or more of the above-mentioned olefinic unsaturated bonds, compounds having 2 to 15 olefinic unsaturated bonds are preferred, compounds having 2 to 10 olefinic unsaturated bonds are more preferred, and compounds having 2 to 6 olefinic unsaturated bonds are even more preferred.

[0868] From the viewpoint of the film strength of the obtained pattern (cured product), the photosensitive resin composition of the present invention preferably contains compounds having two olefinic unsaturated bonds and compounds having three or more of the above-mentioned olefinic unsaturated bonds.

[0869] The molecular weight of the free radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the free radical crosslinking agent is preferably 100 or more.

[0870] Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl, amino, or thioalkyl groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration-fusion reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are preferred, and substitution reactions of unsaturated carboxylic acid esters or amides having leaving substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. Furthermore, as other examples, compounds substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, or allyl ethers can be used instead of the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0871] The free radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at atmospheric pressure. Examples of compounds having a boiling point of 100°C or higher at atmospheric pressure include those described in paragraph 0203 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0872] Other preferred free radical crosslinking agents besides those mentioned above include free radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0873] As free radical crosslinking agents, preferred are dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku Co., Ltd.)), A-TMMT (commercially available as SHIN-NAKAMURA CHEMICAL Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (Nippon Kayaku Co., Ltd.)), A-DPH (commercially available as SHIN-NAKAMURA CHEMICAL Co., Ltd.), and structures in which their (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0874] Commercially available free radical crosslinking agents include, for example, tetrafunctional acrylates SR-494 with four ethoxy groups, difunctional methacrylates SR-209, 231, and 239 with four ethoxy groups (manufactured by Sartomer Company, Inc.), hexafunctional acrylates DPCA-60 with six pentylene groups, trifunctional acrylates TPA-330 with three isobutylene groups (manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, and UA-7200 (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.). (Manufactured by Kyoisha Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOFCORPORATION.), etc.

[0875] As free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, and urethane compounds having an ethylene oxide backbone described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418 are also preferred. Compounds having an amino or thioether structure within the molecule, as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238, can also be used as free radical crosslinking agents.

[0876] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. The free radical crosslinking agent having acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Particularly preferred are compounds in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol in the free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Commercially available examples include, for instance, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO.,LTD.

[0877] The acid value of the free radical crosslinking agent containing acid groups is preferably 0.1 to 300 mg KOH / g, more preferably 1 to 100 mg KOH / g. As long as the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and developability. Furthermore, it has good polymerizability. The above acid value was determined according to the description in JIS K 0070:1992.

[0878] As a free radical crosslinking agent, a free radical crosslinking agent having at least one of the groups selected from urea bonds and urethane bonds is also preferred (hereinafter also referred to as "crosslinking agent U").

[0879] In this invention, the urea bond refers to the bond formed by *-NR. N -C(=O)-NR N -* indicates the key, R N Each symbol represents a hydrogen atom or a monovalent organic group independently, and * represents the bonding site with a carbon atom.

[0880] In this invention, the carbamate bond refers to the bond formed by *-OC(=O)-NR. N -* indicates the key, R NThe symbol represents a hydrogen atom or a monovalent organic group, and * indicates the bonding site with a carbon atom, respectively.

[0881] By including crosslinking agent U in the photosensitive resin composition, chemical resistance, resolution, etc., can sometimes be improved.

[0882] The crosslinking agent U may have only one urea bond or a carbamate bond, or it may have one or more urea bonds and one or more carbamate bonds, or it may have two or more urea bonds but no carbamate bonds, or it may have two or more carbamate bonds but no urea bonds.

[0883] The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0884] When the crosslinking agent U does not have urethane bonds, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0885] When the crosslinking agent U does not have urea bonds, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0886] The free radical polymerizable groups in the crosslinking agent U are not particularly limited, and examples include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0887] When the crosslinking agent U has more than two free radical polymerizable groups, the structures of each free radical polymerizable group can be the same or different.

[0888] The number of free radical polymerizable groups in the crosslinking agent U can be only 1 or more than 2, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0889] The free radical polymerizable group value (mass of compound per mole of free radical polymerizable groups) in crosslinking agent U is preferably 150-400 g / mol.

[0890] From the viewpoint of the chemical resistance of the cured product, the lower limit of the free radical polymerizability group value is more preferably 200 g / mol or more, further preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, even more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more.

[0891] From the viewpoint of radioactivity, the upper limit of the above-mentioned free radical polymerizability group value is more preferably 350 g / mol or less, further preferably 330 g / mol or less, and particularly preferably 300 g / mol or less.

[0892] The polymerizability of the crosslinking agent U is preferably 210–400 g / mol, more preferably 220–400 g / mol.

[0893] The crosslinking agent U is preferably a structure represented by, for example, the following formula (U-1).

[0894] [Chemical Formula 60]

[0895]

[0896] In equation (U-1), R U1 A is a hydrogen atom or a monovalent organic group, and A is -O- or -NR. N -, R N Z is a hydrogen atom or a monovalent organic group. U1 Z is an m-valent organic group. U2 X is an organic group with an n+1 valence, where X is a free radical polymerizable group, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 1.

[0897] R U1 Hydrogen atoms, alkyl or aromatic hydrocarbon groups are preferred, and hydrogen atoms are more preferred.

[0898] R N Hydrogen atoms, alkyl or aromatic hydrocarbon groups are preferred, and hydrogen atoms are more preferred.

[0899] Z U1 Preferred radicals include hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O)2-, and -NR. N - or groups formed by bonding two or more of them, more preferably hydrocarbon groups or hydrocarbon groups combined with groups selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - A group formed by bonding at least one of the groups in the group.

[0900] As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is even more preferred. Examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonds. N It represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.

[0901] Z U2Preferred radicals include hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O)2-, and -NR. N - or groups formed by bonding two or more of them, more preferably hydrocarbon groups or hydrocarbon groups combined with groups selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - A group formed by bonding at least one of the groups in the group.

[0902] As the aforementioned hydrocarbon group, examples can be cited that are similar to those in Z. U1 The hydrocarbon groups mentioned above that have the same hydrocarbon group are preferred in the same way.

[0903] X is not particularly limited and may include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamido, vinylphenyl or maleimide, more preferably (meth)acryloyloxy.

[0904] n is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, even more preferably 1 or 2, and particularly preferably 1.

[0905] m is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, and even more preferably 1 or 2.

[0906] The crosslinking agent U is preferably composed of at least one of hydroxyl, alkeneoxy, amide and cyano groups.

[0907] From the viewpoint of the chemical resistance of the obtained cured film, the hydroxyl group can be an alcoholic hydroxyl group or a phenolic hydroxyl group, but an alcoholic hydroxyl group is preferred.

[0908] From the viewpoint of the chemical resistance of the obtained cured film, the alkene oxide is preferably an alkene oxide with 2 to 20 carbon atoms, more preferably an alkene oxide with 2 to 10 carbon atoms, even more preferably an alkene oxide with 2 to 4 carbon atoms, and even more preferably an ethene oxide or a propene oxide, and particularly preferably an ethylene oxide.

[0909] The alkene oxide can be included in the crosslinking agent U as a polyalkene oxide. In this case, the number of repetitions of the alkene oxide is preferably 2 to 10, more preferably 2 to 6.

[0910] The amide group refers to the group consisting of -C(=O)-NR N - indicates the key. R N As described above. When the crosslinking agent U has an amide group, the crosslinking agent U can contain, for example, RC(=O)-NR. N -* indicates a group or is composed of *-C(=O)-NR N-R represents a group. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0911] The crosslinking agent U can have two or more structures selected from the group consisting of hydroxyl, alkene (wherein, when constituting polyalkene, it is polyalkene), amide and cyano groups, but it is also preferred to have only one in the molecule.

[0912] The aforementioned hydroxyl, alkeneoxy, and cyano groups can exist at any position in the crosslinking agent U. However, from the viewpoint of chemical resistance, in the crosslinking agent U, at least one of the groups selected from the group consisting of the aforementioned hydroxyl, alkeneoxy, and cyano groups is preferably linked to at least one free radical polymerizable group contained in the crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1").

[0913] In particular, when the crosslinking agent U contains only one free radical polymerizable group, the free radical polymerizable group contained in the crosslinking agent U is preferably linked to at least one of the groups selected from hydroxyl, alkene, amide and cyano groups via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").

[0914] When the crosslinking agent U contains an alkene group (wherein, if it constitutes a polyalkene group, it is a polyalkene group) and has the aforementioned linking group L2-1 or the aforementioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or linking group L2-2 of the alkene group (wherein, if it constitutes a polyalkene group, it is a polyalkene group) is not particularly limited, but it is preferable to have a group represented by a hydrocarbon group, a free radical polymerizable group, or a combination thereof. As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, a hydrocarbon group with 18 or fewer carbon atoms is more preferred, and a hydrocarbon group with 16 or fewer carbon atoms is even more preferred. Examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonds. Furthermore, the preferred manner for the free radical polymerizable group is the same as the preferred manner for the free radical polymerizable group in the aforementioned crosslinking agent U.

[0915] When the crosslinking agent U contains an amide group and has the aforementioned linking group L2-1 or L2-2, the structure bonded to the side opposite to the linking group L2-1 or L2-2 of the amide group is not particularly limited, but is preferably a group represented by a hydrocarbon group, a free radical polymerizable group, or a combination thereof. As the aforementioned hydrocarbon group, a hydrocarbon group with 20 or fewer carbon atoms is preferred, more preferably a hydrocarbon group with 18 or fewer carbon atoms, and even more preferably a hydrocarbon group with 16 or fewer carbon atoms. Furthermore, examples of the aforementioned hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by their bonds. The preferred manner for the free radical polymerizable group is the same as the preferred manner for the free radical polymerizable group in the crosslinking agent U. Furthermore, in the above manner, the carbon atom side of the amide group can be bonded to the linking group L2-1 or L2-2, and the nitrogen atom side of the amide group can be bonded to the linking group L2-1 or L2-2.

[0916] Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, the crosslinking agent U preferably has hydroxyl groups.

[0917] From the viewpoint of compatibility with heterocyclic polymers, the crosslinking agent U preferably contains aromatic groups.

[0918] The aromatic groups mentioned above are preferably directly bonded to the urea bonds or urethane bonds contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.

[0919] The aromatic group can be an aromatic hydrocarbon group or an aromatic heterocyclic group, or a structure formed by these forming a fused ring, preferably an aromatic hydrocarbon group.

[0920] As the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 30 carbon atoms is preferred, an aromatic hydrocarbon group with 6 to 20 carbon atoms is more preferred, and a group formed by removing 2 or more hydrogen atoms from the benzene ring structure is even more preferred.

[0921] As the aforementioned aromatic heterocyclic group, a 5-membered or 6-membered aromatic heterocyclic group is preferred. Examples of aromatic heterocycles in such aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetraazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings can be further fused with other rings, such as indole and benzimidazole.

[0922] Nitrogen, oxygen, or sulfur atoms are preferred as heteroatoms contained in the aforementioned aromatic heterocyclic groups.

[0923] The aromatic groups mentioned above are preferably included, for example, in the following linking groups: linking groups that link two or more free radical polymerizable groups and contain urea bonds or urethane bonds; or linking groups that link at least one of the groups selected from the group consisting of hydroxyl, alkoxy, amide and cyano groups and at least one free radical polymerizable group contained in the crosslinking agent U.

[0924] The number of atoms (linking chain length) between the urea bond or urethane bond in the crosslinking agent U and the free radical polymerizable group is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.

[0925] When the crosslinking agent U contains a total of two or more urea bonds or urethane bonds, or contains two or more free radical polymerizable groups, or contains two or more urea bonds or urethane bonds and two or more free radical polymerizable groups, the minimum number of atoms (linking chain length) between the urea bonds or urethane bonds and the free radical polymerizable groups shall be within the above range.

[0926] In this specification, "the number of atoms (linkage chain length) between the urea bond or urethane bond and the polymerizable group" refers to the shortest (minimum number of atoms) path connecting the two atoms or groups of atoms that are the linking objects. For example, in the structure represented by the following formula, the number of atoms (linkage chain length) between the urea bond and the free radical polymerizable group (methacryloyloxy) is 2.

[0927] [Chemical Formula 61]

[0928]

[0929] [Axis of symmetry]

[0930] The crosslinking agent U is preferably a compound without a symmetry axis.

[0931] The absence of a symmetry axis in crosslinking agent U means that it is a compound that is asymmetrical from left to right, and does not possess an axis that would allow the creation of molecules identical to the original molecules by rotating the entire compound. Furthermore, when marking the structural formula of crosslinking agent U on paper, the absence of a symmetry axis in crosslinking agent U means that its structural formula cannot be marked as having a symmetry axis.

[0932] It is believed that since the crosslinking agent U does not have a symmetry axis, the aggregation of crosslinking agents U in the composite film is suppressed.

[0933] [Molecular weight]

[0934] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0935] The method of manufacturing crosslinking agent U is not particularly limited, but for example, it can be obtained by reacting a compound having a free radical polymerizable compound and an isocyanate group with a compound having at least one of hydroxyl or amino groups.

[0936] The following are specific examples of crosslinking agent U, but crosslinking agent U is not limited to these.

[0937] [Chemical Formula 62]

[0938]

[0939] [Chemical Formula 63]

[0940]

[0941] [Chemical Formula 64]

[0942]

[0943] From the viewpoint of pattern resolution and film elasticity, the photosensitive resin composition preferably uses difunctional methacrylates or acrylates.

[0944] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentylene glycol diacrylate, and 1,6-hexanediol diacrylate can be used. 1,6-Hexanediol dimethacrylate, dimethylol-tricyclodecane dimethacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct dimethacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct dimethacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified dimethacrylate, isocyanuric acid EO-modified dimethacrylate, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be mixed as needed.

[0945] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a molecular weight of about 200 for the polyethylene glycol chain.

[0946] From the viewpoint of suppressing warping of the pattern (cured product), the photosensitive resin composition of the present invention preferably uses a monofunctional free radical crosslinking agent as a free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferably used are n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinyl caprolactam, and other N-vinyl compounds, allyl glycidyl ether, etc. As a monofunctional free radical crosslinking agent, in order to suppress volatilization before exposure, compounds having a boiling point of 100°C or higher at ambient pressure are also preferred.

[0947] In addition, examples of allyl compounds, such as diallyl phthalate and trimellitic acid, can be cited as free radical crosslinking agents with two or more functions.

[0948] When a free radical crosslinking agent is present, the content of the free radical crosslinking agent relative to the total solids content of the photosensitive resin composition is preferably more than 0% by mass and less than 60% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0949] A single free radical crosslinking agent can be used alone, or two or more can be used in combination. When two or more are used together, it is preferable that their combined dosage is within the range mentioned above.

[0950] [Other crosslinking agents]

[0951] The photosensitive resin composition of the present invention preferably contains other crosslinking agents different from the free radical crosslinking agents described above.

[0952] Other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents mentioned above. Preferably, they are compounds having multiple groups within the molecule that promote the reaction (forming covalent bonds with other compounds in the composition or their reaction products) through photosensitization by the aforementioned photoacid-producing agents or photoalkali-producing agents. More preferably, they are compounds having multiple groups within the molecule that promote the reaction (forming covalent bonds with other compounds in the composition or their reaction products) through the action of acids or bases.

[0953] The acid or base mentioned above is preferably an acid or base generated from a photoacid generator or a photoalkali generator during the exposure process.

[0954] Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. These descriptions are incorporated herein by reference.

[0955] [Polymerization initiator]

[0956] The photosensitive resin composition of the present invention preferably contains a polymerization initiator.

[0957] The polymerization initiator can be either a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferred to contain a photopolymerization initiator.

[0958] The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible regions is preferred. Furthermore, it can also be a reactive agent that reacts with a photoexcited sensitizer to generate active free radicals.

[0959] The photoradical polymerization initiator preferably contains at least one initiator having a concentration of at least about 50 L·mol⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 ·cm -1 The molar absorptivity of a compound. The molar absorptivity of a compound can be determined using known methods. For example, it is preferably determined using a UV-Vis spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and with ethyl acetate solvent at a concentration of 0.01 g / L.

[0960] As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl biimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron aromatic hydrocarbon complexes. For detailed information on these compounds, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, all of which are incorporated herein by reference.

[0961] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference, may be cited. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) may also be preferably used in commercially available products.

[0962] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators as described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators as described in Japanese Patent No. 4225898 can be used, as these contents are incorporated herein by reference.

[0963] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0964] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0965] As an aminoacetophenone-based initiator, an acylphosphine oxide-based initiator, or a metallocene compound, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 may also be used preferably. This content is incorporated herein by reference.

[0966] Oxime compounds are more preferably selected as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be further improved more effectively. Oxime compounds are particularly preferred because they offer a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0967] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science. The compounds described in andTechnology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Application Publication No. 2004-534797, the compounds described in Japanese Patent Application Publication No. 2017-019766, the compounds described in Japanese Patent Application Publication No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Patent Application Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, and the compounds described in International Publication No. 2013 / 167515, etc., are included in this specification.

[0968] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propionyloxy(imino))but-2-one, 2-(acetoxy(imino))pent-3-one, 2-(acetoxy(imino))-1-phenylprop-1-one, 2-(benzoyloxy(imino))-1-phenylprop-1-one, 3-((4-toluenesulfonyloxy)imino)but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylprop-1-one. In photosensitive resin compositions, the use of oxime compounds as photoradical polymerization initiators is particularly preferred. Oxime compounds used as photoradical polymerization initiators have an intramolecular linking group >C=NOC(=O)-.

[0969] [Chemical Formula 65]

[0970]

[0971] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKACORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), ADEKAARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Oxime compounds with the following structures can also be used.

[0972] [Chemical Formula 66]

[0973]

[0974] [Chemical Formula 67]

[0975]

[0976] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring, oxime compounds having at least one benzene ring in which a carbazole ring forms a naphthalene ring skeleton, and oxime compounds having fluorine atoms can also be used.

[0977] Furthermore, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl substituent bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359, are also permitted to be used. These contents are incorporated herein by reference.

[0978] Furthermore, compounds described in paragraphs 0113 to 0117 of Japanese Patent Application Publication No. 2023-058585 can also be used as photopolymerization initiators. This description is incorporated into the specification of this application.

[0979] When the photosensitive resin composition contains a photopolymerization initiator, its content relative to the total solids content of the photosensitive resin composition is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[0980] In addition, photopolymerization initiators can sometimes also function as thermal polymerization initiators. Therefore, heating with ovens, hot plates, etc., can sometimes further promote crosslinking using photopolymerization initiators.

[0981] [Sensitizer]

[0982] The photosensitive resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in its electronically excited state comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. Consequently, the thermal free radical polymerization initiator or photofree radical polymerization initiator undergoes a chemical change and decomposes, generating free radicals, acids, or bases.

[0983] As usable sensitizers, compounds such as benzophenone, michidone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzylene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethyl, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0984] Examples of sensitizers include milchone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylindanone, and p-dimethylaminoindanone. Benzylindanone, 2-(p-dimethylaminophenylbenzylidene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl 7-Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoate Isoamyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0985] In addition, other sensitizing pigments can also be used.

[0986] For details regarding the sensitizing pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0987] When the photosensitive resin composition contains a sensitizer, the content of the sensitizer relative to the total solids content of the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass. A single sensitizer may be used alone, or two or more may be used in combination.

[0988] [Chain transfer agent]

[0989] The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds, etc., with thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferably used.

[0990] Furthermore, the chain transfer agent can also be the compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0991] When the photosensitive resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the total solids content of the photosensitive resin composition. There may be only one type of chain transfer agent, or there may be two or more types. When there are two or more types of chain transfer agents, it is preferable that their total content falls within the above range.

[0992] Furthermore, the presence of two or more polymerization initiators in the photosensitive resin composition of the present invention is also one of the preferred embodiments of the present invention.

[0993] Specifically, the photosensitive resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0994] By including photopolymerization initiators and thermal polymerization initiators (described later), it is sometimes possible to form patterns using exposure and to easily perform free radical polymerization during curing using the heating process described later, thereby improving properties such as chemical resistance.

[0995] As for the ratio of the photopolymerization initiator and the thermal polymerization initiator (described later), the content of the thermal polymerization initiator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0996] By incorporating photoradical polymerization initiators and photoacid-producing agents, properties such as resolution can sometimes be improved.

[0997] As for the ratio of photopolymerization initiator and photoacid generator, the content of photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, relative to the total content of photopolymerization initiator and photoacid generator.

[0998] [Thermal polymerization initiator]

[0999] Examples of thermal polymerization initiators include thermal free radical polymerization initiators. Thermal free radical polymerization initiators are compounds that generate free radicals through thermal energy and initiate or promote the polymerization reaction of polymerizable compounds. By adding thermal free radical polymerization initiators, polymerization reactions of resins and polymerizable compounds can also be carried out, thus further improving solvent resistance.

[1000] As thermal free radical polymerization initiators, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated in this specification, can be cited.

[1001] When the resin composition contains a thermal polymerization initiator, its content relative to the total solids content of the photosensitive resin composition is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The photosensitive resin composition may contain only one thermal polymerization initiator or may contain two or more. When it contains two or more thermal polymerization initiators, the total amount is preferably within the above range.

[1002] <Alkali-producing agent>

[1003] The resin composition of the present invention may contain an alkali-generating agent. Here, an alkali-generating agent refers to a compound capable of producing alkali through physical or chemical action. Preferred alkali-generating agents include thermal alkali-generating agents and photo-alkali-generating agents.

[1004] In particular, when the resin composition contains a heterocyclic polymer precursor, the resin composition preferably contains an alkali-generating agent. By containing a thermal alkali-generating agent, the resin composition can promote the cyclization reaction of the precursor by heating, thereby becoming a substance with good mechanical properties or chemical resistance of the cured product, for example, improving its performance as an interlayer insulating film for rewiring layers contained in semiconductor packages.

[1005] As an alkali-producing agent, it can be either an ionic or a nonionic alkali-producing agent. Examples of bases produced from the alkali-producing agent include, for instance, secondary and tertiary amines.

[1006] The alkali-generating agent is not particularly limited, and known alkali-generating agents can be used. Examples of known alkali-generating agents include, for instance, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imine salts, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[1007] Specific examples of nonionic alkali-generating agents include the compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[1008] The following compounds can be cited as alkali-producing agents, but are not limited to these.

[1009] [Chemical Formula 68]

[1010]

[1011] The molecular weight of the nonionic alkali-generating agent is preferably below 800, more preferably below 600, and even more preferably below 500. The lower limit is preferably above 100, more preferably above 200, and even more preferably above 300.

[1012] Specific examples of preferred compounds as ionic alkali-generating agents include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[1013] Specific examples of ammonium salts include the following compounds, but are not limited to these.

[1014] [Chemical Formula 69]

[1015]

[1016] The following compounds can be cited as specific examples of imine salts, but are not limited to these.

[1017] [Chemical Formula 70]

[1018]

[1019] Furthermore, from the viewpoint of storage stability and the generation of alkali through deprotection during curing, an amine with an amino group protected by a tert-butoxycarbonyl group is preferred as an alkali-generating agent.

[1020] Examples of amine compounds protected by the tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, and α-[2-(methylamino)ethyl]benzylethanolamine. Compounds containing alcohols, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxobis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxotetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxoundecane, or amino acids and their derivatives, wherein the amino group is protected by a tert-butoxycarbonyl group, but not limited to these.

[1021] When the resin composition contains an alkali-generating agent, the content of the alkali-generating agent is preferably 0.1 to 50 parts by weight relative to 100 parts by weight of resin in the resin composition. The lower limit is more preferably 0.3 parts by weight or more, and even more preferably 0.5 parts by weight or more. The upper limit is more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less, even more preferably 5 parts by weight or less, and particularly preferably 4 parts by weight or less.

[1022] One or more alkali-producing agents can be used. When two or more are used, the total amount is preferably within the above range.

[1023] <Solvent>

[1024] The photosensitive resin composition of the present invention preferably contains a solvent.

[1025] Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[1026] Examples of esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetic acid, ethyl alkoxyacetic acid, butyl alkoxyacetic acid (e.g., methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, methyl 3-ethoxypropionic acid, alkyl 3-ethoxypropionic acid). Alkyl esters of 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred esters.

[1027] Examples of preferred ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[1028] Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[1029] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred cyclic hydrocarbons.

[1030] As a sulfoxide, dimethyl sulfoxide can be cited as a preferred sulfoxide.

[1031] As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine are among the preferred amides.

[1032] Examples of preferred urea types include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[1033] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

[1034] From the perspective of improving the properties of the coating surface, it is also preferable to use a mixture of two or more solvents.

[1035] In this invention, the solvent is preferably selected from one of the following: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucosidone, and dihydroL-glucosidone, or a mixture of two or more solvents. Particularly preferred methods include the use of dimethyl sulfoxide with γ-butyrolactone, dimethyl sulfoxide with γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide with γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone with ethyl lactate. Further addition of approximately 1 to 10% by mass relative to the total mass of these solvents is also a preferred method of the invention.

[1036] In particular, from the viewpoint of the storage stability of the photosensitive resin composition, the inclusion of γ-valerolactone as a solvent is one of the preferred embodiments of the present invention. In this embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and can be 100% by mass. The above content can be determined taking into account the solubility of heterocyclic polymers and other components contained in the photosensitive resin composition.

[1037] Furthermore, when dimethyl sulfoxide and γ-valerolactone are used together, the total mass of the solvent preferably contains 60-90% by mass of γ-valerolactone and 10-40% by mass of dimethyl sulfoxide, more preferably 70-90% by mass of γ-valerolactone and 10-30% by mass of dimethyl sulfoxide, and even more preferably 75-85% by mass of γ-valerolactone and 15-25% by mass of dimethyl sulfoxide.

[1038] From a coating point of view, the solvent content is preferably set at a total solids concentration of 5 to 80% by mass in the photosensitive resin composition of the present invention, more preferably at a total solids concentration of 5 to 75% by mass, even more preferably at a total solids concentration of 10 to 70% by mass, and even more preferably at a total solids concentration of 20 to 70% by mass. The solvent content can be adjusted according to the required coating thickness and coating method. When two or more solvents are contained, it is preferable that their total content is within the above range.

[1039] <Metal Adhesion Modifier>

[1040] From the viewpoint of improving adhesion to metal materials used in electrodes or wiring, the photosensitive resin composition of the present invention preferably contains a metal adhesion modifier. Examples of metal adhesion modifiers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[1041] [Silane coupling agent]

[1042] As silane coupling agents, examples include compounds described in paragraph 0316 of International Patent Publication No. 2021 / 112189 and compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. The following compounds are also preferred as silane coupling agents. In the following formula, Me represents methyl and Et represents ethyl. Furthermore, the following R can be a structure derived from the end-capping isocyanate group. As end-capping agents, they can be selected according to the desorption temperature, and examples include alcohol compounds, phenolic compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of setting the desorption temperature to 160–180°C, caprolactam is preferred. Commercially available examples of this compound include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[1043] [Chemical Formula 71]

[1044]

[1045] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3- Acryloyloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[1046] Furthermore, as a silane coupling agent, compounds of oligomer type having multiple alkoxysilyl groups can also be used.

[1047] Examples of this type of oligomer include compounds containing repeating units represented by the following formula (S-1).

[1048] [Chemical Formula 72]

[1049]

[1050] In equation (S-1), R S1 R represents a monovalent organic group. S2 It represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer from 0 to 2.

[1051] R S1 The structure containing a polymerizable group is preferred. Examples of polymerizable groups include groups having an olefinic unsaturated bond, epoxy groups, oxobutyl groups, benzoxazolyl groups, terminal isocyanate groups, and amino groups. Examples of groups having an olefinic unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl groups), (meth)acrylamido groups, and (meth)acryloyloxy groups. Vinylphenyl, (meth)acrylamido, or (meth)acryloyloxy groups are preferred, vinylphenyl or (meth)acryloyloxy groups are more preferred, and (meth)acryloyloxy groups are even more preferred.

[1052] R S2 Preferably, it is alkoxy, more preferably methoxy or ethoxy.

[1053] n represents an integer from 0 to 2, preferably 1.

[1054] Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer type compound can be the same.

[1055] Here, in the oligomer-type compound, among the plurality of repeating units represented by formula (S-1), it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two.

[1056] As for this type of oligomer compound, commercially available products can be used, such as KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[1057] [Aluminum-based adhesive additives]

[1058] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethyl acetoacetate diisopropoxide aluminum.

[1059] As other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are incorporated in this specification.

[1060] The content of the metal adhesion modifier is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the heterocyclic polymer. By setting the content to the lower limit or above, the adhesion between the pattern and the metal layer becomes good; by setting the content to the upper limit or below, the heat resistance and mechanical properties of the pattern become good. The metal adhesion modifier may be only one type or two or more types. When two or more types are used, it is preferable that their total content is within the above range.

[1061] <Compound X1>

[1062] The photosensitive resin composition of the present invention may contain compound X1.

[1063] Compound X1 is a compound having at least one structure selected from the group consisting of a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure and having a molecular weight of less than 1,000.

[1064] Here, the 1,3-dicarbonyl structure refers to the structure represented by the following formula (DC-1), and the β-hydroxycarbonyl structure refers to the structure represented by the following formula (HC-1).

[1065] [Chemical Formula 73]

[1066]

[1067] In formula (DC-1) or formula (HC-1), * and # represent bonding sites with other structures, respectively. Here, * is preferably a bonding site with a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. And # is preferably a bonding site with a hydrogen atom or carbon atom.

[1068] Here, the structure represented by (DC-1) above can be an enol type as shown in the following formula (DC-2).

[1069] Furthermore, the structure represented by (HC-1) above can be an enol type as shown in the following formula (HC-2).

[1070] [Chemical Formula 74]

[1071]

[1072] In formula (DC-2) or formula (HC-2), * and # represent bonding sites with other structures, respectively. * is preferably a bonding site with a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. And # is preferably a bonding site with a hydrogen atom or carbon atom.

[1073] Compound X1 preferably does not contain metal atoms in its structure. The metal atoms mentioned herein do not include half-metal atoms such as silicon dioxide.

[1074] Furthermore, compound X1 preferably does not coordinate with metal atoms in the photosensitive resin composition.

[1075] [Molecular weight]

[1076] The molecular weight of compound X1 is 1,000 or less, preferably 100 to 500, more preferably 100 to 400, even more preferably 100 to 350, particularly preferably 100 to 300, and even more preferably 100 to 250.

[1077] [Specific example]

[1078] As a specific example of compound X1, and without particular limitation, compounds with the following structures can be cited.

[1079] [Chemical Formula 75]

[1080]

[1081] 〔content〕

[1082] The content of compound X1 relative to the total solids content of the photosensitive resin composition of the present invention is preferably 0.01 to 30% by mass. The lower limit is more preferably 0.02% by mass or more, further preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more. The upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. Furthermore, 1% by mass or less is also one of the preferred embodiments of the present invention.

[1083] Compound X1 can be used alone or in combination with two or more compounds. When two or more compounds are used in combination, it is preferable that their total amount is within the range mentioned above.

[1084] <Migration Inhibitor>

[1085] The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By containing a migration inhibitor, for example, when the photosensitive resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[1086] As migration inhibitors, there are no particular limitations, and examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thiourea and thioalkyl groups, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[1087] As migration inhibitors, ion scavengers that capture anions such as halide ions can also be used.

[1088] Other migration inhibitors may include the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are incorporated herein by reference.

[1089] The following compounds can be cited as specific examples of migration inhibitors.

[1090] [Chemical Formula 76]

[1091]

[1092] When the photosensitive resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, relative to the total solid content of the photosensitive resin composition.

[1093] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that their total number is within the range mentioned above.

[1094] <Polymerization Inhibitor>

[1095] The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[1096] Specific compounds that can be used as polymerization inhibitors include those described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. This content is incorporated herein by reference.

[1097] When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, relative to the total solids content of the photosensitive resin composition.

[1098] There may be only one type of polymerization inhibitor or two or more types. When there are two or more types of polymerization inhibitors, it is preferable that their total number is within the range mentioned above.

[1099] [Urea compounds, carbodiimide compounds, isourea compounds]

[1100] From the viewpoint of elongation at break and adhesion to metal or resin layers, the photosensitive resin composition of the present invention may contain at least one compound selected from the group consisting of compounds having urea bonds (urea compounds), compounds having carbodiimide structures (carbodiimide compounds), and compounds having isourea bonds (isourea compounds) (hereinafter also referred to as "urea compounds, etc.").

[1101] In these, the photosensitive resin composition of the present invention preferably also contains a compound having urea bonds.

[1102] The urea compounds mentioned here do not include compound A above, the polymerizable compounds mentioned above, or compounds corresponding to silane coupling agents.

[1103] Examples of urea compounds include those described in paragraphs 0334 to 0339 of International Publication No. 2022 / 070730.

[1104] Specific examples of urea compounds include dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, diisopropylisourea, etc., but are not limited to these.

[1105] The total content of urea compounds, etc., relative to 100 parts by weight of heterocyclic polymer is preferably 0.1 to 10.0 parts by weight, more preferably 0.5 to 8.0 parts by weight, and even more preferably 1.0 to 6.0 parts by weight.

[1106] Urea compounds can be used alone or in combination with two or more. When two or more alkalis are used in combination in an alkaline treatment solution, their total content is preferably within the range mentioned above.

[1107] <Light Absorber>

[1108] The photosensitive resin composition of the present invention preferably contains a compound (light absorber) that reduces the absorbance of its exposure wavelength due to exposure. The light absorbers mentioned herein do not include compounds corresponding to compound A described above.

[1109] Examples of light absorbers include compounds described in paragraphs 0159 to 0183 of International Patent Publication No. 2022 / 202647 and compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689. These contents are included in this specification.

[1110] The content of light absorber relative to the total solids of the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[1111] <Other Additives>

[1112] The photosensitive resin composition of the present invention may contain various additives as needed within the range required to achieve the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the film properties and other properties can be adjusted. Regarding these components, reference can be made, for example, to paragraphs 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. When formulating these additives, it is preferable that their total content be set to 3% by mass or less of the solid content of the photosensitive resin composition of the present invention.

[1113] <Characteristics of Photosensitive Resin Compositions>

[1114] The viscosity of the photosensitive resin composition of the present invention can be adjusted according to the concentration of the solid components of the photosensitive resin composition. From the viewpoint of coating film thickness, 1,000 mm is preferred. 2 / s~12,000mm 2 / s, more preferably 2,000mm 2 / s~10,000mm 2 / s, further optimized to 2,500mm 2 / s~8,000mm 2 / s. As long as it remains within the above range, a highly uniform coating film can be easily obtained. For example, if it is 1,000 mm... 2 If the speed is above 12,000 mm, it is easy to coat with the film thickness required for reinsertion insulation. 2 When the speed is below / s, a coating film with excellent surface finish can be obtained.

[1115] <Restrictions on the Contents of Photosensitive Resin Compositions>

[1116] The moisture content of the photosensitive resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the photosensitive resin composition is improved.

[1117] Methods for maintaining moisture content include adjusting humidity under storage conditions and reducing the porosity of the storage container.

[1118] From the viewpoint of insulation, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but exclude metals contained as complexes of organic compounds with metals. When multiple metals are included, it is preferable that the total amount of these metals is within the above-mentioned range.

[1119] Furthermore, as a method to reduce metal impurities accidentally included in the photosensitive resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials constituting the photosensitive resin composition of the present invention, filtering the raw materials constituting the photosensitive resin composition of the present invention with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[1120] Regarding the photosensitive resin composition of the present invention, from the viewpoint of wiring corrosion, considering its use as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. Of this, the halogen atom content existing in the form of halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. The total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is preferably within the above-mentioned ranges.

[1121] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[1122] As a container for the photosensitive resin composition of the present invention, conventionally known containers can be used. For the purpose of preventing impurities from contaminating the raw materials or the photosensitive resin composition of the present invention, multi-layered bottles with an inner wall composed of six types of six-layered resins, or bottles with a seven-layered structure formed by six types of resins, are also preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[1123] <Curing of photosensitive resin composition>

[1124] By curing the photosensitive resin composition of the present invention, a cured product of the photosensitive resin composition can be obtained.

[1125] The cured product of the present invention is a cured product obtained by curing a photosensitive resin composition.

[1126] The curing of the photosensitive resin composition is preferably carried out by heating, more preferably at a heating temperature of 120°C to 400°C, even more preferably at 140°C to 380°C, and particularly preferably at 170°C to 350°C. The morphology of the cured photosensitive resin composition is not particularly limited, and can be selected as film, rod, sphere, granule, etc., depending on the application. In this invention, the cured product is preferably in film form. By patterning the photosensitive resin composition, the shape of the cured product can also be selected according to applications such as forming a protective film on a wall surface, forming conductive through-holes, adjusting impedance, electrostatic capacitance or internal stress, or imparting heat dissipation function. The film thickness of the cured product (the film formed by the cured product) is preferably 0.5 μm or more and 150 μm or less.

[1127] The shrinkage rate during curing of the photosensitive resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, shrinkage rate refers to the percentage change in volume of the photosensitive resin composition before and after curing, which can be calculated by the following formula.

[1128] Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[1129] <Characteristics of cured products of photosensitive resin compositions>

[1130] The imidization reaction rate of the cured photosensitive resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, it may sometimes result in a cured product with excellent mechanical properties.

[1131] The cured photosensitive resin composition of the present invention preferably has an elongation at break of 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[1132] The glass transition temperature (Tg) of the cured photosensitive resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[1133] <Preparation of Photosensitive Resin Compositions>

[1134] The photosensitive resin composition of the present invention can be prepared by mixing the above-described components. The mixing method is not particularly limited and can be carried out by conventionally known methods.

[1135] Examples of mixing methods include mixing using stirring blades, mixing using a ball mill, and mixing by rotating a tank.

[1136] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[1137] For the purpose of removing foreign matter such as dust or particles from the photosensitive resin composition of the present invention, filtration using a filter is preferred. Regarding the filter pore size, for example, 5 μm or less is preferred, more preferably 1 μm or less, further preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be a filter pre-cleaned with an organic solvent. In the filter filtration process, multiple filters can be connected in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, an HDPE filter with a pore size of 1 μm can be connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm as the second stage. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a circulating filtration. Filtration can also be performed after pressurization. When filtration is performed after pressurization, the pressurized pressure is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[1138] In addition to filtration using filters, impurity removal can also be performed using adsorption materials. A combination of filtration and impurity removal using adsorption materials can also be used. Known adsorption materials can be used as adsorption materials. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[1139] After filtration, the photosensitive resin composition filled in the bottle can be degassed under reduced pressure.

[1140] (Method for manufacturing solidified products)

[1141] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a photosensitive resin composition onto a substrate to form a film.

[1142] The method for manufacturing the cured material more preferably includes the above-described film forming step, an exposure step for selectively exposing the film formed by the film forming step, and a developing step for developing the film exposed by the exposure step using a developing solution to form a pattern.

[1143] The method for manufacturing the cured material is particularly preferably one of the above-described film forming step, the above-described exposure step, the above-described developing step, a heating step for heating the pattern obtained by the developing step, and a post-developing exposure step for exposing the pattern obtained by the developing step.

[1144] Furthermore, the method for manufacturing the cured material preferably includes the above-mentioned film formation process and the process of heating the above-mentioned film.

[1145] The following is a detailed explanation of each process.

[1146] <Membrane Formation Process>

[1147] The photosensitive resin composition of the present invention can be used in a film forming process in which it is applied to a substrate to form a film.

[1148] The method for manufacturing the cured product of the present invention preferably includes a film forming step of applying a photosensitive resin composition onto a substrate to form a film.

[1149] [Substrate]

[1150] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; vapor-deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, any of the substrates formed of metal and substrates with metal layers formed by methods such as plating or vapor deposition); paper; SOG (Spin-On Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In particular, semiconductor substrates are preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

[1151] An adhesive layer or oxide layer formed of hexamethyldisilazane (HMDS) or similar material can be provided on the surface of these substrates.

[1152] The shape of the substrate is not particularly limited; it can be circular or rectangular.

[1153] Regarding the dimensions of the substrate, if it is circular, the diameter is preferably 100–450 mm, more preferably 200–450 mm. If it is rectangular, the length of the shorter side is preferably 100–1000 mm, more preferably 200–700 mm.

[1154] As a substrate, a plate-like material can be used, preferably a panel-like substrate (substrate).

[1155] When a film is formed by applying a photosensitive resin composition to the surface of a resin layer (e.g., a layer formed by curing) or a metal layer, the resin layer or metal layer becomes a substrate.

[1156] As a method for applying a photosensitive resin composition to a substrate, coating is preferred.

[1157] Specifically, methods used include dip coating, air knife coating, curtain coating, wire-wound bar coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating is preferred; from the viewpoints of film thickness uniformity and productivity, spin coating and slot coating are more preferred. By adjusting the solid content concentration of the photosensitive resin composition or the coating conditions according to the method used, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.

[1158] Furthermore, it is also possible to apply a method of transferring a coating that has been applied and formed on a temporary support in advance by the above-described application method onto a substrate.

[1159] Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 may preferably be used.

[1160] Furthermore, a process can be performed to remove excess film from the ends of the substrate. Examples of such processes include edge bead rinse (EBR) and backwashing.

[1161] Alternatively, a pre-wetting process can be used: before coating the substrate with various solvents to improve the wettability of the substrate, the photosensitive resin composition is then applied.

[1162] <Drying Process>

[1163] After the film formation process (layer formation process), in order to remove the solvent, the above-mentioned film can be supplied to a process for drying the formed film (layer) (drying process).

[1164] That is, the method for manufacturing the cured product of the present invention may include a drying step of drying the film formed by the film forming step.

[1165] The drying process described above is preferably performed after the film formation process and before the exposure process.

[1166] The drying temperature of the membrane in the drying process is preferably 50°C to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 110°C. Furthermore, drying can be carried out under reduced pressure. The drying time can be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[1167] <Exposure Process>

[1168] The above-mentioned film can be used in an exposure process for selectively exposing the film.

[1169] Methods for manufacturing cured materials may include exposure processes that selectively expose films formed through film formation processes.

[1170] Selective exposure refers to exposing a portion of a film. Furthermore, selective exposure creates exposed areas (exposed areas) and unexposed areas (non-exposed areas) on the film.

[1171] The exposure amount is not particularly limited as long as it is sufficient to cure the photosensitive resin composition of the present invention. For example, it is preferably 50 to 10,000 mJ / cm², calculated based on the exposure energy at a wavelength of 365 nm. 2 More preferably 200–8,000 mJ / cm 2 .

[1172] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[1173] Regarding the exposure wavelength, in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide wavelengths (gamma, h, i-rays, etc.), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. Regarding the photosensitive resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferred, and from the viewpoint of exposure sensitivity, exposure using i-rays is more preferred.

[1174] The exposure method is not particularly limited, as long as at least a portion of the film formed by the photosensitive resin composition of the present invention is exposed. Examples include exposure using a photomask and exposure using direct laser imaging.

[1175] <Post-exposure heating process>

[1176] The above-mentioned film can be used in a process of heating after exposure (post-exposure heating process).

[1177] That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.

[1178] The post-exposure heating process can be performed after the exposure process and before the development process.

[1179] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[1180] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[1181] Regarding the heating rate in the post-exposure heating process, the rate from the initial heating temperature to the maximum heating temperature is preferably 1 to 12°C / minute, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[1182] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[1183] The heating method used in the post-exposure heating process is not particularly limited and can use known hot plates, ovens, infrared heaters, etc.

[1184] Furthermore, during heating, it is preferable to conduct the process in a low-oxygen environment by circulating inert gases such as nitrogen, helium, or argon.

[1185] <Developing Process>

[1186] The exposed film can be used in the developing process to form a pattern by developing it with a developing solution.

[1187] That is, the method for manufacturing the cured material of the present invention may include a developing step of developing a film exposed by an exposure step to form a pattern using a developing solution.

[1188] A pattern is formed by removing either the exposed or unexposed portion of the film through development.

[1189] Here, the development process that removes the non-exposed portions of the film is called negative development, and the development process that removes the exposed portions of the film is called positive development.

[1190] [Developing solution]

[1191] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[1192] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred alkaline compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH is preferred. In the total amount of developer, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[1193] When the developer contains an organic solvent, compounds described in paragraph 0387 of International Publication No. 2021 / 112189 may be used as the organic solvent. This content is incorporated into this specification. Furthermore, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., are preferably examples of alcohols, and N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., are preferably examples of amides.

[1194] Furthermore, when the developer contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In this invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is preferred; a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred; and a developer containing cyclopentanone is particularly preferred.

[1195] When the developer contains organic solvents, the content of organic solvents relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content may also be 100% by mass.

[1196] When the developer contains an organic solvent, it may also contain at least one of an alkaline compound and an alkali-generating agent. The alkaline compound and alkali-generating agent in the developer can penetrate into the pattern, sometimes improving properties such as the pattern's elongation at break.

[1197] From the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured material is further heated), organic bases are preferred as alkaline compounds.

[1198] As a basic compound, a basic compound having an amino group is preferred, preferably a primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. To promote the imidization reaction, a primary amine, secondary amine, tertiary amine or ammonium salt is preferred, more preferably a secondary amine, tertiary amine or ammonium salt, further preferably a secondary amine or tertiary amine, and particularly preferably a tertiary amine.

[1199] From the viewpoint of the mechanical properties (elongation at break) of the cured product, compounds that are not easily retained in the cured film (the obtained cured product) are preferred as alkaline compounds. From the viewpoint of promoting cyclization, compounds whose residual amount is not easily reduced by vaporization or the like before heating are preferred.

[1200] Therefore, the boiling point of the alkaline compound is preferably 30°C to 350°C at normal pressure (101,325 Pa), more preferably 80°C to 270°C, and even more preferably 100°C to 230°C.

[1201] The boiling point of the alkaline compound is preferably higher than the temperature obtained by subtracting 20°C from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.

[1202] For example, when the boiling point of the organic solvent is 100°C, the alkaline compound used preferably has a boiling point of 80°C or higher, and more preferably a boiling point of 100°C or higher.

[1203] The developer may contain only one type of alkaline compound or two or more types of alkaline compounds.

[1204] Specific examples of basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diaminopentane, and N-methylhexylamine. N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylamine ethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propanediamine, etc.

[1205] The preferred method for the alkali-generating agent is the same as that for the alkali-generating agent contained in the above composition. In particular, the alkali-generating agent is preferably a thermal alkali-generating agent.

[1206] When the developer contains at least one of an alkaline compound and an alkali-generating agent, the content of the alkaline compound or the alkali-generating agent relative to the total mass of the developer is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit of the above content is not particularly limited, for example, preferably 0.1% by mass or more.

[1207] When the alkaline compound or alkali-generating agent is solid in the environment of using the developer, the content of the alkaline compound or alkali-generating agent is preferably 70 to 100% by mass relative to the total solid content of the developer.

[1208] The developer may contain only one basic compound and at least one alkali-generating agent, or it may contain two or more basic compounds and at least one alkali-generating agent. When there are two or more basic compounds and alkali-generating agents, it is preferable that their total number is within the above range.

[1209] The developer may also contain other ingredients.

[1210] Other components include, for example, well-known surfactants or well-known defoamers.

[1211] [Method for supplying developer]

[1212] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the developer. Methods include: immersing the substrate with the film formed in the developer; swirling immersion development using a nozzle to supply the developer to the film formed on the substrate; or continuous supply of developer. There are no particular restrictions on the type of nozzle; examples include straight nozzles, spray nozzles, and mist nozzles.

[1213] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, it is preferable to supply the developer using a straight nozzle or a continuous supply method using a spray nozzle. From the viewpoint of developer penetration into the image area, a spray nozzle supply method is more preferable.

[1214] Furthermore, the following steps can be adopted: after continuously supplying developer with a straight nozzle, rotating the substrate to remove developer from the substrate, rotating and drying, and then continuously supplying developer with a straight nozzle again, rotating the substrate to remove developer from the substrate, or repeating this step multiple times.

[1215] Methods for supplying developer in the developing process include: a process of continuously supplying developer to a substrate; a process of keeping the developer in a substantially static state on the substrate; a process of vibrating the developer on the substrate using ultrasound or the like; and processes that combine these methods.

[1216] The preferred development time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18°C ​​to 30°C.

[1217] In the developing process, the pattern can be further cleaned (rinsed) using a rinsing solution after treatment with the developing solution. Alternatively, the rinsing solution can be supplied before the developing solution in contact with the pattern has completely dried.

[1218] [Rinse solution]

[1219] When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer can be used as the rinsing solution (e.g., water, an organic solvent different from the organic solvent contained in the developer).

[1220] When the rinsing solution contains an organic solvent, examples of organic solvents that are the same as those exemplified when the developing solution contains an organic solvent can be given.

[1221] The organic solvent contained in the rinsing solution is preferably an organic solvent that is different from the organic solvent contained in the developing solution, and more preferably an organic solvent that has a lower solubility in the pattern compared to the organic solvent contained in the developing solution.

[1222] When the rinsing solution contains organic solvents, one or more organic solvents may be used, or a mixture of two or more may be used. Preferred organic solvents include cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME; more preferably, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME; and even more preferably, cyclohexanone and PGMEA.

[1223] When the rinsing solution contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Furthermore, the organic solvent can be 100% by mass, relative to the total mass of the rinsing solution.

[1224] The rinsing solution may contain at least one of an alkaline compound and an alkali-generating agent.

[1225] While not particularly limited, when the developer contains an organic solvent, the rinsing solution containing at least one of an organic solvent, an alkaline compound, and an alkali-generating agent is also a preferred embodiment of the present invention.

[1226] Examples of alkaline compounds and alkali-generating agents contained in the rinsing solution include alkaline compounds that may be contained in the developer solution when it contains organic solvents, and examples of compounds that are exemplified as alkali-generating agents. The preferred methods are also the same.

[1227] Regarding the alkaline compounds and alkali-generating agents contained in the rinsing solution, their solubility in the solvent of the rinsing solution can be considered when selecting them.

[1228] When the rinsing solution contains at least one of an alkaline compound and an alkali-generating agent, the content of the alkaline compound or the alkali-generating agent relative to the total mass of the rinsing solution is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit of the above content is not particularly limited, for example, preferably 0.1% by mass or more.

[1229] When the alkaline compound or alkali-generating agent is solid in the environment of using the rinsing solution, the content of the alkaline compound or alkali-generating agent is preferably 70 to 100% by mass relative to the total solid content of the rinsing solution.

[1230] When the rinsing solution contains at least one of an alkaline compound and an alkali-generating agent, the rinsing solution may contain only one type of alkaline compound and alkali-generating agent, or it may contain at least two or more types of alkaline compounds and alkali-generating agents. When there are two or more types of alkaline compounds and alkali-generating agents, it is preferable that their total number falls within the above-mentioned range.

[1231] The rinsing solution may also contain other ingredients.

[1232] Other components include, for example, well-known surfactants or well-known defoamers.

[1233] [Method for supplying flushing fl...

Claims

1. A photosensitive resin composition comprising: At least one resin selected from the group consisting of heterocyclic polymers and their precursors; and Compound Aa is a photochromic compound.

2. The photosensitive resin composition according to claim 1, wherein, The compound Aa satisfies the following conditions 1 and 2. Condition 1: The structure changes to compound A when exposed to light with a wavelength of 365 nm. ex , Condition 2: When the absorbance of compound Aa at 365 nm is set to abs365-A1, and compound A... ex The absorbance at 365nm was set to abs365-A ex1 When abs365-A1 exceeds abs365-A ex1 .

3. The photosensitive resin composition according to claim 1, wherein, The membrane containing the resin and the compound Aa satisfies conditions 3 and 4 below. Condition 3: When the membrane is illuminated with light of wavelength 365 nm, the structure of compound Aa in the membrane changes to that of compound A. ex , Condition 4: When the content of compound Aa in the membrane is compared with that of compound Aa and compound A... ex The absorbance at 365 nm of a membrane containing a total content of 1% or more is defined as abs365-A2. Compound A contained in the membrane... ex The content of [a] relative to compound Aa and compound A ex The absorbance at 365 nm of a film with a total content of less than 0.5% by mass is defined as abs365-A. ex2 When abs365-A2 exceeds abs365-A ex2 .

4. The photosensitive resin composition according to claim 1, wherein, The film formed from the photosensitive resin composition satisfies the following conditions 5 and 6. Condition 5: When the membrane is exposed to light with a wavelength of 365 nm, the structure of compound Aa in the membrane changes to that of compound A. ex , Condition 6: When the content of compound Aa in the membrane is compared with that of compound Aa and compound A... ex The absorbance at 365 nm of a membrane containing a total content of 1% or more is defined as abs365-A3. Compound A contained in the membrane... ex The content of [a] relative to compound Aa and compound A ex The absorbance at 365 nm of a film with a total content of less than 0.5% by mass is defined as abs365-A. ex3 When, abs365-A3 exceeds abs365-A ex3 .

5. The resin composition according to claim 4, wherein, The maximum absorption wavelength of compound Aa in the wavelength range of 300 nm to 700 nm is similar to that of compound A. ex The difference in maximum absorption wavelength between 300nm and 700nm is 10nm to 400nm.

6. The photosensitive resin composition according to claim 1, wherein, Compound Aa is a compound represented by any one of the following formulas: (Ab-1) to (Ab-6), (Ac-1), (Ac-2), (Ad-1), (Ad-2), (Ae-1), and (Ae-2). In equation (Ab-1), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, R 4 R can be a hydrogen atom or any organic group. 5 R can be a hydrogen atom or any organic group. 4 With R 5 Optional bonding to form a ring structure, L 1 X is any divalent linker that optionally has substituents, where X is -O-, -S-, or -NR. 6 Any one of Z in - 1 -O-, -S-, -NR 6 Any one of - in R 6 The dashed part represents a hydrogen atom or any organic group. The dashed part indicates a single bond or a double bond. When the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist. In formula (Ab-2) or formula (Ab-3), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, L 1 X is any divalent linker that optionally has substituents, where X is -O-, -S-, or -NR. 6 Any one of - in R 6 Z can be a hydrogen atom or any organic group. 3 =C(R) Z )- or =N-, R Z L can be a hydrogen atom or any organic group. 2 Z is any divalent linking group that optionally has substituents. 1 -O, -S, or -NR 6 When the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist. In equation (Ab-4), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, L 1 X is any divalent linker that optionally has substituents, where X is -O-, -S-, or -NR. 6 Any one of - in R 6 L can be a hydrogen atom or any organic group. 2 Z is any divalent linking group that optionally has substituents. 2 =O, =S, or =NR 7 R 7 It can be a hydrogen atom or any organic group, when the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist. In formula (Ab-5) or formula (Ab-6), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, L 1 X is any divalent linker that optionally has substituents, where X is -O-, -S-, or -NR. 6 Any one of - in R 6 Z can be a hydrogen atom or any organic group. 3 =C(R) Z )- or =N-, R Z L can be a hydrogen atom or any organic group. 2 Z is any divalent linking group that optionally has substituents. 4 -OH, -SH, -N(R) 6 Any one of H, R 6 An is a hydrogen atom or any organic group, where An is a counter anion. When the dashed part is a double bond or R... 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist. In equation (Ac-1), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, L 1 Ar is any divalent linking group with optional substituents. 1 Each is an independent aromatic group. The dashed part represents a single bond or a double bond. When the dashed part represents a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist. In equation (Ac-2), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R is a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, L 1 Ar is any divalent linking group that optionally has substituents. 1 Each is an aromatic group that is optionally substituented, and the dashed part represents a single bond or a double bond. When the dashed part is a double bond, R 3 It does not exist. In equation (Ad-1), R 7 R can be independently a hydrogen atom, a halogen atom, or any organic group. 7 Ar can be optionally bonded together to form a ring structure, and Ar can be independently an aromatic ring structure optionally having substituents. In equation (Ad-2), R 7 R can be independently a hydrogen atom, a halogen atom, or any organic group. 7 They can be optionally bonded together to form a ring structure, R 8 Each of the following is independently a hydrogen atom, a halogen atom, or any organic group, and R is independently an optional ring structure with substituents. In equation (Ae-1), R 9 ~R 16 R can be independently a hydrogen atom, a halogen atom, or any organic group. 9 ~R 16 At least two of them are optionally bonded to form a ring structure, where X is -O-, -S-, or -NR. 6 Any one of - in R 6 It can be a hydrogen atom or any organic group. In equation (Ae-2), R 9 ~R 16 R can be independently a hydrogen atom, a halogen atom, or any organic group. 9 ~R 16 At least two of them are optionally bonded to form a ring structure, where X is -O-, -S-, or -NR. 6 Any one of - in R 6 It can be a hydrogen atom or any organic group.

7. The photosensitive resin composition according to claim 1, wherein, The content of compound Aa is 0.001% to 30% by mass relative to the total solids content of the photosensitive resin composition.

8. A photosensitive resin composition comprising: At least one resin selected from the group consisting of heterocyclic polymers and their precursors; and Compound Ab is represented by any of the formulas (Ab-1) to (Ab-6). In equation (Ab-1), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, R 4 R can be a hydrogen atom or any organic group. 5 R can be a hydrogen atom or any organic group. 4 With R 5 Optional bonding to form a ring structure, L 1 X is any divalent linker that optionally has substituents, where X is -O-, -S-, or -NR. 6 Any one of Z in - 1 -O-, -S-, -NR 6 Any one of - in R 6 The dashed part represents a hydrogen atom or any organic group. The dashed part indicates a single bond or a double bond. When the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist. In formula (Ab-2) or formula (Ab-3), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, L 1 X is any divalent linker that optionally has substituents, where X is -O-, -S-, or -NR. 6 Any one of - in R 6 Z can be a hydrogen atom or any organic group. 3 =C(R) Z )- or =N-, R Z L can be a hydrogen atom or any organic group. 2 Z is any divalent linking group that optionally has substituents. 1 -O, -S, or -NR 6 When the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist. In equation (Ab-4), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, L 1 X is any divalent linker that optionally has substituents, where X is -O-, -S-, or -NR. 6 Any one of - in R 6 L can be a hydrogen atom or any organic group. 2 Z is any divalent linking group that optionally has substituents. 2 =O, =S, or =NR 6 - When the dashed part is a double bond or R 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist. In formula (Ab-5) or formula (Ab-6), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, L 1 X is any divalent linker that optionally has substituents, where X is -O-, -S-, or -NR. 6 Any one of - in R 6 Z can be a hydrogen atom or any organic group. 3 =C(R) Z )- or =N-, R Z L can be a hydrogen atom or any organic group. 2 Z is any divalent linking group that optionally has substituents. 4 -OH, -SH, -N(R) 6 Any one of H, R 6 An is a hydrogen atom or any organic group, where An is a counter anion. When the dashed part is a double bond or R... 2 When the two Rs bond together to form an aromatic ring, the two Rs 3 It does not exist.

9. A photosensitive resin composition comprising: At least one resin selected from the group consisting of heterocyclic polymers and their precursors; and Compound Ac, represented by formula (Ac-1) or formula (Ac-2), In equation (Ac-1), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R can be independently a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, L 1 Ar is any divalent linking group that optionally has substituents. 1 Each is an independent aromatic group. The dashed part represents a single bond or a double bond. When the dashed part represents a double bond or R 2 When two R bonds are bonded to form an aromatic ring, the two R bonds... 3 It does not exist. In equation (Ac-2), R 2 R can be independently a hydrogen atom, a halogen atom, or any organic group. 3 R is a hydrogen atom, a halogen atom, or any organic group. 2 They can optionally bond together to form alicyclic or aromatic rings, L 1 Ar is any divalent linking group that optionally has substituents. 1 Each is an aromatic group that is optionally substituented, and the dashed part represents a single bond or a double bond. When the dashed part is a double bond, R 3 It does not exist.

10. A photosensitive resin composition comprising: At least one resin selected from the group consisting of heterocyclic polymers and their precursors; and Compound Ad, represented by formula (Ad-1) or formula (Ad-2), In equation (Ad-1), R 7 R can be independently a hydrogen atom, a halogen atom, or any organic group. 7 Ar can be optionally bonded together to form a ring structure, and Ar can be independently an aromatic ring structure optionally having substituents. In equation (Ad-2), R 7 R can be independently a hydrogen atom, a halogen atom, or any organic group. 7 They can be optionally bonded together to form a ring structure, R 8 Each of the following is independently a hydrogen atom, a halogen atom, or any organic group, and R is independently an optional ring structure with substituents.

11. A photosensitive resin composition comprising: At least one resin selected from the group consisting of heterocyclic polymers and their precursors; and The compound Ae, represented by formula (Ae-1) or formula (Ae-2), In equation (Ae-1), R 9 ~R 16 R can be independently a hydrogen atom, a halogen atom, or any organic group. 9 ~R 16 At least two of them are optionally bonded to form a ring structure, where X is -O-, -S-, or -NR. 6 Any one of - in R 6 It can be a hydrogen atom or any organic group. In equation (Ae-2), R 9 ~R 16 R can be independently a hydrogen atom, a halogen atom, or any organic group. 9 ~R 16 At least two of them are optionally bonded to form a ring structure, where X is -O-, -S-, or -NR. 6 Any one of - in R 6 It can be a hydrogen atom or any organic group.

12. The photosensitive resin composition according to any one of claims 1 to 11, wherein, The resin is a polyimide or a polyimide precursor.

13. The resin composition according to claim 12, wherein, The imidization rate of the polyimide precursor is 3% to 40%.

14. The resin composition according to claim 13, wherein, The imidization rate is 10% or more and 30% or less.

15. The photosensitive resin composition according to claim 12, wherein, The polyimide precursor contains a structure represented by the following formulas (1-5). R 51 Each is an independent organic group, R 52 It represents a hydrogen atom or an organic group; * indicates a bonding site with the resin structure.

16. The photosensitive resin composition according to claim 12, wherein, The resin has at least one repeating unit selected from the group consisting of the following repeating units: repeating units represented by equation (1-1), repeating units represented by equation (1-2), repeating units represented by equation (1-3), and repeating units represented by equation (1-4). In equation (1-1), X 1 Y is a tetravalent organic group. 1 It is a divalent organic group. In equation (1-2), A 2 For -O- or -NRZ-, R Z R is a hydrogen atom or a monovalent organic group. 2 X is a hydrogen atom or a monovalent organic group. 2 Y is a tetravalent organic group. 2 It is a divalent organic group. In equation (1-3), A 3 For -O- or -NRZ-, R Z R is a hydrogen atom or a monovalent organic group. 3 X is a hydrogen atom or a monovalent organic group. 3 Y is a tetravalent organic group. 3 It is a divalent organic group. In equation (1-4), A 41 and A 42 Each can be independently -O- or -NR. Z -, R Z R is a hydrogen atom or a monovalent organic group. 41 and R 42 Each can be independently a hydrogen atom or a monovalent organic group, X 4 Y is a tetravalent organic group. 4 It is a divalent organic group.

17. The photosensitive resin composition according to claim 16, wherein, The resin contains at least one repeating unit selected from the group consisting of repeating units A-1, A-2, A-3, and A-4. Repeating unit A-1: ​​It is a repeating unit represented by the above formula (1-1), and X1 is a repeating unit of any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure obtained by removing two or more hydrogen atoms from the structure represented by the following formula (V-4). Repeating unit A-2: It is a repeating unit represented by the above formula (1-2), and X2 is a repeating unit of any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure formed by removing two or more hydrogen atoms from the structure represented by the following formula (V-4). Repeating unit A-3: It is a repeating unit represented by the above formula (1-3), and X3 is a repeating unit of any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure obtained by removing two or more hydrogen atoms from the structure represented by the following formula (V-4). Repeating unit A-4: It is a repeating unit represented by the above formula (1-4), and X4 is a repeating unit of any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure obtained by removing two or more hydrogen atoms from the structure represented by the following formula (V-4). In equations (2a) to (2e), L 1 and L 2 Each is an independent divalent group or single bond that is not conjugated with the benzene ring to which it is bonded. 1 ~* 4 These represent the bonding sites with the carbonyl groups described in formulas (1-1), (1-2), (1-3), or (1-4), respectively, in which the hydrogen atoms are optionally substituted with substituents. In equation (V-4), n1 represents an integer greater than or equal to 1.

18. The photosensitive resin composition according to claim 16, wherein, The resin further contains at least one repeating unit selected from the group consisting of repeating unit B-1, repeating unit B-2, repeating unit B-3 and repeating unit B-4. Repeating unit B-1: It is a repeating unit represented by the above formula (1-1), and X1 contains a repeating unit with a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the following formulas (V-1), (V-2), (V-3) and (V-5). Repeating unit B-2: It is a repeating unit represented by the above formula (1-2), and X2 contains a repeating unit with a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the following formulas (V-1), (V-2), (V-3) and (V-5). Repeating unit B-3: It is a repeating unit represented by the above formula (1-3), and X3 contains a repeating unit with a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the following formulas (V-1), (V-2), (V-3) and (V-5). Repeating unit B-4: It is a repeating unit represented by the above formula (1-4), and X4 contains a repeating unit with a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the following formulas (V-1), (V-2), (V-3) and (V-5). In equation (V-2), R X1 Each is independently a hydrogen atom, an alkyl group, or a haloalkyl group. In equation (V-3), R X2 and R X3 Each can independently represent a hydrogen atom or a substituent, R X2 With R X3 They can be optionally bonded to form a ring structure.

19. The photosensitive resin composition according to claim 16, wherein, The resin contains at least one repeating unit selected from the group consisting of the following repeating units: a repeating unit represented by formula (1-1) where Y1 is a structure containing the structures represented by formulas (C-1) to (C-3); a repeating unit represented by formula (1-2) where Y2 is a structure containing the structures represented by formulas (C-1) to (C-3); a repeating unit represented by formula (1-3) where Y3 is a structure containing the structures represented by formulas (C-1) to (C-3); and a repeating unit represented by formula (1-4) where Y4 is a structure containing the structures represented by formulas (C-1) to (C-3). In equation (C-1), R 1 Each can independently represent a hydrogen atom or a monovalent organic group, n1 represents an integer from 0 to 3, n2 represents an integer from 0 to 3, and * indicates a bonding site with other structures. In equation (C-2), R 1 Each can independently represent a hydrogen atom or a monovalent organic group, where n1 represents an integer from 0 to 3, n2 represents an integer from 0 to 3, and R 2 Alkyl or fluoroalkyl groups are indicated independently, and * indicates a bonding site with other structures. In equation (C-3), R 1 Each can be used to independently represent a hydrogen atom or a monovalent organic group, n1 represents an integer from 0 to 3, and * represents a bonding site with other structures.

20. The photosensitive resin composition according to any one of claims 1 to 11, further comprising a photopolymerization initiator and a polymerizable compound.

21. The photosensitive resin composition according to any one of claims 1 to 11, further comprising an alkali-generating agent.

22. The photosensitive resin composition according to any one of claims 1 to 11, further comprising an organometallic complex.

23. The photosensitive resin composition according to any one of claims 1 to 11, further comprising a urea compound.

24. The photosensitive resin composition according to any one of claims 1 to 11, wherein, The polystyrene equivalent weight-average molecular weight (Mw) of the resin is less than 20,000.

25. The photosensitive resin composition according to any one of claims 1 to 11, wherein, The polystyrene resin has a converted weight-average molecular weight of 5,000 or more and 40,000 or less.

26. A cured product formed by curing the photosensitive resin composition according to any one of claims 1 to 11.

27. A laminate comprising two or more layers formed of the cured material of claim 26, and comprising a metal layer between any of the layers formed of the cured material.

28. A method for manufacturing a cured material, comprising: The film forming process involves applying the photosensitive resin composition according to any one of claims 1 to 11 onto a substrate to form a film.

29. The method for manufacturing a cured product according to claim 28, comprising: The exposure process selectively exposes the film; and In the developing process, the film is developed using a developing solution to form a pattern.

30. The method for manufacturing a cured product according to claim 28, comprising: The heating process involves heating the membrane at a temperature of 50°C to 450°C.

31. A method for manufacturing a laminate, comprising the method for manufacturing a cured material as described in claim 28.

32. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured material as described in claim 28.

33. A semiconductor device comprising the cured material of claim 26.

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