Photosensitive resin composition, cured product thereof, semiconductor device using cured product, and display device

Abstract

This photosensitive resin composition comprises: at least one resin (hereinafter, (A-1) resin) that has a structure indicated by formula (1) and that is selected from the group consisting of polyimides, polyamide-imides, polybenzoxazoles, polybenzothiazoles, and precursors thereof; a resin (hereinafter, (A-2) resin) that is different from said (A-1) resin, that has a structure indicated by formula (1), and that is at least one selected from the group consisting of polyimides, polyamide-imides, polybenzoxazoles, polybenzothiazoles, and precursors thereof; and (B) a photoacid generator. The proportion m1(mol%) at which R2s included in said (A-1) resin are alkyl groups having 1-6 carbon atoms or are monovalent acid-dissociable groups having 3-50 carbon atoms when the total of R2s included in said (A-1) resin is defined as 100 mol%, and the proportion m2(mol%) at which R2s included in said (A-2) resin are alkyl groups having 1-6 carbon atoms or are monovalent acid-dissociable groups having 3-50 carbon atoms when the total of R2s included said (A-2) resin is defined as 100 mol% satisfy 0<m1≤100 and / or 0<m2≤100. (In formula (1), R1 represents an organic group having a valence of 3-8 and having 3-50 carbon atoms, R2 represents a hydrogen atom, an alkyl group having 1-6 carbon atoms, or a monovalent acid-dissociable group having 3-50 carbon atoms, A represents an oxygen atom or a sulfur atom, n1 represents an integer of 1-4, * represents a binding site, and a1 and a2 each independently represent an integer of 1 or 2.)　The present invention can form a pattern that does not exhibit any cracks after being developed and that has a large taper angle after being cured.

Description

Photosensitive resin composition and cured product thereof, and semiconductor device and display device using the cured product

[0001] The present invention relates to a photosensitive resin composition, a cured product thereof, and a semiconductor device and a display device using the cured product.

[0002] Polyimides, polybenzoxazoles, and the like, which have excellent heat resistance, electrical insulation properties, and mechanical properties, are widely used in surface protection films and interlayer insulating films used in semiconductor devices, insulating layers in organic electroluminescent devices, and planarizing films for TFT (thin film transistor) substrates. In recent years, photosensitive resin compositions in which these resins themselves or their precursors are given photosensitivity have been used (hereinafter, these photosensitive resin compositions will be referred to as polyimide-based photosensitive resin compositions). The use of polyimide-based photosensitive resin compositions can simplify the pattern processing process and shorten the complicated manufacturing process.

[0003] In particular, positive-type materials in which exposed areas become readily soluble in a developer and can be patterned have the advantage of being able to process patterns with higher resolution, and known examples include polyimides, polybenzoxazoles, polyimide precursors, or polybenzoxazole precursors to which quinone diazide compounds have been added (see, for example, Patent Document 1).More recently, with the aim of achieving even higher sensitivity, polyimides or polybenzoxazole precursors to which photoacid generators have been added containing protecting groups that can be dissociated in the presence of acid (see, for example, Patent Documents 2 and 3) have been known.

[0004] JP 2011-180473 A JP 2011-221173 A JP 2006-349700 A

[0005] However, polyimides containing protecting groups that can be dissociated in the presence of acid have the problem that the steric hindrance of the protecting groups prevents sufficient intermolecular interactions inherent in polyimides, resulting in cracks in the pattern when developed after exposure. Furthermore, polybenzoxazole precursors containing protecting groups that can be dissociated in the presence of acid undergo significant shape changes due to softening during curing, resulting in a small taper angle of the cured pattern, making it difficult to arrange the pattern at high density. These issues become particularly pronounced as the film thickness increases.

[0006] In order to solve the above problems, the present invention has the following configuration: <1> A photosensitive resin composition comprising at least one resin selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, polybenzothiazole, and precursors thereof, having a structure represented by formula (1) (hereinafter referred to as (A-1) resin), at least one resin selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, polybenzothiazole, and precursors thereof, having a structure represented by formula (1), which is different from the (A-1) resin (hereinafter referred to as (A-2) resin), and (B) a photoacid generator, wherein all of the R contained in the (A-1) resin are ２ R in the resin (A-1) when ２ is the proportion m of alkyl groups having 1 to 6 carbon atoms or monovalent acid-dissociable groups having 3 to 50 carbon atoms. １ (mol %), all of the R contained in the (A-2) resin ２ R in the (A-2) resin when ２ is the proportion m of alkyl groups having 1 to 6 carbon atoms or monovalent acid-dissociable groups having 3 to 50 carbon atoms. ２ (mol%) is 0<m １ ≦100 and / or 0<m ２ A photosensitive resin composition satisfying the following condition:

[0007]

[0008] (In formula (1), R １ represents a trivalent to octavalent organic group having 3 to 50 carbon atoms, R ２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-dissociable group having 3 to 50 carbon atoms; A represents an oxygen atom or a sulfur atom; n １ is an integer of 1 to 4, * represents a binding site, a １ and a ２each independently represents an integer of 1 or 2.) <2> The photosensitive resin composition according to <1>, wherein the (A-1) resin is at least one resin selected from the group consisting of polyimide, polyamideimide, and precursors thereof, and the (A-2) resin is at least one resin selected from the group consisting of polybenzoxazole, polybenzothiazole, and precursors thereof. <3> At least one of the polymer terminals in the (A-1) resin is a structure represented by formula (2), formula (3), formula (4), or formula (4), and at least one of the polymer terminals in the (A-2) resin is a structure represented by formula (5), and R ３ , R ５ , R ６ and R ７ The photosensitive resin composition according to <2>, wherein at least one of the above has a thermal crosslinkable group.

[0009]

[0010] (In formulas (2) to (4), R ３ and R ５ represents a residue of a dicarboxylic acid anhydride having 1 to 12 carbon atoms, and R ４ represents a monovalent organic group having 1 to 12 carbon atoms, and R ６ represents a residue of a monoamine having 1 to 12 carbon atoms, and * represents a binding site. ７ represents a residue of a monocarboxylic acid having 1 to 12 carbon atoms, and * represents a bonding site.) <4> R in the formula (5) ７ <5> The photosensitive resin composition according to <3>, wherein R in the formula (1) has a thermal crosslinkable group. ２ <6> The photosensitive resin composition according to any one of <1> to <4>, wherein m is a hydrogen atom or a monovalent acid-dissociable group having 3 to 50 carbon atoms. １ (mol%) is 0<m １ ≦100 and ２ (mol%) is 0≦m ２ <7> The photosensitive resin composition according to any one of <1> to <6>, wherein the mass ratio of the (A-1) resin to the (A-2) resin is 5 / 95 to 95 / 5. <8> The photosensitive resin composition according to any one of <1> to <6>, wherein the mass ratio of the (A-1) resin to the (A-2) resin is 5 / 95 to 95 / 5.１ (mol%) is 20≦m １ <9> The photosensitive resin composition according to any one of <1> to <7>, wherein m ２ (mol%) is 0≦m ２ <50> The photosensitive resin composition according to any one of <1> to <8>, which satisfies <50>. <10> The photosensitive resin composition according to any one of <1> to <9>, wherein the (A-1) resin has at least one structural unit selected from formulas (6) to (8).

[0011]

[0012] (In formula (6), R ８ and R ９ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. １ represents a divalent organic group having 3 to 50 carbon atoms, and X １ represents a tetravalent organic group having 3 to 50 carbon atoms, and Y １ , X １ At least one of the above represents a structure represented by formula (1).

[0013]

[0014] (In formula (7), Y ２ represents a divalent organic group having 3 to 50 carbon atoms, and X ２ represents a tetravalent organic group having 3 to 50 carbon atoms, and Y ２ and X ２ At least one of the above represents a structure represented by formula (1).

[0015]

[0016] (In formula (8), Y ３ represents a divalent organic group having 3 to 50 carbon atoms, and X ３ represents a trivalent organic group having 3 to 50 carbon atoms, and Y ３ and X ３ At least one of the above represents a structure represented by formula (1). <11> The photosensitive resin composition according to any one of <1> to <10>, wherein the (A-2) resin has a structural unit represented by formula (9).

[0017]

[0018] (In formula (9), Y ４ represents a divalent organic group having 3 to 50 carbon atoms and represented by formula (1), and X4 represents a divalent organic group having 3 to 50 carbon atoms.) <12> The photosensitive resin composition according to <10>, wherein the (A-1) resin has a structural unit represented by formula (7). <13> The photosensitive resin composition according to <10>, wherein the (A-1) resin has at least one structural unit selected from formulas (10) to (12), and the (A-2) resin has a structural unit represented by formula (13), and wherein the AR ２ The total number of groups is M1, and AR from the structures of formulas (10) to (12). ２ The molecular weight of the remaining structural portion excluding the group is N1, and the AR included in formula (13) is ２ The total number of groups is M2, and AR from the structure of formula (13) ２ When the molecular weight of the remaining structural portion excluding the group is N2, if M1 / N1≧M2 / N2, m １ ≧m ２ If M1 / N1<M2 / N2, then m １ <m ２ <13> The photosensitive resin composition according to any one of <1> to <12>,

[0019]

[0020]

[0021]

[0022]

[0023] (In formulas (10) to (13), R １ , R ２ , R ８ , R ９ , A, n １ and X １ ~X ４ has the same meaning as the same symbol in the formula (1), and the formulas (6) to (9).) <14> The photosensitive resin composition according to any one of <1> to <13>, wherein at least one of the (A-1) resin and the (A-2) resin has a structure represented by formula (14).

[0024]

[0025] (In formula (14), R ２ , A, a １ and a ２ has the same meaning as the same symbol in the formula (1). L is a direct bond, —SO ２ -, -C(CH ３ ) ２ -, 9H-fluorene-9,9-diyl group. ２ and n ３ are each independently an integer of 0 to 2, provided that 1≦(n ２ +n ３ )≦4. * indicates a bonding site.) <15> R in formula (1) in the resin (A-1) ２ <15> The photosensitive resin composition according to any one of <1> to <14>, wherein at least one of the following is a group represented by formula (15) or formula (16):

[0026]

[0027] (In formula (15) and formula (16), R １０ and R １１ R each independently represents an alkyl group having 1 to 6 carbon atoms. １２ each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms. r represents an integer of 0 to 2, and s represents an integer of 0 to 2. * represents a bonding site.) <16> R in formula (1) in the resin (A-2) ２ The photosensitive resin composition according to any one of <1> to <15>, wherein at least one of the above is a group represented by formula (15) or formula (16). <17> A cured product of the photosensitive resin composition according to any one of <1> to <16>. <18> A semiconductor device having the cured product according to <17>. <19> A display device having the cured product according to <17>.

[0028] The photosensitive resin composition of the present invention does not cause cracks after development and enables the formation of a pattern with a high taper angle after curing.

[0029] FIG. 2 is a schematic diagram showing a taper angle according to the present invention.

[0030] The photosensitive resin composition of the present invention contains an (A-1) resin, an (A-2) resin, and a (B) photoacid generator, and all R contained in the (A-1) resin ２ R in the (A-1) resin when ２ is the proportion m of alkyl groups having 1 to 6 carbon atoms or monovalent acid-dissociable groups having 3 to 50 carbon atoms. １ (mol %), all of the R contained in the (A-2) resin ２ R in the (A-2) resin when ２ is the proportion m of alkyl groups having 1 to 6 carbon atoms or monovalent acid-dissociable groups having 3 to 50 carbon atoms. ２ (mol%) is 0<m １ ≦100 and / or 0<m ２ The photosensitive resin composition satisfies the condition of ≦100.

[0031]

[0032] (In formula (1), R １ represents a trivalent to octavalent organic group having 3 to 50 carbon atoms, and R ２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-dissociable group having 3 to 50 carbon atoms. A represents an oxygen atom or a sulfur atom. n １ is an integer of 1 to 4. * indicates a binding site, and a １ and a ２ each independently represents an integer of 1 or 2. １ The specific formula for calculating (mol %) is as follows:

[0033] m １ (mol %)=(number of alkyl groups having 1 to 6 carbon atoms+number of monovalent acid-dissociable groups having 3 to 50 carbon atoms) / (number of hydrogen atoms+number of alkyl groups having 1 to 6 carbon atoms+number of monovalent acid-dissociable groups having 3 to 50 carbon atoms) ２ The specific formula for calculating (mol %) is as follows:

[0034] m ２(mol %)=(number of alkyl groups having 1 to 6 carbon atoms+number of monovalent acid-dissociable groups having 3 to 50 carbon atoms) / (number of hydrogen atoms+number of alkyl groups having 1 to 6 carbon atoms+number of monovalent acid-dissociable groups having 3 to 50 carbon atoms). The photosensitive resin composition of the present invention contains a photoacid generator (B), and thus can generate an acid in the composition by exposure to light at a wavelength corresponding to the photoacid generator contained therein. This acid promotes solubility in an alkaline aqueous solution, and therefore the photosensitive resin composition of the present invention can form a positive relief pattern in which the exposed areas dissolve. Furthermore, the R ２ is a structure in which, under the action of an acid, A becomes a hydrogen atom accompanied by elimination of an organic group, and when A in formula (1) is an oxygen atom, a hydroxyl group is generated in the resin upon exposure, and when A in formula (1) is a sulfur atom, a mercapto group is generated in the resin upon exposure. Because the hydroxyl group and the mercapto group function as soluble groups in an alkaline aqueous solution, they further promote solubility in an alkaline aqueous solution, enabling the formation of a positive relief pattern with higher sensitivity.

[0035] For this reason, the above-mentioned structure in which the organic group is detached by the action of an acid to become a hydrogen atom is called an "acid-dissociable group." ２ is an acid-dissociable group, -AR in formula (1) ２ The structure of R ２ is an acid-dissociable group, -AR in formula (1) ２ The conversion of the structure to a hydroxyl group or a mercapto group is sometimes called "deprotection."

[0036] In formula (1), R １ is a trivalent to octavalent organic group having 3 to 50 carbon atoms.

[0037] R １ has an aromatic ring, and the aromatic ring is -AR ２ It is preferable that the １ By adopting such a structure, R ２ When R is a hydrogen atom, the acid dissociation constant (pKa) of the hydroxyl group or mercapto group becomes high, and R ２When is an acid-dissociable group, the acid dissociation constant (pKa) of the hydroxyl group or mercapto group after deprotection is increased, improving alkali solubility, thereby facilitating the production of a relief pattern with little residue.

[0038] From the viewpoint of improving sensitivity by promoting alkali solubility, A is preferably an oxygen atom.

[0039] In formula (1), * indicates a binding site, １ and a ２ each independently represents an integer of 1 or 2. From the viewpoint of the heat resistance of the resin, １ = a ２ = 1 or a １ = a ２ Preferably, a = 2, １ = a ２ It is more preferable that .times. ...

[0040] In addition, in formula (1), n １ is an integer of 1 to 4. From the viewpoint of the heat resistance of the resin, n １ is preferably an integer of 1 to 2, and more preferably 2.

[0041] Preferred specific examples of formula (1) include, but are not limited to, the following structures:

[0042]

[0043] In the above structure, R ２ , A, a １ , a ２ and n １ Each symbol has the same meaning as the corresponding symbol in formula (1), and the preferred range is the same as above. * indicates a binding site. n ４ and n ５ are each independently an integer of 0 to 2, provided that 1≦(n ４ +n ５ )≦4. From the viewpoint of the heat resistance of the resin, ４ and n ５ It is more preferable that both are 1.

[0044] Furthermore, from the viewpoint of increasing the taper angle of the pattern after curing, it is preferable that at least one of the resins (A-1) and (A-2) has a structure represented by formula (14).

[0045] It is more preferable that both the (A-1) resin and the (A-2) resin have a structure represented by formula (14).

[0046]

[0047] (In formula (14), R ２ , A, a １ and a ２ have the same meaning as the corresponding symbols in the formula (1). L is a direct bond, —SO ２ -, -C(CH ３ ) ２ -, 9H-fluorene-9,9-diyl group. ２ and n ３ are each independently an integer of 0 to 2, provided that 1≦(n ２ +n ３ )≦4. * indicates a bonding site.) From the viewpoint of increasing the taper angle of the pattern after curing, L is -SO ２ -, -C(CH ３ ) ２ - is more preferred, and -C(CH ３ ) ２ It is more preferable that − is the case.

[0048] From the viewpoint of heat resistance of resin ２ and n ３ are preferably all 1.

[0049] Furthermore, all of the R contained in the (A-1) resin ２ R in the (A-1) resin when ２ is the proportion m of alkyl groups having 1 to 6 carbon atoms or monovalent acid-dissociable groups having 3 to 50 carbon atoms. １ (mol %), all of the R contained in the (A-2) resin ２ R in the (A-2) resin when ２ is the proportion m of alkyl groups having 1 to 6 carbon atoms or monovalent acid-dissociable groups having 3 to 50 carbon atoms.２ (mol%) is 0<m １ ≦100 and / or 0<m ２ ≦100.

[0050] From the viewpoint of improving sensitivity, m １ (mol%) is 0<m １ ≦100 and m ２ (mol%) is 0≦m ２ It is preferable that the value satisfies ≦100.

[0051] Furthermore, from the viewpoint that the taper angle of the pattern after curing becomes high, １ (mol%) is 20≦m １ ≦90, and more preferably 30≦m １ It is more preferable that m １ It is most preferable that ≦80 be satisfied.

[0052] In addition, from the viewpoint of suppressing cracks, ２ (mol%) is 0≦m ２ It is more preferable that m<50, and 5≦m ２ It is more preferable that the ratio satisfies <50.

[0053] Here, m １ The value of (mol %) is the proportion of hydroxyl groups and mercapto groups of the (A-1) resin that are protected with alkyl groups or acid-dissociable groups, m ２ The value of (mol %) indicates the proportion of the hydroxyl groups and mercapto groups of the (A-2) resin that are protected with alkyl groups or acid-dissociable groups. １ (mol%), m ２The (mol %) is sometimes referred to as the "protection ratio". <(A-1) Resin, (A-2) Resin> The positive photosensitive resin composition of the present invention contains at least one resin selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, polybenzothiazole, and precursors thereof, which has a structure represented by formula (1), i.e., resin (A-1), and at least one resin selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, polybenzothiazole, and precursors thereof, which has a structure represented by formula (1), but is different from resin (A-1), i.e., resin (A-2).

[0054] The term "a resin other than the resin (A-1)" used herein refers to, for example, when the resin (A-1) is a polyimide, at least one resin selected from the group consisting of polyimide precursors, polyamideimides, polybenzoxazoles, polybenzothiazoles, polyamideimide precursors, polybenzoxazole precursors, and polybenzothiazole precursors; and when the resin (A-1) is a polyimide or a polyimide precursor, at least one resin selected from the group consisting of polyamideimides, polybenzoxazoles, polybenzothiazoles, polyamideimide precursors, polybenzoxazole precursors, and polybenzothiazole precursors.

[0055] The coexistence of at least two resins, namely (A-1) resin and (A-2) resin, improves the intermolecular interaction of the resins, even in the presence of a protecting group that can be dissociated in the presence of an acid, thereby preventing cracks from occurring. Furthermore, softening of the pattern is suppressed, and a pattern with a high taper angle after curing can be obtained.

[0056]

[0057] (In formula (1), R １ represents a trivalent to octavalent organic group having 3 to 50 carbon atoms, and R ２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-dissociable group having 3 to 50 carbon atoms. A represents an oxygen atom or a sulfur atom. n １ is an integer of 1 to 4. * indicates a binding site, and a １ and a ２each independently represents an integer of 1 or 2.) Polyimide is a polymer containing imide bonds in its repeating units. The polyimide can be synthesized by known methods. For example, the polyimide can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, or a tetracarboxylic acid diester dichloride with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, and then dehydrating and cyclizing the resulting reaction product by heating or by a reaction using a catalyst such as an acid or a base. Therefore, the polyimide has residues of tetracarboxylic acid and / or its derivatives and residues of diamine and / or its derivatives.

[0058] Polyamideimide is a polymer containing imide and amide bonds in its repeating units. Polyamideimide can be synthesized by known methods. For example, it can be obtained by reacting a tricarboxylic acid, a compound in which two of the tricarboxylic acids form an anhydride, or a compound in which the carboxylic acid is acid chloride or methyl esterified with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, and then dehydrating and cyclizing the resulting reaction product by heating or using a catalyst such as an acid or base. Therefore, the polyamideimide has tricarboxylic acid and / or its derivative residues and diamine and / or its derivative residues.

[0059] These reaction products before dehydration and ring closure are called polyimide precursors and polyamideimide precursors, and the process of dehydration and ring closure to form imide bonds is called imidization. When imidization is considered to have progressed 100% after curing at 320°C for 1 hour, and the imidization rate is the proportion of imide structures before curing based on this, polyimides and polyamideimides are those with an imidization rate of 80% or more. From the viewpoints of reducing the amount of gas generated during high-temperature use and improving the reliability of the cured product described below, the imidization rate is preferably 90% or more, and more preferably 95% or more.

[0060] Polybenzoxazoles and polybenzothiazoles are polymers containing oxazole and thiazole bonds in their repeating units. They can be synthesized by known methods. For example, they can be obtained by reacting a dicarboxylic acid or a corresponding dicarboxylic acid dichloride with a diamine having a hydroxyl or mercapto group bonded to the carbon adjacent to the amino group (ortho position), or a corresponding diisocyanate compound or trimethylsilylated diamine, and then subjecting the resulting reaction product to dehydration ring closure by heating or a reaction using an acid or base catalyst. Thus, the polybenzoxazoles and polybenzothiazoles contain residues of dicarboxylic acids and / or their derivatives, and residues of diamines and / or their derivatives with a hydroxyl or mercapto group bonded to the carbon adjacent to the amino group (ortho position).

[0061] The reaction products before dehydration and ring closure are referred to as polybenzoxazole precursors and polybenzothiazole precursors, and the formation of oxazole and thiazole bonds by dehydration and ring closure is referred to as oxazolization and thiazoleization. When cured at 320°C for 1 hour, oxazolization and thiazole formation are considered to have progressed 100%, and based on this, the proportion of oxazole and thiazole structures before curing is taken as the oxazolization rate and thiazole rate. Polybenzoxazoles and polybenzothiazoles have oxazolization rates and thiazole rates of 80% or higher. From the viewpoints of reducing the amount of gas generated during high-temperature use and improving the reliability of the cured product described below, the oxazolization rate and thiazole rate are preferably 90% or higher, and more preferably 95% or higher.

[0062] From the viewpoints of increasing the taper angle of the pattern after curing and suppressing cracks, it is preferred that the (A-1) resin is at least one resin selected from the group consisting of polyimide, polyamideimide, and precursors thereof, and that the (A-2) resin is at least one resin selected from the group consisting of polybenzoxazole, polybenzothiazole, and precursors thereof.

[0063] When the (A-1) resin is at least one resin selected from the group consisting of polyimide, polyamideimide, and precursors thereof, the (A-1) resin preferably has at least one structural unit selected from the following formulas (6) to (8): From the viewpoint of reducing film thickness reduction due to heat treatment, it is preferable to have at least one structural unit selected from formulas (7) and (8), and from the viewpoint of suppressing cracks, it is more preferable to have a structural unit of formula (7).

[0064]

[0065] (In formula (6), R ８ and R ９ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. １ represents a divalent organic group having 3 to 50 carbon atoms, and X １ represents a tetravalent organic group having 3 to 50 carbon atoms, and Y １ and X １ At least one of the above represents a structure represented by formula (1).

[0066]

[0067] (In formula (7), Y ２ represents a divalent organic group having 3 to 50 carbon atoms, and X ２ represents a tetravalent organic group having 3 to 50 carbon atoms, and Y ２ and X ２ At least one of the above represents a structure represented by formula (1).

[0068]

[0069] (In formula (8), Y ３ represents a divalent organic group having 3 to 50 carbon atoms, and X ３ represents a trivalent organic group having 3 to 50 carbon atoms, and Y ３ and X ３ At least one of the above represents a structure represented by formula (1). Formula (6) represents a polyimide precursor structure. In formula (6), R ８ and R ９each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Specific preferred examples of the monovalent organic group having 1 to 10 carbon atoms include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. From the viewpoint of increasing the taper angle of the pattern after curing, a methyl group and an ethyl group are more preferred.

[0070] In formula (6), Y １ represents a divalent organic group having 3 to 50 carbon atoms.

[0071] Y １ represents a structure represented by formula (1), preferred structures include, but are not limited to, residues of the following diamines having a hydroxyl group or a mercapto group, and structures in which the hydroxyl groups and mercapto groups of these residues are partly or entirely protected by acid-dissociable groups.

[0072] 2,4-diaminophenol, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)fluorene, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, 2,4-diaminothiophenol, bis(3-amino-4-mercapto)biphenyl, bis(3-amino-4-mercaptophenyl)methane, bis(3-amino-4-mercaptophenyl)ether, bis(3-amino-4-mercaptophenyl)propane, bis(3-amino-4-mercaptophenyl)fluorene, bis(3-amino-4-mercaptophenyl)hexafluoropropane, bis(3-amino-4-mercaptophenyl)sulfone.

[0073] Also, X １ represents a structure represented by formula (1), Y １ may be a residue of a diamine other than the structure represented by formula (1). Preferred specific examples include, but are not limited to, the following diamine residues.

[0074] Paraphenylenediamine, metaphenylenediamine, toluylenediamine, benzidine, orthotolidine, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ketone, diaminodiphenyl sulfide, bis(aminophenyl)propane, bis(aminophenyl)hexafluoropropane, bis(trifluoromethyl)benzidine, and water additives thereof, butanediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane.

[0075] In formula (6), X １ represents a tetravalent organic group having 3 to 50 carbon atoms. １ When represents a structure represented by formula (1), preferred structures include, but are not limited to, residues of the following acid dianhydrides having a hydroxyl group or a mercapto group, and structures in which the hydroxyl groups and mercapto groups of these residues are partially or entirely protected by alkyl groups or acid-dissociable groups.

[0076] 6,6'-methylenebis(5-hydroxyisobenzofuran-1,3-dione), N,N'-(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-diyl)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), N,N'-(propane-2,2'-diylbis(6-hydroxy-3,1-phenylene))bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), N,N'-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide)) , 6,6'-methylenebis(5-mercaptoisobenzofuran-1,3-dione), N,N'-(4,4'-dimercapto-[1,1'-biphenyl]-3,3'-diyl)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), N,N'-(propane-2,2'-diylbis(6-mercapto-3,1-phenylene))bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), N,N'-((perfluoropropane-2,2-diyl)bis(6-mercapto-3,1-phenylene))bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide).

[0077] Also, Y １ represents a structure represented by formula (1), X １ may be a residue of an acid dianhydride other than the structure represented by formula (1). Preferred specific examples include, but are not limited to, residues of the following acid dianhydrides: diphenyl ether tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, bifevir tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(isopropylidene)diphthalic anhydride, and diphenylmethane tetracarboxylic dianhydride.

[0078] From the viewpoint that the taper angle of the pattern after curing becomes high, Y １represents a structure represented by formula (1), and X １ is preferably a residue of an aliphatic acid dianhydride other than the structure represented by formula (1).

[0079] Preferred X １ Specific examples of include, but are not limited to, the residues of the following acid dianhydrides:

[0080] Cyclohexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione.

[0081] X １ represents a structure represented by formula (1), a １ = a ２ = 2, and Y １ represents a structure represented by formula (1), a １ = a ２ =1.

[0082] Formula (7) represents a polyimide structure. ２ represents a divalent organic group having 3 to 50 carbon atoms, X ２ represents a tetravalent organic group having 3 to 50 carbon atoms.

[0083] Y ２ , X ２ The preferred ranges of Y １ , X １ The preferred range is the same as that of

[0084] Formula (8) represents a polyamideimide structure. ３ represents a divalent organic group having 3 to 50 carbon atoms, X ３ represents a trivalent organic group having 3 to 50 carbon atoms.

[0085] Y ３ The preferred range of Y １ The preferred range is the same as that of

[0086] In formula (8), X ３ represents a trivalent organic group having 3 to 50 carbon atoms. ３When represents a structure represented by formula (1), preferred structures include, but are not limited to, residues of the following tricarboxylic acid anhydrides having a hydroxyl group or a mercapto group, and structures in which the hydroxyl groups and mercapto groups of these residues are partially or entirely protected with alkyl groups or acid-dissociable groups.

[0087] 5-hydroxytrimellitic anhydride, 4-(3-hydroxy-4-carboxyphenyloxy)phthalic acid, 4-(3-hydroxy-4-carboxyphenyl)phthalic acid, 5-mercaptotrimellitic anhydride, 4-(3-mercapto-4-carboxyphenyloxy)phthalic acid, 4-(3-mercapto-4-carboxyphenyl)phthalic acid.

[0088] Also, Y ３ represents a structure represented by formula (1), X ３ may be a residue of a tricarboxylic acid anhydride other than the structure represented by formula (1). Preferred examples include, but are not limited to, the following tricarboxylic acid anhydride residues:

[0089] Trimellitic anhydride, 4-(4-carboxyphenyloxy)phthalic acid, 4-(4-carboxyphenyl)phthalic acid.

[0090] From the viewpoint that the taper angle of the pattern after curing becomes high, Y ３ represents a structure represented by formula (1), and X ３ is preferably a residue of an aliphatic tricarboxylic acid anhydride other than the structure represented by formula (1).

[0091] Preferred X ３ Specific examples of X include, but are not limited to, hydrated trimellitic anhydride. ３ represents a structure represented by formula (1), a １ +a ２ = 3, and Y ３ represents a structure represented by formula (1), a １ = a ２ =1.

[0092] When the resin (A-2) is at least one resin selected from the group consisting of polybenzoxazole, polybenzothiazole, and precursors thereof, the resin (A-2) preferably has a structural unit represented by the following formula (9):

[0093]

[0094] (In formula (9), Y ４ represents a divalent organic group having 3 to 50 carbon atoms and represented by formula (1), and X ４ represents a divalent organic group having 3 to 50 carbon atoms.) Formula (9) represents a polybenzoxazole precursor structure or a polybenzothiazole precursor structure. In formula (9), Y ４ represents a divalent organic group having 3 to 50 carbon atoms, and the hydroxyl group, mercapto group, and organic groups in which these are protected with an alkyl group or an acid-labile group are bonded at the ortho position to the amide group so that polybenzoxazole or polybenzothiazole is formed upon dehydration ring closure.

[0095] In formula (9), Y ４ represents a structure represented by formula (1). Preferred structures include, but are not limited to, residues of the following diamines having hydroxyl groups or mercapto groups, and structures in which the hydroxyl groups and mercapto groups of these residues are partially or entirely protected by alkyl groups or acid-dissociable groups.

[0096] 2,4-diaminophenol, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)fluorene, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, 2,4-diaminothiophenol, bis(3-amino-4-mercapto)biphenyl, bis(3-amino-4-mercaptophenyl)methane, bis(3-amino-4-mercaptophenyl)ether, bis(3-amino-4-mercaptophenyl)propane, bis(3-amino-4-mercaptophenyl)fluorene, bis(3-amino-4-mercaptophenyl)hexafluoropropane, bis(3-amino-4-mercaptophenyl)sulfone.

[0097] In formula (9), X ４ represents a divalent organic group having 3 to 50 carbon atoms. Preferred structures include, but are not limited to, the residues of the following dicarboxylic acids.

[0098] Dicarboxydiphenyl ether, dicarboxydiphenyl sulfone, dicarboxydiphenyl sulfide, dicarboxydiphenyl methane, dicarboxybiphenyl, terephthalic acid, isophthalic acid, dicarboxydiphenyl ketone, 2,2-bis(carboxyphenyl)propane, 2,2-bis(carboxyphenyl)hexafluoropropane, 9,9-bis(carboxyphenyl)fluorene.

[0099] From the viewpoint that the taper angle of the pattern after curing becomes high, ４ is preferably the residue of an aliphatic dicarboxylic acid.

[0100] Preferred X ４ Specific examples of the above include residues of hydrides of the aromatic dicarboxylic acids and residues of the following dicarboxylic acids, but are not limited to these.

[0101] Adipic acid, hexanedicarboxylic acid, dodecanedicarboxylic acid, adamantanedicarboxylic acid.

[0102] Also, X ４ may be a structure represented by formula (1).

[0103] From the viewpoint of suppressing cracking and improving the taper angle, the mass ratio of the (A-1) resin to the (A-2) resin is preferably 5 / 95 to 95 / 5, more preferably 15 / 85 to 85 / 15, and even more preferably 25 / 75 to 75 / 25.

[0104] Furthermore, it is preferable that the mass ratio of either the (A-1) resin or the (A-2) resin is larger, and it is most preferable that the mass ratio is either 25 / 75 to 45 / 55 or 55 / 45 to 75 / 25.

[0105] Furthermore, from the viewpoint of reducing the difference in dissolution rate between two or more resins in an alkaline developer and reducing the film loss in the unexposed area during development, the (A-1) resin has at least one structural unit selected from formulas (10) to (12), the (A-2) resin has a structural unit represented by formula (13), and the (A-3) resin has an AR group included in formulas (10) to (12). ２ The total number of groups is M1, and AR from the structures of formulas (10) to (12). ２ The molecular weight of the remaining structural portion excluding the group is N1, and the AR included in formula (13) is ２ The total number of groups is M2, and AR from the structure of formula (13) ２ When the molecular weight of the remaining structural portion excluding the group is N2, if M1 / N1≧M2 / N2, m １ ≧m ２ If M1 / N1<M2 / N2, then m １ <m ２ It is preferable that the following is satisfied.

[0106]

[0107]

[0108]

[0109]

[0110] (In formulas (10) to (13), R １ , R ２ , R８ , R ９ , A, n １ and X １ ~X ４ has the same meaning as the same symbol in the formula (1) and formulas (6) to (9). For example, in a specific example where resin (A-1) is composed of a structural unit of formula (10), in the case of the following structure, M1 = 2.000 and N1 = 564.9, so M1 / N1 = 0.003540.

[0111]

[0112] Furthermore, in a specific example where the resin (A-1) is composed of a structural unit of formula (11), in the case of the following structure, M1=2.000 and N1=514.5, so M1 / N1=0.003887.

[0113]

[0114] Furthermore, in a specific example where the resin (A-1) is composed of the structural unit of formula (12), in the case of the following structure, M1=1.600 and N1=471.6, so M1 / N1=0.003393.

[0115]

[0116] Furthermore, in the case of the following structure, which is a specific example of the (A-2) resin consisting of the structural unit of formula (13), M2=2.000 and N2=528.7, so M1 / N1=0.003783.

[0117]

[0118] Furthermore, the main chain terminals of the (A-1) resin and / or the (A-2) resin may be capped with a terminal-capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. By capping the main chain terminals with a terminal-capping agent, the storage stability of the photosensitive resin composition can be improved. The incorporation ratio of the monoamine used as the terminal-capping agent is preferably 20 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, and particularly preferably 80 mol% or more, based on the amount of terminal carboxyl groups contained in the (A-1) resin or the (A-2) resin, taken as 100 mol%. The incorporation ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound used as the terminal-capping agent is preferably 20 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, and particularly preferably 80 mol% or more, based on the amount of terminal amino groups contained in the (A-1) resin or the (A-2) resin, taken as 100 mol%. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

[0119] From the viewpoint of improving chemical resistance after curing, the (A-1) resin is at least one resin selected from the group consisting of polyimide, polyamideimide, and precursors thereof, and at least one of the polymer terminals in the (A-1) resin has a structure represented by formula (2), formula (3), or formula (4); the (A-2) resin is at least one resin selected from the group consisting of polybenzoxazole, polybenzothiazole, and precursors thereof, and at least one of the polymer terminals in the (A-2) resin has a structure represented by formula (5); and R ３ , R ５ , R ６ and R ７ It is preferable that at least one of the above has a thermal crosslinkable group.

[0120] When one of the resins (A-1) and (A-2) has a thermally crosslinkable group at its terminal, there is an advantage that the chemical resistance of the other resin, which does not contain a thermally crosslinkable group at its terminal, is also improved.

[0121]

[0122] (In formulas (2) to (4), R ３ and R ５ represents a residue of a dicarboxylic acid anhydride having 1 to 12 carbon atoms, and R ４ represents a monovalent organic group having 1 to 12 carbon atoms, and R ６ represents a residue of a monoamine having 1 to 12 carbon atoms, and * represents a binding site. ７ represents a residue of a monocarboxylic acid having 1 to 12 carbon atoms, and * represents a bonding site.) Specific examples of the thermally crosslinkable group include, but are not limited to, a methylol group, an alkoxymethyl group, a vinyl group, an ethynyl group, an epoxy group, a glycidyl group, an oxetanyl group, an acrylic group, and a methacrylic group.

[0123] Preferred are vinyl groups, ethynyl groups, acrylic groups and methacrylic groups, and more preferred are acrylic groups and methacrylic groups.

[0124] In the formula (2), R ４ represents a monovalent organic group having 1 to 12 carbon atoms. Preferred specific examples include saturated hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group, but are not limited to these.

[0125] In the formula (2) and the formula (3), R ３ and R ５ represents a residue of a dicarboxylic acid anhydride having 1 to 12 carbon atoms.

[0126] Preferred specific examples include saturated hydrocarbon groups such as a methylene group, an ethylene group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and aromatic groups such as a phenyl group, a naphthyl group, and a hydroxyphenyl group. Preferred specific examples having a thermal crosslinkable group include, but are not limited to, those having the structures shown below.

[0127]

[0128] In the above structure, R ４has the same meaning as the same symbol in the formula (2), and the preferred range is the same as above. * indicates a binding site.

[0129] In the formula (4), R ６ represents a residue of a monoamine having 1 to 12 carbon atoms. Preferred specific examples include saturated hydrocarbons such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, cyclopentyl, hexyl, and cyclohexyl groups, and aromatic groups such as phenyl, naphthyl, and hydroxyphenyl groups, or specific examples having a thermal crosslinkable group include, but are not limited to, those having the structures shown below.

[0130]

[0131] * indicates the binding site.

[0132] In the formula (5), R ７ represents a residue of a monocarboxylic acid having 1 to 12 carbon atoms. Preferred specific examples include saturated hydrocarbons such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, cyclopentyl, hexyl, and cyclohexyl groups, and aromatic groups such as phenyl, naphthyl, and hydroxyphenyl groups, or preferred specific examples having a thermal crosslinkable group include those with the structures shown below, but are not limited to these.

[0133]

[0134] * indicates the binding site.

[0135] From the viewpoint of improving chemical resistance after curing, R is more preferable. ７ has a thermal crosslinkable group, and most preferably R ３ , R ５ , R ６ has a thermal crosslinkable group, and R ７ has a thermal crosslinkable group.

[0136] The weight average molecular weight of the (A-1) resin and / or the (A-2) resin is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 7,000 to 60,000, in terms of polystyrene, as measured by gel permeation chromatography. By setting the weight average molecular weight of the (a) component within the above range, it is possible to easily achieve good solvent solubility, good solubility in a developer, and high mechanical strength. <Acid-dissociable group> In formula (1), R ２ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-dissociable group having 3 to 50 carbon atoms.

[0137] Examples of the alkyl group having 1 to 6 carbon atoms include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group, and branched alkyl groups such as an isopropyl group, an isobutyl group, an isopentyl group, and a t-butyl group, but are not limited to these.

[0138] From the viewpoint of improving sensitivity, it is preferably a hydrogen atom or a monovalent acid-dissociable group having 3 to 50 carbon atoms.

[0139] Examples of the acid-dissociable group include, but are not limited to, a t-butoxycarbonyl group, a tetrahydropyranyl group, an (α-oxyalkyl) alkylene group, and the like.

[0140] From the viewpoint of achieving high sensitivity during pattern processing, the acid-dissociable group is preferably an (α-oxyalkyl) alkylene group.

[0141] Preferred (α-oxyalkyl)alkylene groups include, but are not limited to, the structures shown below.

[0142]

[0143] In the above structure, R １３ ~R １８ , R ２０ represents a monovalent organic group, and R １９ and R ２１ indicates a divalent organic group. * indicates a bonding site. The number of carbon atoms in the structure is 3 to 30.

[0144] Examples of the monovalent organic group include an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, and an alkoxycyclic alkyl group having 6 to 16 carbon atoms.

[0145] Examples of the divalent organic group include a propane-1,3-diyl group, a butane-1,3-diyl group, a pentane-1,3-diyl group, and an organic group in which a hydrogen atom of a functional group selected from the group consisting of a propane-1,3-diyl group, a butane-1,3-diyl group, and a pentane-1,3-diyl group is substituted with a functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxyalkyl group having 2 to 8 carbon atoms.

[0146] More preferred (α-oxyalkyl) alkylene groups include those having a structure represented by formula (17).

[0147]

[0148] In formula (17), R ２２ represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms. ２３ and R ２４ represents an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms. ２５ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an alkoxycyclic alkyl group having 6 to 16 carbon atoms. ２３ , R ２４ and R ２５ may be bonded to each other to form a cyclization. * indicates the bonding site.

[0149] Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups.

[0150] Specific examples of alkoxyalkyl groups having 2 to 8 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, a propoxymethyl group, a propoxyethyl group, a propoxypropyl group, and a propoxybutyl group.

[0151] Specific examples of the cyclic alkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclopentylethyl group, a cyclohexylethyl group, a cycloheptylethyl group, a cyclopentylpropyl group, a cyclohexylpropyl group, and a cycloheptylpropyl group.

[0152] Specific examples of alkoxy cyclic alkyl groups having 6 to 16 carbon atoms include a methoxypentyl group, an ethoxypentyl group, a propoxypentyl group, a dimethoxypentyl group, a diethoxypentyl group, a dipropoxypentyl group, a trimethoxypentyl group, a triethoxypentyl group, a tripropoxypentyl group, a methoxyhexyl group, an ethoxyhexyl group, a propoxyhexyl group, a dimethoxyhexyl group, a diethoxyhexyl group, a dipropoxyhexyl group, a trimethoxyhexyl group, a triethoxyhexyl group, a tripropoxyhexyl group, a methoxyheptyl group, an ethoxyheptyl group, a propoxyheptyl group, a dimethoxyheptyl group, a diethoxyheptyl group, a dipropoxyheptyl group, a trimethoxyheptyl group, a triethoxyheptyl group, and a tripropoxyheptyl group.

[0153] Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and a hexoxy group.

[0154] Formula (17) is -AR in formula (1). ２ At least one of the acid-dissociable groups is a group represented by formula (17), whereby -AR ２Therefore, even if only a small amount of acid is generated in the photosensitive composition upon light irradiation, deprotection can be achieved, and a highly sensitive photosensitive resin composition can be obtained.

[0155] From the viewpoint of increasing sensitivity during pattern processing, R in formula (1) of resin (A-1) ２ or at least one of R in formula (1) of resin (A-2). ２ It is preferable that at least one of the groups is a group represented by formula (15) or formula (16), which represents a specific structure of formula (17).

[0156]

[0157] In formulas (15) and (16), R １０ and R １１ R each independently represents an alkyl group having 1 to 6 carbon atoms. １２ each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms. r represents an integer of 0 to 2, and s represents an integer of 0 to 2. * represents a bonding site. Here, r=0 means a five-membered ring, r=1 means a six-membered ring, and r=2 means a seven-membered ring.

[0158] From the viewpoint of increasing sensitivity during pattern processing, R in formula (1) of resin (A-1) ２ is a group represented by formula (15) or formula (16), and R in formula (1) of resin (A-2) ２ It is more preferable that at least one of the groups is a group represented by formula (15) or formula (16).

[0159] R ２ is a monovalent acid-dissociable group having 3 to 50 carbon atoms, -AR ２can be obtained by reacting a resin having a hydroxyl group or a mercapto group with a protecting agent, for example, in the presence of an acid or a base at a reaction temperature of −20 to 50° C., without a solvent or in a solvent such as toluene, hexane, propylene glycol monomethyl ether acetate, or cyclopentanone.

[0160] The protecting agent in the present invention is a compound capable of protecting a hydroxyl group or a mercapto group, and the protecting group introduced thereby can be deprotected by the action of an acid or a base. As the protecting agent, any known protecting agent capable of protecting a hydroxyl group or a mercapto group can be used.

[0161] Examples of the protective agent include R ２ When is a 1-ethoxyethyl group, ethyl vinyl ether can be used, and when is a 2-tetrahydropyranyl group, 3,4-dihydro-2H-pyran, etc. can be used.

[0162] Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. Organic acid salts such as pyridinium p-toluenesulfonate can also be preferably used.

[0163] Examples of the base include amine compounds such as pyridine, N,N-diethyl-4-aminopyridine, triethylamine, and diisopropylamine. <(B) Photoacid Generator> The photoacid generator used in the present invention is a compound that has the function of generating an acid upon exposure to light. Any known photoacid generator can be used as long as it does not impair the effects of the present invention.

[0164] Specific examples of photoacid generators include ester compounds of polyhydric phenol compounds and naphthoquinone diazide sulfonic acid compounds, onium salt-type ionic photoacid generators, and nonionic photoacid generators. An onium salt is a compound formed when a compound having an electron pair not involved in a chemical bond forms a coordinate bond with another cationic compound via that electron pair. The cation portion of the onium salt determines the photochemical properties of the ionic photoacid generator, such as the molar absorption coefficient, absorption wavelength, and quantum yield, while the anion portion of the onium salt determines the strength of the acid generated. On the other hand, a nonionic photoacid generator is a photoacid generator in which the light-absorbing portion is covalently bonded to an acid.

[0165] The ionic photoacid generator is preferably one that does not contain heavy metals or halogen ions, and more preferably a triorganosulfonium salt compound. Specific examples of the triorganosulfonium salt compound include triphenylsulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, and perfluoro-1-butanesulfonate ("SP-056", product name, manufactured by ADEKA Corporation); the sulfonates of dimethyl-1-naphthylsulfonium; the sulfonates of dimethyl(4-hydroxy-1-naphthyl)sulfonium; the sulfonates of dimethyl(4,7-dihydroxy-1-naphthyl)sulfonium; and the sulfonates of diphenyliodonium.

[0166] As the nonionic photoacid generator, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylate compounds, sulfonimide compounds, phosphate compounds, sulfonebenzotriazole compounds, etc. can be used.

[0167] A specific example of the diazomethane compound is bis(4-methylphenylsulfonyl)diazomethane ("WPAG-199", trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0168] Specific examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, etc. Preferred examples of the sulfone compound include 2-(p-toluenesulfonyl)acetophenone and bis(phenylsulfonyl)methane.

[0169] Specific examples of the sulfonate ester compound include alkylsulfonate esters, haloalkylsulfonate esters, arylsulfonate esters, iminosulfonate ester compounds, etc. Preferred specific examples include benzoin-4-tolyl sulfonate, pyrogallol tris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, and 2,6-(dinitrobenzyl)phenyl sulfonate.

[0170] Specific examples of carboxylic acid ester compounds include carboxylic acid 2-nitrobenzyl esters.

[0171] From the viewpoint of achieving high sensitivity during pattern processing, a nonionic photoacid generator is preferred as the photoacid generator (B). By including a nonionic photoacid generator as the photoacid generator (B), a photosensitive resin composition with higher sensitivity can be obtained.

[0172] More preferred examples of the photoacid generator (B) include oxime sulfonate compounds and / or imide sulfonate compounds. Oxime sulfonate compounds and imide sulfonate compounds are nonionic photoacid generators, and the acidic group generated by light is sulfonic acid, which has a high acid dissociation constant (pKa), allowing for a photosensitive resin composition with higher sensitivity.

[0173] The oxime sulfonate compound can be represented by the following structure:

[0174]

[0175] R ２６is a monovalent organic group having 1 to 12 carbon atoms. Specific examples of the monovalent organic group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a trifluoromethanesulfonic acid group, a nonafluorobutyl group, a perfluorooctyl group, a (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl group, a benzyl group, a phenyl group, a tosyl group, and a naphthyl group.

[0176] R ２７ and R ２８ is a monovalent organic group having 1 to 30 carbon atoms. ２７ and R ２８ may be the same or different. Specific examples of the monovalent organic group having 1 to 30 carbon atoms include a cyano group, a trifluoromethyl group, a hexafluoropropyl group, a pentafluorobutyl group, a dodecafluorohexyl group, a phenyl group, a 4-methoxyphenyl group, a 2-fluorenyl group, and a 4-(3-(4-(2,2,2-trifluoro-1-(((propylsulfonyl)oxy)imino)ethyl)phenoxy)propoxy)phenyl group.

[0177] R ２９ is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of the monovalent organic group having 3 to 30 carbon atoms include the following structures.

[0178]

[0179] * indicates the binding site.

[0180] Specific examples of the oxime sulfonate include "Irgacure" (registered trademark), PAG-103 (benzeneacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene), PAG-121 (benzeneacetonitrile, 2-methyl-α-[[(4-methylphenyl)oxy]imino]-3(2H)-thienylidene), PAG-108 (benzeneacetonitrile, 2-methyl-α-[[(n-octyl)oxy]imino]-3(2H)-thienylidene), and PAG-203 (all manufactured by BASF Japan Ltd.), and PAI-101 ((Z)-4-methoxy-N-(tosyloxy)benzimidoyl cyanide, manufactured by Midori Chemical Industry Co., Ltd.).

[0181] The imidosulfonate compound can be represented by the following structure:

[0182]

[0183] R ３０ is a monovalent organic group having 1 to 12 carbon atoms. Specific examples of the monovalent organic group having 1 to 12 carbon atoms include R ２６ Examples of the groups include those given as specific examples of the above.

[0184] R ３１ and R ３２ is a monovalent organic group having 1 to 30 carbon atoms. ３１ and R ３２ may be the same or different. Specific examples of the monovalent organic group having 1 to 30 carbon atoms include R ２７ and R ２８ Examples of the groups include those given as specific examples of the above.

[0185] R ３３ is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of divalent organic groups having 3 to 30 carbon atoms include the following structures:

[0186]

[0187] R ３４is a monovalent organic group having 1 to 12 carbon atoms. v is an integer of 0 to 2. Specific examples of monovalent organic groups having 1 to 12 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a butyl group, a 2-butyl group, an isobutyl group, a t-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecanyl group, a 1-(hex-1-en-1-yl) group, and a 1-(4-butoxyphenethyl) group. * indicates a bonding site.

[0188] Examples of the imide sulfonate compound include N-hydroxynaphthalimide triflate, "ADEKA ARCLES" (registered trademark) SP-606 (4-butyl-N-hydroxy-naphthalimide triflate, manufactured by ADEKA Corporation), NA-101 (N-hydroxynaphthalimide-p-toluenesulfonate), and NA-106 (N-hydroxynaphthalimide camphorsulfonate, all manufactured by Midori Chemical Industry Co., Ltd.).

[0189] In the photosensitive resin composition of the present invention, in view of the difference in dissolution rate between the exposed and unexposed portions and the tolerance range of sensitivity, the content of the photoacid generator (B) is preferably 1 to 100 parts by mass, and more preferably 1 to 40 parts by mass, per 100 parts by mass of the total of the resin (A-1) and the resin (A-2).

[0190] <Solvent> The positive photosensitive resin composition of the present invention preferably further contains a solvent (hereinafter, may be referred to as "solvent (C)"). By containing a solvent, the coating property is improved, and a homogeneous positive photosensitive resin film can be obtained.

[0191] The (C) solvent is not particularly limited as long as it can dissolve or disperse the (A-1) resin, the (A-2) resin, and the (B) photoacid generator. Suitable solvents include amide-based solvents, ester-based solvents, alcohol-based solvents, ether-based solvents, ketone-based solvents, and dimethyl sulfoxide.

[0192] Specific examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyric acid amide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N,N-dimethylpropylene urea.

[0193] Specific examples of the ester solvent include γ-butyrolactone, δ-valerolactone, propylene carbonate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetoacetate, and cyclohexanol acetate.

[0194] Specific examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, and propylene glycol.

[0195] Specific examples of ether solvents include diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether.

[0196] Specific examples of ketone solvents include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, and dicyclohexyl ketone.

[0197] The (C) solvent preferably includes an aprotic solvent having a relative dielectric constant in the range of 5 to 20, more preferably includes an aprotic solvent having a relative dielectric constant in the range of 6 to 19, and further preferably includes an aprotic solvent having a relative dielectric constant in the range of 7 to 19.

[0198] When the solvent (C) contains an aprotic solvent having a relative dielectric constant in the range of 5 to 20, the storage stability of the positive photosensitive resin composition as a solution is improved.

[0199] Examples of aprotic solvents having a dielectric constant in the range of 5 to 20 include tetrahydrofuran (dielectric constant 7.6), propylene glycol monomethyl ether acetate (dielectric constant 8.3), methyl isobutyl ketone (dielectric constant 13.1), cyclopentanone (dielectric constant 14.5), cyclohexanone (dielectric constant 18.3), and methyl ethyl ketone (dielectric constant 18.5).

[0200] The solvent (C) is preferably an aprotic solvent having 3 to 12 carbon atoms, and more preferably an aprotic solvent having 4 to 10 carbon atoms. The aprotic solvent having 3 to 12 carbon atoms has excellent solubility for the component (a) used in the positive photosensitive resin composition of the present invention. Therefore, by using an aprotic solvent having 3 to 12 carbon atoms in the photosensitive resin composition of the present invention, the solids concentration of the photosensitive resin composition can be increased, and by applying a composition containing such a solvent, it becomes easy to obtain a thick film of the photosensitive resin composition having a thickness of, for example, 1 μm or more.

[0201] In the present invention, the content of the (C) solvent is preferably 100 parts by mass or more relative to 100 parts by mass of the resin component in order to enhance the stability of the solution, while it is preferably 1,500 parts by mass or less in order to form a thick film of the photosensitive resin composition, specifically a film with a thickness of 1 μm or more.

[0202] <Other Components> The photosensitive resin composition of the present invention may contain a dissolution promoter, a sensitizer, a silane coupling agent, a surfactant, etc., within a range that does not impair the object of the present invention or for the purpose of imparting additional functions.

[0203] <Cured Product> The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. That is, curing refers to conversion of a polybenzoxazole precursor into polybenzoxazole.

[0204] As for the curing conditions, a temperature of 150°C to 320°C is applied to promote the thermal crosslinking reaction, improving heat resistance and chemical resistance. This heat treatment can be carried out by selecting a temperature and increasing the temperature stepwise, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but 170°C or higher is more preferable in order to promote sufficient curing. The upper limit of the curing conditions is preferably 280°C or lower.

[0205] <Method for producing a patterned cured film> The method for producing a cured film on a substrate of the present invention includes the steps of applying the photosensitive resin composition of the present invention containing a solvent onto a substrate and drying to form a dried photosensitive resin composition film, exposing the dried photosensitive resin composition film to light to form a latent image in the film, developing the exposed photosensitive resin composition film with an aqueous alkaline solution, and curing the developed photosensitive resin composition film.

[0206] The patterned cured product obtained in this manner is a cured product mainly composed of polybenzoxazole, and therefore has excellent heat resistance, electrical insulation properties, and mechanical properties.

[0207] The method for producing a cured product of the present invention includes a step of applying the photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin film.

[0208] The substrate on which the cured film is formed is not particularly limited, but is preferably selected from the group consisting of glass, silicon wafer, ceramic deposition substrate, metal-plated substrate, sapphire, and gallium arsenide. Furthermore, electrical parts or elements such as electrical wiring, electrodes, semiconductor elements, and pixels made of light-emitting materials may be formed on these substrates.

[0209] The photosensitive composition of the present invention can be applied to a substrate by any known method, including, for example, a full-surface coating apparatus such as spin coating, dip coating, curtain flow coating, spray coating, or slit coating, or a printing apparatus such as screen printing, roll coating, microgravure coating, or inkjet printing.

[0210] After coating, a drying step is carried out to remove the solvent, forming a film of dried photosensitive resin composition. Drying is carried out using a vacuum drying device or a heating device such as a hot plate or oven. When using a heating device, drying is preferably carried out at a temperature range of 50°C to 150°C for 30 seconds to 30 minutes. The film thickness of the dried photosensitive resin composition is preferably 0.1 mm to 100 μm.

[0211] The method for producing a cured product of the present invention includes a step of exposing the dried film of the photosensitive resin composition to light.

[0212] In the exposure step, the film-form photosensitive resin composition is exposed through a mask having a desired pattern to form a latent image. The wavelength of the exposure light to be irradiated is not particularly limited, and examples include light having a wavelength of 300 to 450 nm, such as g-line (436 nm), i-line (365 nm), and h-line (405 nm). Of these, light having a wavelength of 365 nm is preferred. Examples of light sources used in the exposure step include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, and metal halide lamps. Furthermore, the wavelength of the irradiated light may be adjusted, if necessary, through a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a bandpass filter.

[0213] After exposure, post-exposure baking may be performed as necessary. By performing post-exposure baking, effects such as improved resolution after development or an increased tolerance for development conditions can be expected. For post-exposure baking, an oven, a hot plate, infrared radiation, a flash annealing device, a laser annealing device, or the like can be used. The post-exposure baking temperature is preferably 50 to 170°C, more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to 1 hour, more preferably 30 seconds to 30 minutes.

[0214] The method for producing a cured product of the present invention includes a step of developing the exposed portion of the exposed photosensitive resin composition film by dissolving or removing it with an alkaline aqueous solution.

[0215] To form a pattern of the photosensitive resin composition, after exposure, the exposed area is removed using a developer. The developer used for development is typically an alkaline aqueous solution in which an alkaline compound is dissolved. Examples of alkaline compounds include tetramethylammonium hydroxide, potassium hydroxide, and sodium carbonate. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added, either alone or in combination, to these alkaline aqueous solutions.

[0216] After development, it is preferable to perform a rinse treatment with an organic solvent or water. When an organic solvent is used, in addition to the above-mentioned developer, examples of the organic solvent include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. When water is used, a hydrophilic organic solvent such as an alcohol such as ethanol or isopropyl alcohol, or an ester such as ethyl lactate or propylene glycol monomethyl ether acetate may be added to the water for rinsing treatment.

[0217] Next, the developed film of the photosensitive resin composition is cured.

[0218] After development, a temperature of 150°C to 320°C is applied to convert the polybenzoxazole precursor to polybenzoxazole, and if a crosslinking agent is used, a thermal crosslinking reaction is promoted, improving heat resistance and chemical resistance. This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but more preferably 180°C or higher to promote sufficient curing. The upper limit of the curing conditions is preferably 280°C or lower.

[0219] A cured product obtained by curing the photosensitive resin composition of the present invention can be used for electronic components. Examples of electronic components include active components having semiconductors, such as transistors, diodes, integrated circuits (ICs), and memories, as well as passive components, such as resistors, capacitors, inductors, and antenna elements. Electronic components using semiconductors are also referred to as semiconductor devices. <Semiconductor Device> The semiconductor device of the present invention includes the cured product of the present invention. The term "semiconductor device" as used herein refers to any device that can function by utilizing the characteristics of semiconductor elements. Semiconductor devices include electro-optical devices in which semiconductor elements are connected to a substrate, semiconductor circuit boards, stacks of multiple semiconductor elements, and electronic devices containing these. Semiconductor devices also include electronic components such as interposers for connecting semiconductor elements to a substrate. Specifically, the cured product obtained by curing the photosensitive resin composition of the present invention has excellent electrical insulation, mechanical strength, adhesion, and heat resistance. Therefore, it is preferable for these materials to be used in semiconductor devices in which they are used as surface protection films, such as passivation films and buffer coat films, interlayer insulating films between rewirings formed on the surface of semiconductor elements, insulating films between elements when multiple semiconductor elements are bonded, or insulating films between wiring layers in multilayer wiring boards for high-density packaging or interposers.

[0220] More preferably, the photosensitive resin composition of the present invention is cured and disposed as a semiconductor surface protective film or an interlayer insulating film between rewirings in a semiconductor device. By disposing a cured film of the photosensitive composition as a semiconductor surface protective film or an interlayer insulating film between rewirings, a highly reliable semiconductor device can be obtained.

[0221] More preferably, the semiconductor device has the rewiring and the interlayer insulating film repeatedly arranged in 2 to 10 layers. By repeatedly arranging the rewiring and the interlayer insulating film in 2 to 10 layers, the semiconductor device can be miniaturized.

[0222] Specific examples of semiconductor devices in which the rewiring and the interlayer insulating film are repeatedly arranged in 2 to 10 layers include fan-out wafer level packages and fan-out panel level packages.

[0223] <Display Device> The display device of the present invention has the cured product of the present invention. Specifically, the display device of the present invention is a display device including a first electrode formed on a substrate, an insulating layer formed so as to define pixels provided on the first electrode, and a second electrode provided opposite the first electrode, and the insulating layer is preferably the cured product of the present invention. The insulating layer can be formed by applying and drying the photosensitive resin composition of the present invention to a substrate on which a first electrode has been formed, or by laminating a sheet-like photosensitive resin composition, and then going through the steps of exposure, development, and curing to form a pattern of the insulating layer produced from the cured product of the present invention.

[0224] Another embodiment of the display device of the present invention is a display element comprising a thin film transistor (TFT) formed on a substrate and a planarizing film that covers irregularities on the substrate on which the TFT is formed, wherein the planarizing film is the cured product of the present invention.

[0225] Specifically, the display device preferably has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, with either or both of the planarization layer and the insulating layer being the cured product of the present invention. Taking an active matrix display device as an example, a display device may have a TFT and wiring located on the sides of the TFT and connected to the TFT on a substrate such as glass or a resin film, a planarization layer disposed thereon to cover the irregularities, and a display device further disposed on the planarization layer. The display device and the wiring are connected via contact holes formed in the planarization layer. The cured product obtained by curing the photosensitive resin composition of the present invention has excellent planarization properties and pattern dimensional stability, and is therefore preferably provided as a planarization layer in a display device. In particular, flexible display devices have become mainstream in recent years, and the display device may have a substrate having the driving circuit described above made of a resin film.

[0226] Furthermore, with regard to μLEDs, which have been developed in recent years, the cured product of the present invention can be preferably applied to a structure in which 2 to 10 layers of rewiring and interlayer insulating films are repeatedly arranged, which is given as a specific example of a semiconductor device, in addition to the insulating layer and planarizing film.

[0227] The present invention will be explained in more detail below by way of examples, but the present invention should not be construed as being limited to these specific examples. In addition, the names of the compounds used, for which abbreviations are used, are shown below.

[0228] (Diamine compounds) BAP: 2,2-bis(3-amino-3-hydroxyphenyl)propane 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (Acid dianhydride, dicarboxylic acid derivative) 6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride ODPA: 4,4'-oxydiphthalic anhydride TDA-100: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione 6FDC: 4,4'-(hexafluoroisopropylidene)bis(benzoyl chloride) DEDC: 4,4'-oxybis(benzoyl chloride) ADC: adipic acid dichloride (End-capping agent) PAPAC: 4-ethynylaniline EBA: 4-ethynylbenzoic acid chloride (photoacid generator) PAG-103: "Irgacure" (registered trademark) PAG-103 (benzeneacetonitrile, 2-methyl-α-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene, manufactured by BASF Japan Ltd.) NQD-1: naphthoquinone diazide sulfonic acid ester of 4,4'-(1-(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl)diphenol (compound synthesized in Synthesis Example 47).

[0229] (Others) Lutidine: 2,6-lutidine CP: Cyclopentanone NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone MPA: 3-methoxy-N,N-dimethylpropanamide IPVE: Isopropyl vinyl ether BOC: Di-tert-butyl dicarbonate (1) Protection rate of hydroxyl group The protection rate is 400 MHz, １ Measurement was performed using a H-NMR (nuclear magnetic resonance) spectrometer (AL-400 manufactured by JEOL Ltd.). Specifically, measurements were performed in a deuterated dimethyl sulfoxide solution with 16 cumulative measurements. The integral value of the protons of the phenolic hydroxyl groups observed in the vicinity of 9 ppm to 11 ppm in the resin before protection was defined as M, and the integral value of the protons of the phenolic hydroxyl groups observed in the vicinity of 9 ppm to 11 ppm in the resin after protection was defined as N. The value calculated using the following formula was rounded to one decimal place to obtain the protection rate.

[0230] Protection rate (%) = (M - N) / M x 100 (2) Solids concentration The solids concentration of the resin solution was determined by the following method. 1.5 g of the solution was weighed into an aluminum cup and heated at 180 ° C for 30 minutes using a hot plate to evaporate the liquid. The weight of the solids remaining in the aluminum cup after heating was weighed, and the ratio to the weight before heating was calculated, and the value was rounded to one decimal place to obtain the solids concentration.

[0231] (3) Sensitivity A sample photosensitive resin composition was applied onto an 8-inch silicon wafer by spin coating using an ACT-8 coater / developer (manufactured by Tokyo Electron Limited), and heated at 100°C for 2 minutes to produce a pre-baked film of the photosensitive resin composition with a film thickness of 4.0 μm. The film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (manufactured by SCREEN Holdings Co., Ltd.) under a refractive index of 1.629. Thereafter, using an i-line stepper NSR-2005i9C (manufactured by Nikon Corporation), the film was exposed to light at an exposure dose of 5 to 300 mJ / cm through a mask having a 20 μm contact hole pattern. ２ in the range of 5 mJ / cm ２ After the exposure, the film was developed for 10 to 80 seconds using the ACT-8 developing device with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter, referred to as TMAH) (manufactured by Tama Chemicals Co., Ltd.) as a developer, and then rinsed with distilled water and spun off to dry, thereby obtaining a relief pattern.

[0232] The relief pattern was observed at a magnification of 20 times using an FDP microscope MX61 (manufactured by Olympus Corporation), and the opening diameter of the contact hole was measured. The minimum exposure dose at which the opening diameter of the contact hole reached 20 μm was determined, and this was taken as the sensitivity. The results were evaluated as follows, and the sensitivity was 500 mJ / cm ２ A, B and C, which are less than 100%, were rated as passing. A is the best.

[0233] A: Sensitivity is 150 mJ / cm ２ B: Sensitivity is less than 150 mJ / cm ２ More than 300mJ / cm ２ C: Sensitivity is less than 300 mJ / cm２ More than 500mJ / cm ２ D: Sensitivity is less than 500 mJ / cm ２ (4) Taper Angle A relief pattern was prepared in the same manner as in (3) and heat-treated in a clean oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less). The cross section of the 20 μm contact hole pattern at the minimum exposure dose determined in (3) was then observed with a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation), and the angle of the portion shown in FIG. 1 was measured. The value was rounded to the nearest whole number to obtain the taper angle. A taper angle of 50° or greater was deemed acceptable. (5) Crack Resistance A relief pattern was prepared in the same manner as in (4), except that the coating rotation speed by spin coating was adjusted to prepare films with film thicknesses of 0.5 μm, 1 μm, and then 11 μm, varying in 1 μm increments, after heat treatment at 250°C for 30 minutes. At this time, the presence or absence of cracks at the pattern edges of the contact holes at the minimum exposure dose at which the opening diameter of the contact holes reached 20 μm was observed at 20x magnification using an FDP microscope MX61 (manufactured by Olympus Corporation), and the maximum film thickness at which no cracks occurred was used as an index of crack resistance. At this time, if no cracks occurred even at a film thickness of 11 μm, it was rated as >10 μm. A maximum film thickness of 1 μm or more was rated as passing for crack resistance. (6) Amount of Developed Film Loss A sample photosensitive resin composition was applied to an 8-inch silicon wafer by spin coating using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Limited), and heated at 100°C for 2 minutes to produce a pre-baked film of the photosensitive resin composition with a film thickness of 4.0 μm. This film was developed for 60 seconds without exposure using the ACT-8 developing device with a 2.38% by mass aqueous TMAH solution (manufactured by Tama Chemicals Co., Ltd.), then rinsed with distilled water and spun dry, and the film thickness T1 (μm) after development was measured. The film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (manufactured by SCREEN Holdings Co., Ltd.) under the condition of a refractive index of 1.629.

[0234] The amount of film loss due to development (ΔT1) was calculated by the following formula: ΔT1=4−T1 The results for ΔT1 were judged as follows, and A and B, which are ΔT1 of less than 0.8 μm, were rated as passing. A is the best.

[0235] A: ΔT1 is less than 0.3 μm B: ΔT1 is 0.3 μm or more and less than 0.8 μm C: ΔT1 is 0.8 μm or more (7) Chemical Resistance A sample photosensitive resin composition was applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Limited), heated at 100 ° C for 2 minutes, and then, without exposing or developing, the film was heat-treated at 250 ° C for 30 minutes under a nitrogen gas flow (oxygen concentration 20 ppm or less) using a clean oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.). At this time, the coating rotation speed by the spin coating method was adjusted so that the film thickness after 30 minutes of heat treatment at 250 ° C was 4.0 μm. The heat-treated film was immersed in acetone and treated at 23 ° C for 10 minutes, and the film thickness T2 (μm) after treatment was measured. The film thickness was measured using an optical interference film thickness measuring device Lambda Ace STM-602 (manufactured by SCREEN Holdings Co., Ltd.) under the condition of a refractive index of 1.629.

[0236] The amount of film loss (ΔT2) in the acetone treatment was calculated using the following formula: ΔT2=4-T2. The chemical resistance was evaluated as follows, with A+, A, B+, and B being grades that indicated a ΔT2 of less than 1.0 μm, and were considered to be acceptable. A+ is the most excellent.

[0237] A+: ΔT2 is less than 0.3 μm A: ΔT2 is 0.3 μm or more and less than 0.5 μm B+: ΔT2 is 0.5 μm or more and less than 0.8 μm B: ΔT2 is 0.8 μm or more and less than 1 μm C: ΔT2 is 1 μm or more Synthesis Example 1 Synthesis of Polyimide Precursor (PAA-01) In a dry nitrogen stream, 44.4 g (100 mmol) of 6FDA and 9.21 g (200 mmol) of ethanol were dissolved in 180 g of NMP in a three-necked flask, and then 20.4 g (202 mol) of triethylamine was added and stirred at room temperature for 24 hours. 76.7 g (200 mmol) of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate was dissolved in this solution, and then 36.6 g (100 mmol) of 6FAP was added together with 30 g of NMP, followed by stirring at room temperature for 8 hours. After completion of the reaction, the above solution was poured into a 2 liter solution prepared by mixing pure water and ethanol in a mass ratio of 3:1, causing the precipitation of a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain a polyimide precursor (PAA-01). The results are shown in Table 1.

[0238] Synthesis Example 2 Synthesis of Polyimide (PI-01) Under a dry nitrogen stream, 33.0 g (90 mmol) of 6FAP was dissolved in 180 g of NMP in a three-neck flask, followed by the addition of 44.4 g (100 mmol) of 6FDA along with 40 g of NMP. After stirring at 60°C for 2 hours, 1.86 g (20 mmol) of aniline was added along with 40 g of NMP, and stirring was continued for another 2 hours at 60°C. The solution was heated to 200°C and further stirred for 6 hours. After completion of the reaction, the solution was poured into 2 liters of pure water to precipitate a white precipitate. The precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain polyimide (PI-01). The results are shown in Table 1.

[0239] Synthesis Examples 3, 4, 8 to 12 Synthesis of Polyimides (PI-02 to PI-08) Polyimides were synthesized in the same manner as in Synthesis Example 2, except that the types and amounts of the acid dianhydrides, diamines, and monoamines were changed to those shown in Table 1. The results are shown in Table 1.

[0240] Synthesis Example 5 Synthesis of Polybenzoxazole Precursor (PBO-01) Under a dry nitrogen stream, 36.6 g (100 mmol) of 6FAP was dissolved in 150 g of MPA in a three-neck flask. The solution was then cooled to -15°C. After confirming that the solution temperature had reached -15°C, 36.5 g (85 mmol) of 6FDC was added along with 30 g of MPA. After stirring at -10°C for 30 minutes, the solution was heated to 20°C and stirred for an additional 2 hours. The solution was again cooled to -15°C. After confirming that the solution temperature had reached -15°C, 3.14 g (30 mmol) of methacryl chloride was added along with 10 g of MPA. After completion of the dropwise addition, stirring was continued for 2 hours at 20°C. After completion of the reaction, the above solution was poured into 2 liters of pure water to precipitate a white precipitate. The precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50° C. for 72 hours to obtain a polybenzoxazole precursor (PBO-01). The results are shown in Table 1.

[0241] Synthesis Examples 6, 7, 13 to 18 Synthesis of polybenzoxazole precursors (PBO-02 to PBO-09) Synthesis was performed in the same manner as in Synthesis Example 5, except that the types and amounts of the dicarboxylic acid derivative, diamine, and monocarboxylic acid derivative were changed to those shown in Table 1. The results are shown in Table 1.

[0242]

[0243] Synthesis Example 19 Synthesis of Resin (PAA-A1) in which Hydroxyl Groups are Protected 17.3 g of PAA-01 as a base polymer and 34.6 g of CP as a solvent were weighed and dissolved in a three-necked flask under a dry nitrogen stream. 5.91 g of IPVE was added as a protecting agent, and the mixture was stirred at 0°C for 1 hour. Next, 0.483 g of trifluoroacetic acid was added as a catalyst, and the mixture was stirred at 0°C for 3 hours. After stirring was completed, the acid catalyst was neutralized with a saturated aqueous sodium bicarbonate solution, and the water bath was removed. The organic layer was further washed twice with water. Thereafter, low-boiling point residues were removed using a rotary evaporator in order to remove unreacted isopropyl vinyl ether. Thereafter, the solids concentration of the solution was measured, and CP was added so that the solids content was 40.0% by mass, and a 40.0% by mass solids solution of resin (PAA-A1) in which hydroxyl groups were protected with 1-isopropoxyethyl groups, which are acid-decomposable groups, was obtained. The ratio of phenolic hydroxyl groups protected with acid-labile groups (protection rate) was 98 mol %. The results are shown in Table 2.

[0244] Synthesis Examples 20 to 26 and 32 to 38: Synthesis of Resins with Protected Hydroxyl Groups (PI-A1 to PI-A10, PBO-A1 to PBO-A4) The resins were synthesized in the same manner as in Synthesis Example 8, except that the type and amount of base polymer, amount of solvent, amount of protecting agent, and amount of catalyst were changed to those shown in Table 2. The results are shown in Table 2.

[0245] Synthesis Example 27: Synthesis of Resin (PI-B1) with Protected Hydroxyl Groups

[0063] 10.3 g of PI-03 as a base polymer was placed in a three-neck flask under a dry nitrogen stream and dissolved in 50 g of MPA. 1.31 g of BOC and 0.0367 g of 4-dimethylaminopyridine were then added, and the mixture was allowed to react at 20°C for 1 hour.

[0246] After the reaction was completed, the solution was poured into 500 mL of pure water to precipitate a white precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain polyimide resin (PI-B1). The proportion of phenolic hydroxyl groups protected with acid-dissociable groups (protection rate) was 15 mol%. The results are shown in Table 2.

[0247] Synthesis Examples 28 to 31 and 39 to 45: Synthesis of Resins with Protected Hydroxyl Groups (PI-B2 to PI-B3, PBO-B1 to PBO-B7) These resins were synthesized in the same manner as in Synthesis Example 16, except that the type and amount of base polymer, the amount of protecting agent, and the amount of catalyst were changed to those shown in Table 2. The results are shown in Table 2.

[0248]

[0249] Synthesis Example 47 Synthesis of Photoacid Generator (NQD-1) Under a dry nitrogen stream, 21.2 g (50 mmol) of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) and 36.3 g (135 mmol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to cool to room temperature. A solution of 15.2 g of triethylamine dissolved in 50.0 g of 1,4-dioxane was added dropwise to the solution so that the temperature in the system was 35°C or less. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The resulting precipitate was then filtered and collected. The precipitate was dried in a vacuum dryer to obtain the quinone diazide compound NQD-1 represented by formula (18).

[0250]

[0251] In formula (18), * represents the bonding site with the oxygen atom. The esterification rate was 90 mol %.

[0252] Example 1 Under yellow light, 2,425 mg of PAA-A1 as the (A-1) resin, 30 mg of PBO-B1 as the (A-2) resin, 150 mg of PAG-103 as the (B) photoacid generator, 615 mg of CP and 887 mg of GBL as the solvent, and 5 mg of lutidine as an additive were mixed and stirred to prepare a photosensitive resin composition. The types and mass ratios of the (A-1) resin and the (A-2) resin, the type and amount of the (B) photoacid generator, the type and amount of the solvent, and the type and amount of the additive of this photosensitive resin composition are shown in Table 3-1.

[0253] The prepared photosensitive resin compositions were evaluated for (3) sensitivity, (4) taper angle, (5) crack resistance, (6) film loss upon development, and (7) chemical resistance. The results are shown in Table 3-2.

[0254]

[0255]

[0256] Examples 2 to 18 and Comparative Examples 1 and 2 Photosensitive resin compositions were prepared and evaluated in the same manner as in Example 1, except that the types and mass ratios of the (A-1) resin and the (A-2) resin, the type and amount of the (B) photoacid generator, the type and amount of the solvent, and the type and amount of the additive were changed as shown in Table 3-1. The results are shown in Table 3-2.

[0257] Examples 19 to 37 Photosensitive resin compositions were prepared and evaluated in the same manner as in Example 1, except that the types and mass ratios of the (A-1) resin and the (A-2) resin, the type and amount of the (B) photoacid generator, the type and amount of the solvent, and the type and amount of the additive were changed as shown in Table 4-1. The results are shown in Table 4-2.

[0258]

[0259]

[0260] 1 Silicon wafer 2 Photosensitive resin composition 3 Taper angle of pattern

Claims

1. A composition comprising at least one resin selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, polybenzothiazole, and precursors thereof, having a structure represented by formula (1) (hereinafter referred to as (A-1) resin), at least one resin selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, polybenzothiazole, and precursors thereof, having a structure represented by formula (1), which is different from the (A-1) resin (hereinafter referred to as (A-2) resin), and (B) a photoacid generator, wherein all of the R contained in the (A-1) resin ２ R in the resin (A-1) when ２ is the proportion m of alkyl groups having 1 to 6 carbon atoms or monovalent acid-dissociable groups having 3 to 50 carbon atoms. １ (mol %), all of the R contained in the (A-2) resin ２ R in the (A-2) resin when ２ is the proportion m of alkyl groups having 1 to 6 carbon atoms or monovalent acid-dissociable groups having 3 to 50 carbon atoms. ２ (mol%) is 0<m １ ≦100 and / or 0<m ２ A photosensitive resin composition satisfying the following condition: (In formula (1), R １ represents a trivalent to octavalent organic group having 3 to 50 carbon atoms, R ２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a monovalent acid-dissociable group having 3 to 50 carbon atoms; A represents an oxygen atom or a sulfur atom; n １ is an integer of 1 to 4, * represents a binding site, a １ and a ２ each independently represents an integer of 1 or 2.

2. The photosensitive resin composition according to claim 1, wherein the (A-1) resin is at least one resin selected from the group consisting of polyimide, polyamideimide, and precursors thereof, and the (A-2) resin is at least one resin selected from the group consisting of polybenzoxazole, polybenzothiazole, and precursors thereof.

3. At least one of the polymer terminals in the (A-1) resin is a structure represented by formula (2), formula (3), formula (4), or formula (5), and at least one of the polymer terminals in the (A-2) resin is a structure represented by formula (5), and R ３ , R ５ , R ６ and R ７ The photosensitive resin composition according to claim 2 , wherein at least one of the above has a thermal crosslinkable group. (In formulas (2) to (4), R ３ and R ５ represents a residue of a dicarboxylic acid anhydride having 1 to 12 carbon atoms, and R ４ represents a monovalent organic group having 1 to 12 carbon atoms, and R ６ represents a residue of a monoamine having 1 to 12 carbon atoms, and * represents a binding site. ７ represents a residue of a monocarboxylic acid having 1 to 12 carbon atoms, and * represents a bonding site.) 4. R in the formula (5) ７ The photosensitive resin composition according to claim 3 , wherein the compound (I) has a thermal crosslinkable group.

5. R in the formula (1) ２ The photosensitive resin composition according to any one of claims 1 to 4, wherein is a hydrogen atom or a monovalent acid-dissociable group having 3 to 50 carbon atoms.

6. Said m １ (mol%) is 0<m １ ≦100 and ２ (mol%) is 0≦m ２ The photosensitive resin composition according to any one of claims 1 to 4, wherein the photosensitive resin composition satisfies the following condition: ≦100.

7. The photosensitive resin composition according to any one of claims 1 to 4, wherein the mass ratio of the (A-1) resin to the (A-2) resin is 5 / 95 to 95 / 5.

8. Said m １ (mol%) is 20≦m １ The photosensitive resin composition according to any one of claims 1 to 4, which satisfies ≦90.

9. Said m ２ (mol%) is 0≦m ２ The photosensitive resin composition according to any one of claims 1 to 4, wherein the composition satisfies <50.

10. The photosensitive resin composition according to any one of claims 1 to 4, wherein the resin (A-1) has at least one structural unit selected from the formulas (6) to (8). (In formula (6), R ８ and R ９ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. １ represents a divalent organic group having 3 to 50 carbon atoms, and X １ represents a tetravalent organic group having 3 to 50 carbon atoms, and Y １ , X １ At least one of the above represents a structure represented by formula (1). (In formula (7), Y ２ represents a divalent organic group having 3 to 50 carbon atoms, and X ２ represents a tetravalent organic group having 3 to 50 carbon atoms, and Y ２ and X ２ At least one of the above represents a structure represented by formula (1). (In formula (8), Y ３ represents a divalent organic group having 3 to 50 carbon atoms, and X ３ represents a trivalent organic group having 3 to 50 carbon atoms, and Y ３ and X ３ At least one of the above represents a structure represented by formula (1).

11. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (A-2) resin has a structural unit represented by formula (9). (In formula (9), Y ４ represents a divalent organic group having 3 to 50 carbon atoms and represented by formula (1), and X ４ represents a divalent organic group having 3 to 50 carbon atoms.

12. The photosensitive resin composition according to claim 10, wherein the resin (A-1) has a structural unit represented by formula (7).

13. The (A-1) resin has at least one structural unit selected from formulas (10) to (12), the (A-2) resin has a structural unit represented by formula (13), and AR included in formulas (10) to (12) ２ The total number of groups is M1, and AR from the structures of formulas (10) to (12). ２ The molecular weight of the remaining structural portion excluding the group is N1, and the AR included in formula (13) is ２ The total number of groups is M2, and AR from the structure of formula (13) ２ When the molecular weight of the remaining structural portion excluding the group is N2, if M1 / N1≧M2 / N2, m １ ≧m ２ If M1 / N1<M2 / N2, then m １ <m ２ The photosensitive resin composition according to any one of claims 1 to 4, which satisfies the above. (In formulas (10) to (13), R １ , R ２ , R ８ , R ９ , A, n １ and X １ ~X ４ has the same meaning as the same symbol in the formula (1) and formulas (6) to (9).

14. The photosensitive resin composition according to any one of claims 1 to 4, wherein at least one of the resin (A-1) and the resin (A-2) has a structure represented by formula (14). (In formula (14), R ２ , A, a １ and a ２ has the same meaning as the same symbol in the formula (1). L is a direct bond, —SO ２ -, -C(CH ３ ) ２ -, 9H-fluorene-9,9-diyl group. ２ and n ３ are each independently an integer of 0 to 2, provided that 1≦(n ２ +n ３ )≦4. * indicates a binding site.

15. R in formula (1) in the resin (A-1) ２ The photosensitive resin composition according to any one of claims 1 to 4, wherein at least one of the following is a group represented by formula (15) or formula (16): (In formula (15) and formula (16), R １０ and R １１ R each independently represents an alkyl group having 1 to 6 carbon atoms. １２ each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms; r represents an integer of 0 to 2, and s represents an integer of 0 to 2. * represents a bonding site.

16. R in formula (1) in the resin (A-2) ２ The photosensitive resin composition according to any one of claims 1 to 4, wherein at least one of the following is a group represented by formula (15) or formula (16):

17. A cured product of the photosensitive resin composition according to any one of claims 1 to 4.

18. A semiconductor device comprising the cured product according to claim 17.

19. A display device comprising the cured product according to claim 17.

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