Resin, resin composition and cured product thereof, and semiconductor device, display device, secondary battery, and capacitor using cured product

Abstract

Provided is a resin which has an amide bond in a structural unit of the polymer main chain, wherein a part or all of the amide bond is protected by an acid-dissociable group. This resin is capable of forming a multilayer laminate resin film, and is suited to a processing process at a lower temperature.

Description

Resins, resin compositions and their cured products, and semiconductor devices, display devices, secondary batteries and capacitors using the cured products.

[0001] The present invention relates to resins, resin compositions and their cured products, and semiconductor devices, display devices, secondary batteries, and capacitors using the cured products.

[0002] Polyimides, polyamideimides, polyamides, polybenzoxazoles, and polybenzothiazoles are used as protective films for semiconductor chips, interlayer insulating films for rewiring of semiconductor packages, insulating films for multilayer wiring substrates, and insulating films and planarization films for organic EL displays and liquid crystal displays, due to their heat resistance, electrical properties, and mechanical properties (high strength, high elongation). In recent years, their application to lithium-ion secondary batteries and electric double-layer capacitors is also being considered as high-strength binders to suppress the expansion and contraction of electrode active materials during charging and discharging.

[0003] Generally, polyimides and polybenzoxazoles are dissolved in a solvent in their precursor state, coated onto a suitable substrate, and then subjected to heat treatment at 200°C or higher to remove the solvent and dehydrate the ring, forming imide and oxazole rings, respectively, to obtain a resin insoluble in the solvent (see, for example, Patent Documents 1-2).

[0004] On the other hand, polyamides and polyamide-imides that do not use precursors are generally dissolved in a solvent, coated and processed, and then subjected to heat treatment for solvent removal (see, for example, Patent Documents 3-4).

[0005] For these polyamides and polyamide-imides, amide-based solvents such as N-methyl-2-pyrrolidone have been preferred as solvents because they have a high interaction with imide and amide groups, making it easy for the resin to solvate.

[0006] In recent years, with the lowering of processing temperatures, research has been underway to replace amide solvents with ester-based, ketone-based, and alcohol-based solvents that offer high solvent removal during heat treatment. Methods for dissolving polyamides and polyamide-imides in these solvents include introducing a flexible backbone into the polymer's main chain and substituting hydrogen atoms bonded to nitrogen in amide groups with organic groups (see, for example, Patent Documents 5 and 6).

[0007] Japanese Patent Publication No. 2021-138952, Japanese Patent Publication No. Hei 1-6947, Japanese Patent Publication No. Hei 5-310916, International Publication No. 2017 / 099172, Japanese Patent Publication No. 2007-138000, International Publication No. 2001 / 000733

[0008] However, when attempting to obtain a multilayer laminated resin film using the resins described in Patent Documents 5-6, there was a problem in that the lower resin composition layer, which had been desolvented after heat treatment, would dissolve during the formation of the upper resin composition layer. The present invention aims to provide a resin that can form a multilayer laminated resin film and can also withstand low temperatures in the processing process.

[0009] To solve the above problems, the present invention has the following configuration: <1> A resin having amide bonds in the structural units of the polymer main chain, wherein some or all of the amide bonds are protected by an acid-dissociable group (hereinafter referred to as "(A) resin"). <2> The resin according to <1>, wherein the (A) resin is selected from the group consisting of polyamides, polyamide-imides, polyimide precursors and copolymers thereof. <3> The resin according to <1> or <2>, wherein the acid-dissociable group has an oxycarbonyl group. <4> The resin according to any one of <1> to <3>, wherein the (A) resin has one or more structural units selected from formulas (1) to (5).

[0010]

[0011] (In formula (1), R １ and R ２ Each of these independently represents a hydrogen atom or an acid-dissociable group having 1 to 50 carbon atoms, R １ and R ２ At least one of them represents an acid-dissociable group having 1 to 50 carbon atoms. １ This represents a divalent organic group with 2 to 50 carbon atoms, X １ (This represents a divalent organic group with 1 to 50 carbon atoms.)

[0012]

[0013] (In formula (2), R ３ This represents an acid-dissociable group with 1 to 50 carbon atoms, Y ２ This represents a divalent organic group with 2 to 50 carbon atoms, X２ represents a trivalent organic group having 3 to 50 carbon atoms.)

[0014]

[0015] (In formula (3), R ４ and R ５ each independently represent a hydrogen atom or an acid dissociable group having 1 to 50 carbon atoms, and at least one of R ４ and R ５ represents an acid dissociable group having 1 to 50 carbon atoms. R ６ and R ７ each independently represent a hydrogen atom or an acid dissociable group having 1 to 50 carbon atoms. Y ３ represents a tetravalent organic group having 4 to 50 carbon atoms, and X <了 ３ represents a divalent organic group having 1 to 50 carbon atoms.)

[0016]

[0017] (In formula (4), R ８ and R ９ each independently represent a hydrogen atom or an acid dissociable group having 1 to 50 carbon atoms, and at least one of R ８ and R ９ represents an acid dissociable group having 1 to 50 carbon atoms. R １０ and R １１ each independently represent a monovalent organic group having 1 to 10 carbon atoms. Y ４ represents a divalent organic group having 2 to 50 carbon atoms, and X ４ represents a tetravalent organic group having 4 to 50 carbon atoms.)

[0018]

[0019] (In formula (5), R １２ and R [[ID=SS]] １３ each independently represent a hydrogen atom or an acid dissociable group having 1 to 50 carbon atoms, and at least one of R １２ and R １３ represents an acid dissociable group having 1 to 50 carbon atoms. R １４ and R １５ each independently represent a hydrogen atom or an acid dissociable group having 1 to 50 carbon atoms. R １６ and R １７Each of these independently represents a monovalent organic group having 1 to 10 carbon atoms. ５ represents a tetravalent organic group with 4 to 50 carbon atoms, X ５ X represents a tetravalent organic group having 4 to 50 carbon atoms.) <5> In formulas (1) to (5) above, X １ ~X ５ and Y1 is an organic group that does not contain an amide bond, the resin according to any one of <1> to <4>. <6> The resin according to any one of <1> to <5>, wherein the structural units of (a-1) and (a-2) below account for 60 mol% or more of the total structural units of the (A) resin. (a-1) Structural units of formulas (1) to (5) (a-2) In formulas (1) to (5), R １ ~R ５ , R ８ , R ９ , R １２ , and R １３ A structural unit in which all are hydrogen atoms <7> In the above formula (1), X １ is an organic group having an aromatic ring, -NR １ -CO- group and -NR ２ The aromatic ring is directly bonded to the carbonyl group of the -CO- group, and Y １ is an organic group having an aromatic ring, -NR １ -CO- group and -NR ２ A resin according to any one of <1> to <6>, wherein the aromatic ring is directly bonded to the nitrogen atom of the -CO- group. <8> A resin according to any one of <1> to <7>, wherein when the (A) resin is applied to a substrate in a solution in a solvent and dried on a hot plate at 100°C for 2 minutes, the absorbance A1 per 1 μm of film thickness and the absorbance A2 per 1 μm of film thickness when the film is heat-treated in an oven at 250°C for 1 hour after drying are 0.003 < A1 < 0.3 and A2 ≥ 0.3. <9> A resin composition comprising the (A) resin according to any one of <1> to <8> and a solvent (B). <10> The resin composition according to <9>, wherein the tensile modulus of the film heat-treated at 250°C for 1 hour is 3.5 GPa or more and 20 GPa or less. <11> When the total amount of the (B) solvent is 100% by mass, the Hansen solubility parameter is 22.5 (MPa). １／２A resin composition according to <9> or <10>, wherein the solvent less than 50% by mass of the total solvent. <12> A resin composition according to any one of <9> to <11>, further comprising (C) a thermal acid generator. <13> A resin composition according to any one of <9> to <12>, further comprising (D) a photoacid generator. <14> A cured product of a resin composition according to any one of <9> to <13>. <15> A method for producing (A) resin according to any one of <1> to <8>, comprising the step of reacting a resin having an amide bond in the structural unit of the polymer main chain with a compound represented by formula (11).

[0020]

[0021] (In formula (11), R ２８ and R ２９ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms.) <16> A substrate comprising a multilayer wiring structure, wherein the interlayer insulating film in the multilayer wiring structure is made of the cured product described in <14>. <17> A semiconductor device having the cured product described in <14>. <18> A semiconductor device comprising a substrate comprising a multilayer wiring structure and a semiconductor element bonded to the substrate, wherein the interlayer insulating film in the multilayer wiring structure is made of the cured product described in <14>. <19> The semiconductor device according to <18>, further comprising a printed circuit board, wherein the side of the substrate comprising the multilayer wiring structure that is not bonded to the semiconductor element is directly bonded to the printed circuit board without the use of another organic substrate. <20> A communication device comprising the semiconductor device described in <18>. <21> A communication device comprising the semiconductor device described in <19>. <22> A display device having the cured product described in <14>. <23> A secondary battery having the cured product described in <14>. <24> A capacitor having the cured product described in <14>.

[0022] The resin of the present invention exhibits excellent solubility in ester-based solvents, ketone-based solvents, and alcohol-based solvents that have high solvent-removal properties during heat treatment. Furthermore, by dissociating the acid-dissociable groups bound to the resin, it becomes possible to make the resin insoluble in the solvent in which it was dissolved before dissociation. Therefore, when forming a multilayer structure by repeatedly forming a resin film using the resin of the present invention and dissociating the acid-dissociable groups, the resin of the lower layer, after the dissociation treatment is complete, does not dissolve during the formation of the upper layer.

[0023] This is a cross-sectional view of a semiconductor device according to an embodiment of the present invention. This is a cross-sectional view showing the sputter film formation process in the simultaneous formation of a conductive wiring layer M2 and through-wiring MM1. This is a cross-sectional view showing the resist pattern formation process in the simultaneous formation of a conductive wiring layer M2 and through-wiring MM1. This is a cross-sectional view showing the copper plating process in the simultaneous formation of a conductive wiring layer M2 and through-wiring MM1. This is a cross-sectional view showing the resist stripping process in the simultaneous formation of a conductive wiring layer M2 and through-wiring MM1. This is a cross-sectional view showing the sputter film etching process in the simultaneous formation of a conductive wiring layer M2 and through-wiring MM1. This is a plan view showing the arrangement of bumps M7 of a semiconductor element C1. This is a plan view showing the arrangement of bumps M7 of a semiconductor element C2. This is a cross-sectional view showing the arrangement of mold resin 30. This is a plan view showing the process of forming a conductive wiring layer M1. This is a plan view showing the process of forming an interlayer insulating film L1 (and through-hole LL1). This is a plan view showing the process of forming a conductive wiring layer M2 and through-wiring MM1. This is a plan view showing the process of forming an interlayer insulating film L2 (and through-hole LL2). This is a plan view showing the process of forming the interlayer insulating film L5 (and through-hole LL5). This is a plan view showing the process of forming the electrode pad M6 on LL5.

[0024] The resin according to the embodiment of the present invention is a resin having amide bonds in the structural units of the polymer main chain, wherein some or all of the amide bonds are protected by acid-dissociable groups (hereinafter referred to as "(A) resin"). Furthermore, in the following description, a resin film containing (A) resin is referred to as "(A-1) resin film," and a resin film after the acid-dissociable groups of (A) resin in the (A-1) resin film have been dissociated is referred to as "(A-2) post-dissociation resin film."

[0025] Furthermore, an acid-dissociable group refers to an organic group represented by R when the -NH- of the amide bond in a resin is protected as -NR-, and which has the function of dissociating from its bond with nitrogen to become -NH- upon the action of an acid.

[0026] In this case, an amide bond in which the hydrogen atom of -NH- is replaced by an acid-dissociable group is called an "amide bond protected by an acid-dissociable group," and the dissociation of the acid-dissociable group into -NH- due to the action of an acid is called "deprotection."

[0027] (A) In resin, some or all of its amide bonds are protected by acid-dissociable groups, which weakens the intermolecular hydrogen bonds formed by the -NH- groups in the amide bonds. In addition, the steric hindrance of the acid-dissociable groups themselves improves the solubility of resin (A) in organic solvents. Due to these effects, resin (A) becomes soluble in polar solvents such as ester solvents, ketone solvents, and alcohol solvents.

[0028] Furthermore, after the acid-dissociable groups of resin (A) are dissociated, -NH- amide bonds are formed, reducing its solubility in organic solvents. By utilizing this property, when a resin film (A-1) is formed and the acid-dissociable groups are dissociated to obtain a dissociated resin film (A-2), the elution of the lower layer (A-2) dissociated resin film during the formation of the upper layer (A-1) resin film is reduced, and a multilayer structure of the dissociated resin film (A-2) can be formed. Hereafter, a multilayer structure having one or more layers of the dissociated resin film (A-2) obtained by such an operation will be referred to as a "multilayer structure of resin film (A-2)".

[0029] The multilayer structure of the resin film described above may be a laminate of one or more resin films, or it may be a substrate 10 including a multilayer wiring structure in which resin films and wiring are alternately laminated, as shown in Figure 1. In this case, the layers of resin film (L1 to L4) sandwiched between the wiring layers are called interlayer insulating films.

[0030] The acid used in the dissociation treatment of the acid-dissociable groups described above can be supplied by methods such as applying or spraying an acid-containing solution onto the (A-1) resin film, impregnating the (A-1) resin film with an acidic solution, or exposing the (A-1) resin film to an acidic atmosphere. Alternatively, as will be described later, a thermal acid generator or a photoacid generator may be added to the (A) resin together with the (B) solvent, and the resin composition may be used in which the acid-dissociable groups are dissociated by the acid generated by heat or light.

[0031] <(A) Resin> In resin (A), the amide bond may be included in either the main chain portion or the side chain portion of the polymer's structural unit, but it is preferable that it be included in the main chain portion. Preferred resins (A) include resins selected from the group consisting of polyamides, polyamide-imides, polyimide precursors, and copolymers thereof.

[0032] Of these, it is more preferable that the resin has one or more structural units selected from formulas (1) to (5).

[0033]

[0034] In formula (1), R １ and R ２ Each of these independently represents a hydrogen atom or an acid-dissociable group having 1 to 50 carbon atoms, R １ and R ２ At least one of them represents an acid-dissociable group having 1 to 50 carbon atoms. １ This represents a divalent organic group with 2 to 50 carbon atoms, X １ This represents a divalent organic group with 1 to 50 carbon atoms.

[0035]

[0036] In formula (2), R ３ This represents an acid-dissociable group with 1 to 50 carbon atoms, Y ２ This represents a divalent organic group with 2 to 50 carbon atoms, X ２ This represents a trivalent organic group with 3 to 50 carbon atoms.

[0037]

[0038] In formula (3), R ４ and R ５ Each of these independently represents a hydrogen atom or an acid-dissociable group having 1 to 50 carbon atoms, R ４ and R ５ At least one of them represents an acid-dissociable group having 1 to 50 carbon atoms. ６ and R ７ Each of these independently represents a hydrogen atom or an acid-dissociable group having 1 to 50 carbon atoms. ３ This represents a tetravalent organic group with 4 to 50 carbon atoms, X ３ This represents a divalent organic group with 1 to 50 carbon atoms.

[0039]

[0040] In formula (4), R ８ and R ９ each independently represents a hydrogen atom or an acid dissociable group having 1 to 50 carbon atoms, and at least one of R ８ and R ９ represents an acid dissociable group having 1 to 50 carbon atoms. R １０ and R １１ each independently represents a monovalent organic group having 1 to 10 carbon atoms. Y ４ represents a divalent organic group having 2 to 50 carbon atoms, and X ４ represents a tetravalent organic group having 4 to 50 carbon atoms.

[0041]

[0042] In formula (5), R １２ and R １３ each independently represents a hydrogen atom or an acid dissociable group having 1 to 50 carbon atoms, and at least one of R １２ and R １３ represents an acid dissociable group having 1 to 50 carbon atoms. R １４ and R １５ each independently represents a hydrogen atom or an acid dissociable group having 1 to 50 carbon atoms. R １６ and R １７ each independently represents a monovalent organic group having 1 to 10 carbon atoms. Y ５ represents a tetravalent organic group having 4 to 50 carbon atoms, and X ５ represents a tetravalent organic group having 4 to 50 carbon atoms.

[0043] Formula (1) represents a polyamide structure. Formula (2) represents a polyamideimide structure. Formula (3) represents a polybenzoxazole precursor structure. Formula (4) and the aforementioned formula (5) represent polyimide precursor structures.

[0044] The acid dissociable group in formulas (1) to (5) means that the acid generated by heat or light irradiation forms an amide group in formulas (1) to (5), -NR １ -, -NR ２ -, -NR ３ -, -NR ４ -, -NR ５ -, -NR ８-1. -NR ９ -1. -NR １２ -1. -NR １３ -A functional group that can be converted to -NH- by acting on -, and -OR in formulas (3) and (5) ６ , -OR ７ , -OR １４ , -OR １５ -Refers to a functional group that can be converted to -OH (phenolic hydroxyl group) by acting on -

[0045] -In this case, -NR １ -, -NR ２ -, -NR ３ -, -NR ４ -, -NR ５ -, -NR ８ -, -NR ９ -, -NR １２ -, -NR １３ -The structure of - is the "amide bond protected by an acid dissociable group" mentioned above, and the conversion of these structures to -NH- is the "deprotection" mentioned above.

[0046] -Also, -OR ６ , -OR ７ , -OR １４ , -OR １５ -The structure of - may be referred to as a "hydroxyl group protected by an acid dissociable group". Furthermore, the conversion of these structures to -OH is also referred to as "deprotection".

[0047] -Also, among the -NH- before protection, the ratio converted to -NR １ -, -NR ２ -, -NR ３ -, -NR ４ -, -NR ５ -, -NR ８ -, -NR ９ -, -NR １２ -, -NR １３ -by reaction with a protecting agent, and the ratio of -OH before protection converted to -OR ６ , -OR ７ , -OR １４ , -OR １５ -by reaction with a protecting agent is referred to as the "protection rate".

[0048] Preferred acid-dissociable groups in formulas (1) to (5) include those with structures represented by formulas (6) to (10).

[0049]

[0050] In equations (6) to (10), * represents a connection point.

[0051] In formula (6), R １８ and R １９ Each of these independently represents an alkyl group having 1 to 6 carbon atoms. Preferred specific examples of alkyl groups having 1 to 6 carbon atoms include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, isohexyl, t-butyl, and t-amyl groups. From the viewpoint of reducing resin shrinkage during curing, the alkyl group having 1 to 6 carbon atoms is more preferably a methyl or ethyl group.

[0052] In formula (7), R ２０ This 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.

[0053] Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, isopentyl group, isohexyl group, t-butyl group, and t-amyl group.

[0054] Specific examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and hexyloxy groups.

[0055] Specific examples of alkoxyalkyl groups having 2 to 8 carbon atoms include methoxymethyl group, methoxyethyl group, ethoxyethyl group, ethoxymethyl group, and butoxybutyl group.

[0056] From the perspective of minimizing resin shrinkage during curing, R ２０ The alkyl group is preferably a C1-C6 alkyl group, and more preferably a methyl group, ethyl group, propyl group, or isopropyl group.

[0057] p represents an integer between 0 and 2. Here, p=0 means a five-membered ring, p=1 means a six-membered ring, and p=2 means a seven-membered ring. From the viewpoint of the stability of the protecting group, it is preferable that p is 1.

[0058] q represents an integer between 0 and 2. From the viewpoint of minimizing contraction during curing, it is preferable that q be 0.

[0059] In formula (8), R ２１ R 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. Preferred R ２１ A concrete example is R ２０ It is the same as this.

[0060] r represents an integer between 0 and 2. Here, r=0 means a five-membered ring, r=1 means a six-membered ring, and r=2 means a seven-membered ring. The preferred range of r is the same as that of p.

[0061] s represents an integer between 0 and 2. The preferred range of s is the same as that of q.

[0062] In equations (9) and (10), R ２２ ~R ２７ This represents an alkyl group having 1 to 6 carbon atoms.

[0063] Preferred examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, isohexyl, t-butyl, and t-amyl groups. From the viewpoint of minimizing shrinkage during curing, methyl and ethyl groups are more preferred among C1-C6 alkyl groups.

[0064] From the viewpoint of resin solubility, a more preferable acid-dissociable group is one having an oxycarbonyl group. Preferred structures for acid-dissociable groups having an oxycarbonyl group include the following:

[0065]

[0066] * indicates a connection point.

[0067] (A-2) In the process of producing a multilayer structure of resin films, from the viewpoint of improving the proportion of the lower layer (A-2) post-dissociation resin film that is retained without dissolving when the upper layer (A-1) resin film is formed, the preferred protection rate of amide groups by acid-dissociable groups is preferably 20 mol% or more, more preferably 50 mol%, even more preferably 75 mol%, and most preferably 85 mol%, when the total amount of amide groups in the (A) resin is 100 mol.

[0068] (A-2) In the process of producing a multilayer structure of resin films, from the viewpoint of improving the proportion of the lower layer (A-2) post-dissociation resin film that is retained without dissolving when the upper layer (A-1) resin film is formed, the preferred protection rate of hydroxyl groups by acid-dissociable groups is preferably 5 mol% or more, more preferably 20 mol%, even more preferably 50 mol%, and most preferably 60 mol%, when the total hydroxyl groups in the (A) resin are 100 mol.

[0069] In formula (1), X １ This is a divalent organic group with 1 to 50 carbon atoms. From the viewpoint of the heat resistance of the resin, X １ It is preferable that the organic group does not contain an amide bond.

[0070] Preferred X １ Specific examples include, but are not limited to, residues of terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, diphenyl sulfon dicarboxylic acid, diphenyl thioether dicarboxylic acid, biphenyl dicarboxylic acid, 2,2'-bis(4-carboxy)hexafluoropropane, 2,2'-bis(4-carboxy)propane, diphenyl ketone dicarboxylic acid, or residues of compounds in which some of the hydrogen atoms of these aromatic rings are substituted with alkyl or halogen atoms, or residues of aliphatic dicarboxylic acids in which these aromatic rings are hydrogenated, such as cyclohexyl dicarboxylic acid. These dicarboxylic acids can be used individually or in combination of two or more.

[0071] In formula (1), Y １ This is a divalent organic group with 2 to 50 carbon atoms. From the viewpoint of the heat resistance of the resin, Y １It is preferable that the organic group does not contain an amide bond.

[0072] Preferred Y １ Specific examples include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl} ether Examples include, but are not limited to, residues of tel, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, and 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, or residues of compounds in which some of the hydrogen atoms of these aromatic rings are substituted with alkyl or halogen atoms, or residues of aliphatic diamines in which these aromatic rings are hydrogenated, such as cyclohexyldiamine and methylenebiscyclohexylamine. These diamines can be used individually or in combination of two or more.

[0073] (A-2) In the process of fabricating a multilayer structure of resin films, from the viewpoint of improving the proportion in which the lower layer (A-2) post-dissociation resin film is retained without dissolving during the formation of the upper layer (A-1) resin film, in formula (1), X １ is an organic group having an aromatic ring, -NR １ -CO- group and -NR ２The aromatic ring is directly bonded to the carbonyl group of the -CO- group, and Y １ is an organic group having an aromatic ring, -NR １ -CO- group and -NR ２ It is preferable that the aromatic ring is directly bonded to the nitrogen atom of the -CO- group. In other words, it is preferable that formula (1) is a fully aromatic polyimide structure.

[0074] In formula (2), X ２ This is a trivalent organic group with 3 to 50 carbon atoms. From the viewpoint of the heat resistance of the resin, X ２ It is preferable that the organic group does not contain an amide bond.

[0075] Preferred X ２ Specific examples include, but are not limited to, residues of trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, or residues of compounds in which some of the hydrogen atoms of these aromatic rings are substituted with alkyl or halogen atoms, or residues of hydrogenated tricarboxylic acids. These tricarboxylic acids can be used individually or in combination of two or more.

[0076] In formula (2), preferred Y ２ A concrete example of this is Y in equation (1). １ The same things can be listed.

[0077] In formula (3), X ３ This is a divalent organic group with 1 to 50 carbon atoms. From the viewpoint of the heat resistance of the resin, X ３ It is preferable that the organic group does not contain an amide bond.

[0078] Preferred X ３ A concrete example of this is X in equation (1). １ The same things can be listed.

[0079] In formula (3), the preferred -Y ３ (OR ６ ) ( OR ７Specific examples of these include 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-methyl Examples include, but are not limited to, residues of bis(3-amino-4-mercaptophenyl)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, and residues of compounds in which some or all of the hydroxyl groups of these diamines are protected by acid-dissociable groups.

[0080] R in equation (4) １０ , R １１ , R in equation (5) １６ , R １７ Preferred specific examples include saturated hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, and t-amyl groups, and organic groups containing unsaturated groups such as propenyl, butenyl, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, ethyl methacrylamide, propyl methacrylamide, ethyl acrylamide, and propyl acrylamide.

[0081] X in equation (4) ４ , X in equation (5) ５ This is a tetravalent organic group with 4 to 50 carbon atoms. From the viewpoint of the heat resistance of the resin, X ４ , X ５ It is preferable that the organic group does not contain an amide bond.

[0082] Preferred X ４ , X ５Specific examples include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, and 1,1-bis(2,3-dicarboxyphenyl)ethane. Examples of tetracarboxylic acids include, but are not limited to, residues of aromatic tetracarboxylic acids such as bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, and 3,4,9,10-perylenetetracarboxylic acid, as well as residues of aliphatic tetracarboxylic acids such as cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1.]heptanetetracarboxylic acid, bicyclo[3.3.1.]tetracarboxylic acid, bicyclo[3.1.1.]hept-2-enetetracarboxylic acid, bicyclo[2.2.2.]octanetetracarboxylic acid, and adamatanetetracarboxylic acid. These tetracarboxylic acids can be used individually or in combination of two or more.

[0083] In formula (4), preferred Y ４ A concrete example of this is Y in equation (1). １ The same things can be listed.

[0084] In formula (5), the preferred -Y ５ (OR １４ ) ( OR １５ A concrete example of this is -Y in equation (3). ３ (OR ６ ) ( OR ７ ) can be listed as the same thing.

[0085] In formulas (1) to (5), in order to improve the adhesion of the (A-2) post-dissociation resin film to silicon-based substrates or glass substrates after the dissociation of the acid-dissociable groups, or after additional heat treatment after the dissociation of the acid-dissociable groups, or to increase its resistance to oxygen plasma and UV ozone treatment used for cleaning, etc., within a range that does not reduce heat resistance, Y １ , Y ２ , Y ３ , Y ４ , Y ５ A siloxane structure may be included as a copolymer component. Specific Y １ , Y ２ , Y ３ , Y ４ , Y ５ Examples of these include residues such as bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane. １ , Y ２ , Y ３ , Y ４ , Y ５ In each case, it is preferable that the amount is in the range of 1 to 10 mol% of the total.

[0086] In formulas (1) to (5), in order to improve the adhesion of the (A-2) post-dissociation resin film to the metal substrate after the dissociation of the acid-dissociation group, or after additional heat treatment after the dissociation of the acid-dissociation group, Y is used within a range that does not reduce heat resistance. １ , Y ２ , Y ３ , Y ４ , Y ５ An aliphatic structure having a polyalkylene oxide group may be included as a copolymer component. Specific examples of such structures include residues from "Jeffermin" (registered trademark) KH-511, Jeffermin ED-600, Jeffermin ED-900, Jeffermin ED-2003, Jeffermin EDR-148, Jeffermin EDR-176, Jeffermin D-200, Jeffermin D-400, Jeffermin D-2000, and Jeffermin D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.). These can be used individually or in combination of two or more. １ , Y ２ , Y３ , Y ４ , Y ５ It is preferable that it is included in the range of 1 to 30 mol% of the total.

[0087] (A-2) In the process of manufacturing a multilayer structure of a resin film, from the viewpoint of improving the proportion of the lower layer (A-2) post-dissociation resin film that is retained without dissolving when the upper layer (A-1) resin film is formed, it is preferable that the structural units of (a-1) and (a-2) below are 60 mol% or more with respect to 100 mol% of the total structural units of the resin (A). The structural units of (a-1) and (a-2) are more preferably 80 mol% or more, even more preferably 90 mol% or more, and most preferably 95 mol% or more. (a-1) Structural units of formulas (1) to (5) (a-2) In formulas (1) to (5), R １ ~R ５ , R ８ , R ９ , R １２ , and R １３ A structural unit in which all atoms are hydrogen atoms.

[0088] (A) The resin is synthesized by the methods listed below, but is not limited to these. A preferred method is to first polymerize the polymer, and then protect the hydrogen atoms of the amide group with an acid-dissociable group.

[0089] In the case of structures represented by formula (1) or formula (3), the polymer is generally polymerized by dissolving a diamine or a hydroxyl group-containing diamine in a solvent such as NMP, DMF, DMAC, GBL, or DMSO, and then adding a dicarboxylic acid to carry out the reaction. The reaction temperature is generally -20°C to 100°C, with 0°C to 50°C being preferred. The reaction time is generally 1 minute to 100 hours, with 2 hours to 24 hours being preferred. During the reaction, it is preferable to prevent moisture from entering the system by flowing nitrogen. In a typical reaction, a dicarboxylic acid chloride is reacted with a diamine solution, and then a polyamide can be obtained by heat treatment at 100°C to 300°C for 1 minute to 24 hours.

[0090] Subsequently, in the case of the structure represented by formula (1), the hydrogen atoms of the amide group in the polymer are protected with an acid-dissociating group, and in the case of the structure represented by formula (3), the hydrogen atoms of the amide group and hydroxyl group in the polymer are protected with an acid-dissociating group. As a protection method, for example, when protecting with an acid-dissociating group containing an oxycarbonyl group, a protective agent such as di-tert-butyl dicarbonate or di-tert-amyl dicarbonate is mixed with a base catalyst such as dimethylaminopyridine, and the reaction is carried out at room temperature to 100°C for several minutes to about 10 hours. At this time, the degree of protection of the amide group in the polymer can be adjusted by changing the amount of protective agent added.

[0091] In the case of the structure represented by formula (2), the polymer is generally polymerized by dissolving the diamine in a solvent such as NMP, DMF, DMAC, GBL, or DMSO, and then adding a tricarboxylic acid to carry out the reaction. The reaction temperature is generally -20°C to 100°C, with 0°C to 50°C being preferred. The reaction time is generally 1 minute to 100 hours, with 2 hours to 24 hours being preferred. During the reaction, it is preferable to prevent moisture from entering the system by flowing nitrogen through it.

[0092] A common reaction involves reacting a diamine solution with tricarboxylic acid chloride, followed by a heat treatment at 100°C to 300°C for 1 minute to 24 hours to obtain polyamide-imide. In this case, the reaction can be accelerated by adding acid anhydrides such as acetic anhydride or bases such as triethylamine, pyridine, or picoline as catalysts at a concentration of 0.1 to 10% by weight relative to the amount of polymer. Alternatively, polyamide-imide can be obtained by polymerizing diamine and trimellitic anhydride chloride in the presence of pyridine, triethylamine, etc., then isolating the polymer as a solid, and finally heating the solid at a temperature of 100 to 300°C for 1 minute to 24 hours.

[0093] In the case of the structure represented by formula (2), the amino group of the diamine compound used in polymer polymerization is replaced with an isocyanate, and the polymer is reacted with a tetracarboxylic dianhydride, a tricarboxylic anhydride, and possibly a tin-based catalyst or a base catalyst at a temperature range of room temperature to 200°C for 1 minute to 24 hours. This method is preferable because it does not produce water as a by-product.

[0094] Subsequently, the hydrogen atoms of the amide groups in the polymer are protected with acid-dissociable groups. The protection method is the same as that used for the structure represented by formula (1).

[0095] In the case of the structure represented by formula (4) or formula (5), the polymer is generally polymerized by dissolving the diamine in a solvent such as N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), gamma-butyrolactone (GBL), or dimethyl sulfoxide (DMSO), and then adding a tetracarboxylic dianhydride to carry out the reaction. The reaction temperature is generally -20°C to 100°C, with 0°C to 50°C being preferred. The reaction time is generally 1 minute to 100 hours, with 2 hours to 24 hours being preferred. During the reaction, it is preferable to prevent moisture from entering the system by flowing nitrogen. Subsequently, a polyamic acid ester can be obtained by reacting the polymer with an acetal compound such as dimethylformamide dialkyl acetal. The esterification rate can be adjusted by changing the amount of acetal compound added.

[0096] In the case of the structure represented by formula (4), the following method can also be used as an alternative method for polymerizing the polymer. First, the tetracarboxylic dianhydride is mixed with an alcohol such as ethanol, propanol, or butanol and a base catalyst such as pyridine or triethylamine, and the mixture is reacted at room temperature to 100°C for several minutes to 10 hours to obtain a dicarboxylic acid diester compound. In order to obtain the dicarboxylic acid diester compound, the tetracarboxylic dianhydride may be directly dispersed in the alcohol, or the tetracarboxylic dianhydride may be dissolved in a solvent such as NMP, DMAC, DMF, DMSO, or GBL, and then reacted with the alcohol and base catalyst.

[0097] The obtained dicarboxylic acid diester is heated in thionyl chloride or reacted with oxalo dichloride to obtain a dicarboxylic acid chloride diester. The obtained dicarboxylic acid chloride diester is recovered by distillation or other methods and added dropwise to a solution in which the diamine is dissolved in a solvent such as NMP, DMAC, DMF, DMSO, or GBL in the presence of pyridine or triethylamine. The dropwise addition is preferably carried out at -20°C to 30°C. After the dropwise addition is complete, the reaction is carried out at -20°C to 50°C for 1 to 100 hours to obtain a polyamic acid ester.

[0098] Furthermore, since using dicarboxylic acid dichloride diesters results in the formation of hydrochloride salts as byproducts, it is preferable to react the diamine with a peptide condensation reagent such as dicyclohexylcarbodiimide, rather than heat-treating the dicarboxylic acid diester in thionyl chloride or reacting it with oxalo dichloride.

[0099] Subsequently, in the case of the structure represented by formula (4), the hydrogen atoms of the amide group in the polymer are protected with an acid-dissociating group, and in the case of the structure represented by formula (5), the hydrogen atoms of the amide group and hydroxyl group in the polymer are protected with an acid-dissociating group. The protection method is the same as that used for the structure represented by formula (1).

[0100] A preferred method for protecting the hydrogen atoms of the amide and hydroxyl groups of a polymer with acid-dissociable groups is a method that includes the step of reacting a resin having amide bonds in the structural units of the polymer main chain with a compound represented by formula (11).

[0101]

[0102] In formula (11), R ２８ and R ２９ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms. Preferred specific examples of hydrocarbon groups having 1 to 20 carbon atoms include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, amyl, hexyl, cyclohexyl, cyclopentyl, and 1,1-dimethylbutyl groups.

[0103] From the viewpoint of improving the imidization rate, it is more preferable that the compound represented by formula (11) is at least one selected from the compounds represented below.

[0104]

[0105] (A) In the polymerization reaction for synthesizing the polymer of the resin, the molar ratio of acidic components such as tetracarboxylic acid, tricarboxylic acid, and dicarboxylic acid to diamine or diisocyanate is preferably 100 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, and most preferably 85 mol% or less, relative to 100 mol% of diamine or diisocyanate. When there is a higher proportion of diamine or diisocyanate, the terminal amine and isocyanate groups have the effect of improving the adhesion between the (A) resin and the filler, conductive substrate, or conductive wiring.

[0106] Alternatively, resin (A) may be obtained by precipitation in a poor solvent for the resin, such as methanol or water, after the completion of polymer polymerization and / or after protection with an acid-dissociable group, followed by washing and drying. Precipitation has the advantage of improving heat resistance because by-products from the esterifying agent, condensing agent, and acid chloride used during polymerization, as well as low molecular weight components of the resin precursor, can be removed.

[0107] <(B) Solvent> The resin composition according to the embodiment of the present invention preferably contains the (A) resin and the (B) solvent. Preferably used as the (B) solvent are ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether; acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; ketones such as acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, and 2-heptanone. Examples include alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; and N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone. These can be used individually or in combination.

[0108] (A-2) In the process of fabricating a multilayer structure of resin films, from the viewpoint of improving the proportion in which the lower layer (A-2) post-dissociation resin film is retained without dissolving during the formation of the upper layer (A-1) resin film, (B) when the total amount of solvent is 100% by mass, the Hansen solubility parameter (HSP value: δ) is 22.5 (MPa). １／２ Preferably, the following solvents make up 50% by mass or more of the total solvent. More preferably, 70% by mass or more, even more preferably 80% by mass or more, and most preferably 90% by mass or more.

[0109] By reducing the polarity of the solvent, the interaction between the polar groups of the resin (A) and the solvent is reduced, and it is thought that the intermolecular forces between polyimides after heat treatment will be strengthened.

[0110] Preferred examples include, but are not limited to, methylene chloride (δ=19.8), dioxane (δ=19.8), anisole (δ=19.6), tetrahydrofuran (δ=19.5), propylene glycol monomethyl ether acetate (δ=19.3), methyl ethyl ketone (δ=19.1), chloroform (δ=18.9), toluene (δ=18.2), xylene (δ=18.1), benzene (δ=18.5), ethyl acetate (δ=18.2), butyl butyrate (δ=16.8), butyl acetate (δ=17.4), methyl isobutyl ketone (δ=17.0), cyclohexane (δ=16.8), propylene glycol monomethyl ether (δ=20.4), cyclohexanone (δ=20.3), cyclopentanone (δ=22.1), ethyl lactate (δ=21.7), and diacetone alcohol (δ=20.8).

[0111] In this invention, the Hansen solubility parameter (HSP value: δ) is a value published by Charles M. Hansen in 1967 that is used to predict the solubility of a substance, and is calculated from the energies of δd (dispersion force term), δp (dipole term), and δh (hydrogen bond term). ２ = (δd) ２ + (δp) ２ + (δh) ２ It is calculated as follows. The value of δ tends to decrease as the polarity of the solvent decreases.

[0112] The Hansen solubility parameters used here are those listed in Hansen, Charles (2007). Hansen Solubility Parameters: A user's handbook, Second Edition. Boca Raton, Fla: CRC Press. The values ​​are calculated using the software HSPiP (Hansen Solubility Parameter in Practice) (manufactured by HSP Science), which calculates the Hansen solubility parameters. The results can also be obtained by quoting from the HSP value calculation results (1218 substances: source: https: / / www.stevenabbott.co.uk / practical-solubility / hsp-basics.php) published by Professor Steven Abbott.

[0113] In the resin composition, the concentration of (A) the resin and the viscosity of the resin composition are preferably in the range of 1 mPa·s to 1000 Pa·s at a concentration of 1 to 50% by weight and a viscosity of 1 mPa·s to 1000 Pa·s, and more preferably at a concentration of 5 to 30% by weight and a viscosity of 100 mPa·s to 100 Pa·s. This range allows for the formation of a uniform film without unevenness.

[0114] From the viewpoint of suppressing crack formation in multilayer structures during thermal cycling tests and improving the reliability of multilayer structures, it is preferable that the tensile modulus of the film obtained by heat-treating the resin composition of the present invention at 250°C for 1 hour is 3.5 GPa or more and 20 GPa or less. Having the tensile modulus within this range makes it possible to suppress deformation of the substrate during thermal cycling tests, leading to crack suppression. Preferably, it is 4.0 GPa or more and 20 GPa or less.

[0115] In this invention, the tensile modulus is calculated by cutting a single interlayer insulating film with a thickness of 10 μm into strips 1 cm wide and approximately 9 cm long, and performing a tensile test on the film under the following conditions, and taking the average of the top 5 measurement results: Temperature: 23°C, Humidity: 45% RH, Chuck distance: 5 cm, Full-scale load: 25 N, Crosshead speed: 50 mm / min, Breakage detection sensitivity: 1.0%.

[0116] In the resin composition according to the embodiment of the present invention, (A) the resin is preferably such that the absorbance A1 per 1 μm of film thickness of the film, when applied to a substrate in a solution dissolved in a solvent and dried at 100°C for 2 minutes using a hot plate, and the absorbance A2 per 1 μm of film thickness of the film, when heat-treated at 250°C for 1 hour using an oven after drying, are 0.003 < A1 < 0.3 and A2 ≥ 0.3.

[0117] When photosensitivity is imparted to a resin composition, the less light absorption by the resin (A) before heat treatment, the more light the photosensitive agent in the resin film (A-1) absorbs during exposure, resulting in higher sensitivity. From this viewpoint, it is more preferable that A1 be less than 0.07, and even more preferable that it be less than 0.03.

[0118] Furthermore, if the multilayer structure is a multilayer wiring structure, (A-1) ultraviolet light used in the exposure process of the resin film can degrade the adhesion between the underlying (A-2) dissociated resin film and the wiring.

[0119] If the light absorption after heat treatment is high (A-2), ultraviolet light transmission within the resin film after dissociation is suppressed, which can suppress delamination within the multilayer wiring structure during thermal cycle testing and lead to improved reliability of the multilayer structure. From this viewpoint, it is more preferable that A2 be greater than 0.4, and even more preferable that it be greater than 0.8.

[0120] <(C) Thermal acid generator> From the viewpoint of promoting the detachment of acid-dissociable groups bonded to the amide group at lower temperatures, it is preferable that the resin composition according to the embodiment of the present invention further contains (C) a thermal acid generator in addition to (A) the resin and (B) the solvent. Specific examples of (C) thermoacid generators that are preferably used include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, ​​SI-160L, SI-180L (all manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, their methanesulfonates, trifluoromethanesulfonates, camphorsulfonates, and p-toluenesulfonates. More preferably, these are 4-hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, their methanesulfonates, trifluoromethanesulfonates, camphorsulfonates, and p-toluenesulfonates. These compounds may be used individually or in combination of two or more.

[0121] In the resin composition, the preferred content of (C) the thermal acid generator is 0.01 to 10 parts by weight, and more preferably 0.01 to 0.5 parts by weight, per 100 parts by weight of (A) the resin.

[0122] <(D) Photoacid Generator> From the viewpoint that the acid generated by light promotes the detachment of acid-dissociable groups bonded to the amide group at a lower temperature, the resin composition according to the embodiment of the present invention may further contain (D) a photoacid generator in addition to (A) the resin and (B) the solvent. In this case, the resin composition may further contain (C) a thermal acid generator.

[0123] By including (D) a photoacid generator in the resin composition, when a film obtained from the resin composition is partially irradiated with light, the detachment of acid-dissociable groups can be carried out only in the irradiated area. By developing the film after light irradiation with a solvent that can dissolve (A) the resin (for example, solvent (B)), only the unirradiated areas where the detachment of acid-dissociable groups has not occurred are eluted, and a negative-type relief pattern can be obtained. Specific examples of (D) photoacid generators include ester compounds of polyvalent phenol compounds and naphthoquinone diazidosulfonic acid compounds, onium salt type ionic photoacid generators, and nonionic photoacid generators. An onium salt refers to a compound formed when a compound having an electron pair that does not participate in chemical bonding coordinates with another cationic compound using that electron pair. In the case of the ionic photoacid generator, the cation part of the onium salt determines the photochemical properties (molar extinction coefficient, absorption wavelength, quantum yield), and the anionic part determines the strength of the acid produced. On the other hand, nonionic photoacid generators are photoacid generators in which a light-absorbing site and an acid are bonded via an ester bond.

[0124] As an ionic photoacid generator, one that does not contain heavy metals or halogen ions is preferred, and triorganosulfonium salt compounds are more preferred. Specific examples of triorganosulfonium salt compounds include, for example, methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, and perfluoro-1-butanesulfonate of triphenylsulfonium ("SP-056", trade name, manufactured by ADEKA Corporation); the aforementioned sulfonate of dimethyl-1-naphthylsulfonium; the aforementioned sulfonate of dimethyl(4-hydroxy-1-naphthyl)sulfonium; the aforementioned sulfonate of dimethyl(4,7-dihydroxy-1-naphthyl)sulfonium; and the aforementioned sulfonate of diphenyliodonium.

[0125] Nonionic photoacid generators that can be used include diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, sulfonimide compounds, phosphate ester compounds, and sulfonebenzotriazole compounds.

[0126] A specific example of a diazomethane compound is bis(4-methylphenylsulfonyl)diazomethane ("WPAG-199", trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0127] Specific examples of sulfone compounds include, for example, β-ketosulfone compounds and β-sulfonylsulfone compounds. Preferred sulfone compounds include 2-(p-toluenesulfonyl)acetophenone and bis(phenylsulfonyl)methane.

[0128] Specific examples of sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and iminosulfonic acid ester compounds. Preferred specific examples include benzoin-4-tolylsulfonate, pyrogalloltris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthuryl-2-sulfonate, and 2,6-(dinitrobenzyl)phenylsulfonate.

[0129] A specific example of a carboxylic acid ester compound is, for instance, 2-nitrobenzyl carboxylic acid.

[0130] From the viewpoint of promoting the detachment of the acid-dissociable group bonded to the amide group, preferred photoacid generators (D) include oximesulfonate compounds and / or imidosulfonate compounds.

[0131] Specific examples of oxime sulfonates 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), PAG-203 (all manufactured by BASF Japan), PAI-101 ((Z)-4-methoxy-N-(tosiloxy)benzimidoylcyanide, manufactured by Midori Chemical Co., Ltd.).

[0132] Specific examples of imidosulfonate compounds include N-hydroxynaphthalimide triflate, “ADEKA ARCULUS” (registered trademark) SP-606 (4-butyl-N-hydroxynaphthalimide triflate, manufactured by ADEKA Corporation), NA-101 (N-hydroxynaphthalimide-p-toluenesulfonate), and NA-106 (N-hydroxynaphthalimide camphor sulfonate, all manufactured by Midori Chemical Co., Ltd.).

[0133] In the resin composition, the content of (D) the photoacid generator is preferably 1 to 100 parts by mass, and more preferably 1 to 40 parts by mass, per 100 parts by mass of (A) resin, from the viewpoint of the difference in dissolution rates between the exposed and unexposed areas and the tolerance range of sensitivity.

[0134] <Other Components> In the resin composition according to the embodiment of the present invention, when negative photosensitivity is imparted using a resin having a structural unit of formula (4) or formula (5), R in formula (4) １０ , R １１ , or R in equation (5) １６ , R １７ However, it is preferable that the group is one having an ethylenically unsaturated double bond, such as an ethyl methacrylate group, an ethyl acrylate group, a propyl methacrylate group, a propyl acrylate group, an ethyl methacrylamide group, a propyl methacrylamide group, an ethyl acrylamide group, or a propyl acrylamide group.

[0135] The resin composition according to the embodiment of the present invention may contain a photopolymerizable compound to improve its photosensitivity. Examples of photopolymerizable compounds include, but are not limited to, 2-hydroxyethyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, methylene bismethacrylamide, and methylene bisacrylamide.

[0136] In the resin composition, the content of the photopolymerizable compound is preferably in the range of 1 to 30 parts by weight per 100 parts by weight of the resin (A). Within this range, a (A-2) post-dissociation resin film can be obtained that has high sensitivity and good mechanical properties after dissociation of the acid-dissociable group, or after additional heat treatment after dissociation of the acid-dissociable group. These photopolymerizable compounds can be used individually or in combination of two or more.

[0137] The resin composition according to the embodiment of the present invention may contain a photopolymerization initiator from the viewpoint of improving the negative-type photosensitive properties. Examples of photopolymerization initiators include, but are not limited to, aromatic amines such as N-phenyldiethanolamine and N-phenylglycine, aromatic ketones such as Michla's ketone, cyclic oxime compounds represented by 3-phenyl-5-isoxazolone, chain-like oxime compounds represented by 1-phenylpropanedione-2-(o-ethoxycarbonyl)oxime, benzophenone derivatives such as benzophenone, o-benzoylmethyl benzoate, dibenzyl ketone, and fluorenone, and thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone.

[0138] In the resin composition, the content of the photopolymerization initiator is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, per 100 parts by weight of resin (A). It is also preferably 30 parts by weight or less, and more preferably 20 parts by weight or less. Within this range, a (A-2) post-dissociation resin film can be obtained that has high sensitivity and good mechanical properties after dissociation of the acid-dissociable groups, or after additional heat treatment after dissociation of the acid-dissociable groups. These photopolymerization initiators can be used alone or in combination of two or more.

[0139] The resin composition according to the embodiment of the present invention is more preferably to include a photosensitizer from the viewpoint of further improving the negative-type photosensitive properties. Examples of photosensitizers include aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone, aminocoumarins such as 7-diethylaminobenzoylcoumarin and 3,3'-carbonylbis(diethylaminocoumarin), and aromatic ketones such as benzantrone and phenanthrenequinone, which are generally used in photocurable resins. Other photosensitizers used as charge transfer agents in electrophotographic photoreceptors may also be preferably used.

[0140] In the resin composition, the content of the photosensitizer is preferably 0.01 parts by weight, more preferably 0.1 parts by weight or more, per 100 parts by weight of resin (A). It is also preferably 30 parts by weight or less, and more preferably 20 parts by weight or less. Within this range, a (A-2) post-dissociation resin film can be obtained that has high sensitivity and good mechanical properties after dissociation of the acid-dissociable groups, or after additional heat treatment after dissociation of the acid-dissociable groups. These photosensitizers can be used alone or in combination of two or more.

[0141] The resin composition according to the embodiment of the present invention can also be used as a slurry containing a filler. When the resin composition according to the embodiment of the present invention is used in a resin film contained in semiconductors, displays, multilayer wiring substrates, etc., the inclusion of a filler in the resin composition can be expected to further reduce linear expansion, increase strength, and control the refractive index, dielectric constant, and magnetic permeability. When the resin composition according to the embodiment of the present invention is used in secondary batteries or capacitors, the filler acts as an active material, enabling it to function as a positive electrode or negative electrode.

[0142] Preferred fillers for use in semiconductors, displays, and multilayer wiring substrates include, but are not limited to, silicon oxide, titanium oxide, alumina, barium titanate, aluminum nitride, zirconium oxide, silicon nitride, and titanium nitride.

[0143] Preferred fillers for use in secondary batteries and capacitors include compounds containing atoms such as carbon, silicon, tin, germanium, titanium, iron, cobalt, nickel, manganese, copper, silver, zinc, indium, bismuth, antimony, or chromium. Preferably, the compound contains at least one atom from carbon, manganese, cobalt, nickel, iron, silicon, titanium, tin, and germanium, and more preferably, it contains at least one atom from silicon and titanium.

[0144] The above resin composition and slurry can be obtained by mixing and kneading (A) resin, and optionally (B) solvent and other additives. Mixing methods include stirring and dissolving in a glass flask or stainless steel container using a mechanical stirrer, dissolving with ultrasound, or stirring and dissolving with a planetary stirring and defoaming device. Kneading methods include using a planetary mixer, a three-roll mixer, a ball mill, or a homogenizer. The conditions for mixing and kneading are not particularly limited.

[0145] Furthermore, to remove foreign matter, the resin composition or slurry after mixing and kneading may be filtered through a filter with a pore size of 0.01 μm to 100 μm. Suitable materials for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE), but polyethylene and nylon are preferred. In addition, if the resin composition contains fillers or organic pigments, it is preferable to use a filter with a pore size larger than the particle size of these.

[0146] The resin composition according to the embodiment of the present invention may contain, to the extent that it does not hinder the objective of the present invention, and for the purpose of providing additional functions, dissolution accelerators, thermal crosslinking agents, silane coupling agents, surfactants, etc.

[0147] <Cured Product> The cured product according to the embodiment of the present invention is obtained by curing the resin composition according to the embodiment of the present invention. Curing refers to the process in which a composition containing resin (A) is heat-treated, causing the acid-dissociable groups bonded to the amide groups of resin (A) to be removed and converted into hydrogen, resulting in a conversion to a resin with different solubility in organic solvents.

[0148] The curing temperature is preferably between 100°C and 320°C. This heat treatment can be carried out by selecting a temperature and gradually increasing it, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. One example is a method of heat treatment at 130°C and 200°C for 30 minutes each. The lower limit of the heating temperature is more preferably 170°C or higher in order to allow sufficient curing to proceed. The upper limit of the heating temperature is preferably 280°C or lower.

[0149] <Method for Manufacturing Cured Products> A preferred method for manufacturing cured products according to embodiments of the present invention is a method comprising the steps of (a) applying and drying a resin composition according to embodiments of the present invention onto a substrate to form a resin film, and then (d) heat-treating the applied and dried resin film.

[0150] If the resin composition is photosensitive, the steps of (b) exposing the resin film through a photomask and (c) developing the exposed portion with an alkaline aqueous solution are included in this order between steps (a) and (d).

[0151] The substrate is not particularly limited, but it is preferably selected from the group consisting of glass, silicon wafer, ceramic deposited substrate, metal plated substrate, sapphire, and gallium arsenide.

[0152] A known method can be used to apply the resin composition onto the substrate. Examples of equipment used for application include full-surface coating equipment such as spin coating, dip coating, curtain flow coating, spray coating, or slit coating, or printing equipment such as screen printing, roll coating, microgravure coating, or inkjet.

[0153] After application, the resin film is dried to form. Drying is performed using a vacuum drying apparatus or a heating device such as a hot plate or oven. When using a heating device, it is preferable to dry the film at a temperature range of 50 to 150°C for 30 seconds to 30 minutes. The thickness of the resin film is preferably 0.1 to 100 μm.

[0154] In the heat treatment process, a temperature of 150°C to 320°C is applied to promote the detachment of acid-dissociable groups. This heat treatment can be carried out by selecting a temperature and gradually increasing it, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. One example is a method of heat treatment at 130°C and 200°C for 30 minutes each. The lower limit of the heating temperature is preferably 170°C or higher to allow sufficient hardening to proceed. The upper limit of the heating temperature is preferably 280°C or lower.

[0155] In the process of exposing a resin film, the wavelength of the exposure light is not particularly limited, and examples include light having wavelengths of 300 to 450 nm, such as the g-line (436 nm), i-line (365 nm), and h-line (405 nm). Among these, it is preferable to irradiate with light having a wavelength of 365 nm. Examples of light sources used in the exposure process 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 as needed by passing it through spectral filters such as long-wavelength cut filters, short-wavelength cut filters, and bandpass filters.

[0156] After exposure, post-exposure baking may be performed as needed. Post-exposure baking can be expected to improve resolution after development or increase the tolerance range of development conditions. Post-exposure baking can be performed using an oven, hot plate, infrared, flash annealing device, laser annealing device, etc. The post-exposure baking temperature is preferably 50 to 170°C, and more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to 1 hour, and more preferably 30 seconds to 30 minutes.

[0157] In the developing process, the developing solution used is either an organic solvent or an alkaline aqueous solution containing an alkaline compound.

[0158] Examples of organic solvents include 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, either individually or in combination of several of these.

[0159] Examples of alkaline compounds include tetramethylammonium hydroxide, potassium hydroxide, and sodium carbonate. In some cases, the solvents listed above as organic solvents may be added to these alkaline aqueous solutions.

[0160] After development, it is preferable to rinse with an organic solvent or water. When using an organic solvent, in addition to the developer mentioned above, examples include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. When using water, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the water for rinsing.

[0161] <Elements and Articles Containing Cured Materials> Examples of elements and articles containing the above-mentioned cured materials include electronic components and electronic devices. Examples of electronic components include semiconductor devices, antennas, display devices, metal-clad laminates, wiring boards, semiconductor packages, and active or passive components including semiconductor devices. Examples of display devices include organic EL displays, quantum dot displays, micro-light-emitting diode (hereinafter referred to as "LED") displays, mini-LED displays, or liquid crystal displays.

[0162] A preferred embodiment of an element and article comprising the cured product of the present invention is a substrate including a multilayer wiring structure, wherein the interlayer insulating film in the multilayer wiring structure is made of the cured product of the present invention.

[0163] These substrates can also be suitably used as substrates for mounting semiconductor and LED chips.

[0164] <Semiconductor Device> The semiconductor device according to the embodiment of the present invention has the cured product described above. In the present invention, a semiconductor device refers to any device that can function by utilizing the characteristics of a semiconductor element. Electro-optical devices and semiconductor circuit boards in which semiconductor elements are connected to a substrate, stacks of multiple semiconductor elements, and electronic devices including these are all included in semiconductor devices. Electronic components such as interposers for connecting semiconductor elements to a substrate, and printed circuit boards to which interposers are connected are also included in semiconductor devices. The cured product described above has excellent electrical insulation, mechanical strength, adhesion, and heat resistance, so it is preferable to use it as a surface protective film such as a passivation film or buffer coat film for semiconductor elements, an interlayer insulating film between rewirings formed on the surface of a semiconductor element, an insulating film between elements when multiple semiconductor elements are joined together, and an insulating film between wiring layers of a multilayer wiring board for high-density mounting or an interposer.

[0165] More preferably, as an embodiment of the present invention, the above-mentioned cured product is disposed as a surface protective film or interlayer insulating film between redistributions on a substrate including a semiconductor or the multilayer wiring structure. This makes it possible to create a highly reliable semiconductor device.

[0166] A more preferred embodiment of the present invention is a semiconductor device comprising a substrate including the multilayer wiring structure and a semiconductor element bonded to the substrate, wherein the interlayer insulating film in the multilayer wiring structure is made of the cured product of the present invention. This enables high-density semiconductor devices.

[0167] Most preferably, as an embodiment of the present invention, the semiconductor device comprises a substrate including the multilayer wiring structure and semiconductor elements bonded to the substrate, in addition to a printed circuit board, wherein the side of the substrate including the multilayer wiring structure that is not bonded to the semiconductor elements is directly bonded to the printed circuit board without the need for another organic substrate.

[0168] <Devices Equipped with Semiconductor Devices> Examples of devices equipped with semiconductor devices according to embodiments of the present invention include televisions, car navigation systems, smartphones, servers, mobile phone base stations, personal computers, routers, modems, tablets, communication satellites, digital cameras, home appliances, medical equipment, and industrial robots. Preferably, they are communication devices capable of bidirectional data transmission and reception with the outside, such as smartphones, servers, personal computers, and tablets.

[0169] <Display Device> A display device according to an embodiment of the present invention has the above-described cured product. Specifically, the display device of the present invention is a display device comprising a first electrode formed on a substrate, an insulating layer formed to partition pixels provided on the first electrode, and a second electrode provided opposite the first electrode, wherein the insulating layer is preferably the above-described cured product. The insulating layer can be formed by applying and drying the above-described photosensitive resin composition on a substrate on which the first electrode is formed, and then going through exposure, development, and curing steps to form a pattern of the insulating layer produced by the above-described cured product.

[0170] Another embodiment of the display device according to 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 described above.

[0171] Specifically, it is preferable that the display element has a drive circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and that either or both of the planarization layer and the insulating layer are the cured material described above. Taking an active matrix type display element as an example, it has a TFT and wiring located on the side of the TFT and connected to the TFT on a substrate such as glass or a resin film, and a planarization layer is provided on top of that so as to cover the irregularities, and a display element is further provided on the planarization layer. The display element and the wiring are connected via contact holes formed in the planarization layer.

[0172] Because the above-mentioned cured product exhibits excellent planarization and pattern dimensional stability, it is preferable to incorporate it into the display device as a planarization layer. In particular, in recent years, flexible display devices have become mainstream, and the substrate having the aforementioned drive circuit may be made of a resin film.

[0173] <Capacitor, Secondary Battery> The capacitor and secondary battery according to the embodiment of the present invention each have the above-mentioned cured material.

[0174] By adding the aforementioned filler, as well as conductive additives such as acetylene black, Ketjenblack, and carbon nanotubes, to the resin composition according to the embodiment of the present invention and forming a slurry, it can be used as an electrode slurry for secondary batteries and capacitors.

[0175] By applying an electrode slurry to one or both sides of a current collector such as copper foil, aluminum foil, or stainless steel foil, and curing it through heat treatment, electrodes for secondary batteries or capacitors can be obtained. Multiple positive and negative electrodes obtained in this way are stacked with separators in between, and then placed together with an electrolyte in an outer material such as a metal case and sealed to obtain energy storage devices such as secondary batteries and capacitors.

[0176] Examples of separators include polyolefins such as polyethylene and polypropylene, as well as microporous films and nonwoven fabrics such as cellulose, polyphenylene sulfide, aramid, and polyimide. To improve heat resistance, the surface of the separator may be coated with ceramic or other materials.

[0177] As solvents for the electrolyte, carbonate compounds such as propylene carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and vinylene carbonate, as well as acetonitrile, sulfolane, and γ-butyrolactone can be used. Two or more of these may be used.

[0178] Examples of electrolytes include lithium salts such as lithium hexafluorophosphate, lithium borofluoride, and lithium perchlorate, and ammonium salts such as tetraethylammonium tetrafluoroborate and triethylmethylammonium tetrafluoroborate.

[0179] Furthermore, the cured product according to the embodiment of the present invention can also be preferably used as an insulating film to prevent short circuits between the positive and negative electrodes.

[0180] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The compositions and multilayer structures in the examples were evaluated by the following methods.

[0181] (1) (A) Protection rate of amide groups and hydroxyl groups of resin. The protection rate is 400 MHz. １ The measurements were performed using a 1H-NMR (nuclear magnetic resonance) spectrometer (AL-400, manufactured by JEOL Ltd.). Specifically, measurements were taken in a deuterated dimethyl sulfoxide solution with 16 cumulative measurements. When M1 is the integral value of the protons of the amide group in the resin before protection, M2 is the integral value of the protons of the amide group in the resin after protection, N1 is the integral value of the protons of the hydroxyl group in the resin before protection, and N2 is the integral value of the protons of the hydroxyl group in the resin after protection, the protection rates for each group are calculated using the following formulas: Protection rate of amide group (%) = (M1 - M2) / M1 × 100 Protection rate of hydroxyl group (%) = (N1 - N2) / N1 × 100.

[0182] (2) Evaluation of solvent solubility The state of the solutions of resin compositions 1 to 39 was observed visually. Solutions that were transparent were deemed acceptable (OK), while solutions that were opaque, such as those in a suspended state, even though no polymer precipitate was observed, or those in which polymer precipitate was observed, were deemed unacceptable (NG).

[0183] (3) After the film thickness measurement, the film thickness of the coating was measured using an optical interference film thickness measuring device (Lambda Ace STM-602, manufactured by SCREEN Holdings Co., Ltd.) under conditions of a refractive index of 1.629.

[0184] (4) Evaluation of the proportion of the lower layer that is retained without dissolution during the formation of the upper layer when a multilayer structure is formed (evaluation of film thickness retention rate) Resin compositions 1-3, 6-10, 18, 19, 22, 27, and 28 were applied to a 4-inch silicon wafer by spin coating using a spinner (Mikasa Corporation: MS-A150) and dried on a hot plate at 100°C for 5 minutes. After placing this wafer in an inert oven (Koyo Thermo Systems Co., Ltd.: CLH-21CD-S) at room temperature, the temperature was raised to 200°C at 3.5°C / min with an oxygen concentration of 20 ppm or less, and heat treatment was performed at 200°C for 1 hour to produce a resin composition film with a film thickness of 4.0 μm after heat treatment. After that, the wafer was immersed in the same solvent used for the resin composition for 1 minute, rinsed with isopropanol, dried, and the film thickness was measured again. When the film thickness before and after immersion was denoted as T1 and T2, respectively, a score of T2 / T1 ≥ 0.6 was considered a pass, and a score of T2 / T1 < 0.6 was considered a fail.

[0185] For resin compositions 4, 5, 11, 12, 23-26, and 36-39, the compositions were applied to a 4-inch silicon wafer by spin coating using a spinner (Mikasa Corporation: MS-A150) and dried on a 100°C hot plate for 5 minutes. This wafer was then subjected to a 3000 mJ / cm² test using a mask aligner (Union Optical Co., Ltd.: PEM-6M). ２ A film of a resin composition with a post-exposure thickness of 4.0 μm was prepared by full-surface exposure. Subsequently, the wafer was immersed in the same solvent used for the resin composition for 1 minute, rinsed with isopropanol, dried, and the film thickness was measured again. When the film thickness before and after exposure were denoted as T1 and T2, respectively, T2 / T1 ≥ 0.6 was considered a pass, and T2 / T1 < 0.6 was considered a fail.

[0186] (5) Measurement of the absorbance of resin (A) The resin (A) used in the preparation of resin compositions 1 to 5, 18, 19, 22 to 28, and 36 to 39 was dissolved in N-methyl-2-pyrrolidone at a concentration of 30%, and the mixture was spin-coated onto a quartz substrate using a spinner (Mikasa Corporation, MS-A150), and dried on a hot plate (AS ONE Corporation, HP-2) at 100°C for 2 minutes. At this time, the rotation speed of the spin coating was adjusted so that the film thickness after drying was 10 μm.

[0187] The absorbance of the dried substrate was measured using a spectrophotometer (Hitachi High-Tech Corporation, U-2910), and the absorbance A1 per 1 μm was calculated.

[0188] Next, the dried substrate was cured in an inert oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere (oxygen concentration of 20 ppm or less) at 140°C for 30 minutes, and then further heated to 250°C for 1 hour to harden.

[0189] The film thickness and absorbance after heat treatment were measured, and the absorbance A2 per 1 μm was calculated.

[0190] (6) Measurement of the tensile modulus of the resin composition Resin compositions 1-5, 18, 19, 22-28, and 36-39 were spin-coated onto a 6-inch silicon wafer using a spinner (MS-A150, manufactured by Mikasa Corporation), and dried on a hot plate (HP-2, manufactured by AS ONE Corporation) at 100°C for 2 minutes. The dried substrate was then cured in an inert oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) at 140°C for 30 minutes under a nitrogen atmosphere (oxygen concentration of 20 ppm or less), and then further heated to 250°C for 1 hour. The rotation speed of the spin coating was adjusted so that the film thickness after heat treatment was 10 μm.

[0191] Next, the film was peeled off the substrate by immersion in hydrofluoric acid for 1 to 4 minutes, air-dried, and then cut into strips approximately 1 cm wide and 9 cm long to be used as the measurement sample. A "Tensilon" (manufactured by Orientec Co., Ltd., RTM-100) was used for measurement, and the average value of the top 5 scores was calculated from the results measured under the following conditions: Temperature: 23°C, Humidity: 45% RH, Chuck distance: 5 cm, Load full scale: 25 N, Crosshead speed: 50 mm / min, Breakage detection sensitivity: 1.0%.

[0192] (7) Measurement of the sensitivity of the resin composition Resin compositions 4, 5, 23-26, and 36-39 were spin-coated onto a 6-inch silicon substrate using a spinner (MS-A150, Mikasa Corporation) and dried on a hot plate (HP-2, AS ONE Corporation) at 120°C for 3 minutes. At this time, the spin rotation speed was adjusted so that the film thickness was 8 μm. This film was subjected to a sensitivity test from 0 to 1000 mJ / cm² and 50 mJ / cm² using an i-line stepper NSR-2005i9C (Nikon Corporation) through a photomask with a square through-hole size of 10 μm × 10 μm. ２ The film was exposed in a step-by-step manner. After exposure, the film was heat-treated at 120°C for 3 minutes on a hot plate (AS ONE Corporation, HP-2). After heat treatment, it was developed with cyclopentanone for 100 seconds and rinsed with propylene glycol monomethyl ether.

[0193] The sensitivity was defined as the minimum exposure dose required to make the dimension of the portion of the pattern formed on this film that is in contact with the substrate 9.5 to 10.5 μm relative to the 10 μm pattern dimension of the photomask.

[0194] (8) Formation of the outermost film L5 and interlayer insulating films L1 to L4 (through-hole pattern formation) (8-1) Resin compositions 4, 5, 23 to 26, and 36 to 39 were spin-coated onto the coated substrate using a spinner (Mikasa Corporation, MS-A150). At this time, the spin rotation speed was adjusted so that the film thickness after curing of L1 to L5 was 8 μm.

[0195] (8-2) The product was dried at 120°C for 3 minutes on a pre-baking hot plate (manufactured by AS ONE Corporation, HP-2).

[0196] (8-3) Exposure An i-line stepper NSR-2005i9C (manufactured by Nikon) was used to expose the image at 500 mJ / cm2 through a photomask having predetermined through-hole dimensions.

[0197] (8-4) Development: Developed using cyclopentanone as the developer and propylene glycol monomethyl ether as the rinse solution until the predetermined through-hole dimensions were achieved.

[0198] (8-5) Using a curing oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.), the material was cured at 140°C for 30 minutes under a nitrogen atmosphere (oxygen concentration of 20 ppm or less), and then further heated to 250°C for 1 hour to harden.

[0199] (9) Simultaneous formation of conductive wiring layers M1 to M5, electrode pads M6, and through-wirings MM1 to MM5 (9-1) Sputtered film deposition As shown in Figure 2A, a conductive wiring layer 62 is formed on the interlayer insulating film or on the support substrate 61, and through-holes 64 are formed by the next interlayer insulating film 63. A magnetron sputtering apparatus (ULVAC, Inc., SH-450) was used to sputter deposit a Ti layer 65 and a Cu layer 66 on the substrate in that order under the following conditions: Vacuum pressure: 8.0 × 10 －４ Deposition pressure below Pa: 0.1 Pa (adjusted by Ar flow rate) Power: 2.3 kW (Ti), 3.8 kW (Cu) Film thickness: 150 nm (Ti), 600 nm (Cu).

[0200] (9-2) Formation of Photoresist Pattern for Wiring Formation As shown in Figure 2B, a photoresist film 67 (P-CY1000: manufactured by Tokyo Ohka Kogyo Co., Ltd.) was formed on a Cu sputtered film under the following conditions to form a pattern with through-holes 68. Coating: Spin coating using a spinner (Mikasa Corporation, MS-A150). The rotation speed of the spin coating was adjusted so that the film thickness after development was 10 μm. Pre-bake: Drying at 130°C for 5 minutes using a hot plate (AS ONE Corporation, HP-2). Exposure: 1000 mJ / cm using an i-line stepper (Nikon Corporation, NSR-2005i9C) through a predetermined photomask. ２Exposure and post-exposure baking: Process at 80°C for 3 minutes using a hot plate (AS ONE Corporation, HP-2). Development: Add 2.38% by mass of TMAH (Tama Chemical Industry Co., Ltd.) to the developer and distilled water to the rinse solution, and develop until the predetermined pattern dimensions are open.

[0201] (9-3) Wiring Formation by Electroplating As shown in Figure 2C, copper plated wiring 69 was formed in the resist pattern by electroplating under the following conditions: Plating solution: Aqueous solutions of sulfuric acid and copper sulfate at concentrations of 2 M and 0.2 M, respectively. Plating temperature: 25°C Current density: 1 A / dm ２ Plating time: Adjust M1 to M5 so that the height is 8 μm, and adjust M6 so that the height is 2 μm.

[0202] (9-4) As shown in Figure 2D of the resist peeling, the substrate was immersed in the peeling solution 502A (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 60°C for 5 minutes to peel off the photoresist film 67.

[0203] (9-5) Etching the sputtered film outside the wiring area As shown in Figure 2E, the substrate was immersed for 1 minute in a solution of 98% concentrated sulfuric acid, 30% hydrogen peroxide, and pure water in a volume ratio of 1:1:5 to etch and remove the sputtered film of the Cu layer 66 and Ti layer 65 outside the wiring area.

[0204] (9-6) The surface treatment substrate was cleaned of wiring and insulating film surfaces using a plasma etching apparatus (Hitachi High-Tech Corporation, SPC-100B) under the following conditions: Power: 1000W Processing time: 1 minute Processing temperature: 25℃ Gas: O ２ Gas flow rate: 50 sccm. Processing pressure: 15 Pa.

[0205] (10) Fabrication of semiconductor elements C1 and C2 A pattern of cured resin composition 23 (through-hole dimensions of 30 μm × 30 μm) was formed on an 8-inch silicon substrate using the same procedure as in (8) so that the film thickness after curing was 8 μm.

[0206] Next, Ti and Cu sputtered films were formed on the entire surface of the cured resin film using the same procedure as in (9-1), and a photoresist pattern with a thickness of 35 μm and through-hole dimensions of 30 μm × 30 μm was formed using the same procedure as in (9-2). At this time, the photoresist pattern was formed with alignment so that its position matched that of the cured film of the resin composition 23.

[0207] Next, solder bumps were formed within the resist pattern by electroplating under the following conditions: Plating solution: Aqueous solutions of sulfuric acid, tin sulfate, and copper sulfate at concentrations of 2 M, 0.2 M, and 0.008 M, respectively. Plating temperature: 25°C Current density: 1 A / dm ２ Plating time: Adjusted so that the height is 30 μm.

[0208] Afterward, the same procedure as (9-4) to (9-6) was followed for cleaning, and finally, the circuit board was heat-treated in a ventilated oven at 170°C for 30 seconds to reflow the solder bumps and form hemispherical bumps M7.

[0209] Next, the back surface of the wafer, where no bumps were formed, was ground using a backgrinding device (DISCO Corporation, DAD3350) until the wafer thickness was 100 μm. Finally, the chips were separated into individual pieces using a dicing device (DISCO Corporation, DFD-6240) to obtain semiconductor devices.

[0210] The arrangement of bumps M7 on semiconductor elements C1 and C2 after individualization is shown in Figures 3A and 3B.

[0211] (11) Bonding of semiconductor elements C1 and C2 The semiconductor elements C1 and C2 were bonded to a substrate 10 including a multilayer wiring structure using a bonding apparatus (Trytech Co., Ltd., DB-100).

[0212] (12) A liquid encapsulant was molded on a substrate containing a multilayer wiring structure to which encapsulated chips made of mold resin 30 were bonded, using a mold at 155°C as shown in Figure 4, and after demolding from the mold, it was cured at 175°C for 2 hours.

[0213] (13) Laser delamination The glass substrate was delaminated by irradiating it with a laser from the side where the L1 layer was formed under the following conditions: Laser wavelength: 308 nm Irradiation energy: 200 mJ / cm ２ .

[0214] (14) Thermal cycle evaluation Substrates K1 to K10 containing multilayer wiring structures and semiconductor devices H1 to H10 were subjected to thermal cycling from -65°C to 150°C using a thermal cycle tester (PL-3 model, manufactured by Tabai Espec Co., Ltd.). Every 50 cycles, an ultrasonic flaw detection device (FS300III, manufactured by Hitachi Power Solutions, Ltd.) was used to observe for defects such as cracks and delamination within the substrates and semiconductor devices, and the minimum number of cycles at which defects were detected was measured.

[0215] (15) Fabrication of substrates K1 to K10 including multilayer wiring structure (15-1) Formation of conductive wiring layer M1 As shown in Figure 5A, a copper conductive wiring layer M1 with a width of 10 μm was formed on a glass substrate (60 mm x 60 mm) 50 as a support substrate, such that the center lines of the wiring are located at intervals of 0.05 mm parallel to the Y axis of the substrate, with the X axis of the substrate ranging from 3 mm to 57 mm.

[0216] (15-2) Formation of interlayer insulating film L1 Resin compositions 4, 5, 23-26, and 36-39 were applied to the entire substrate to cover M1 and pre-baked. As shown in Figure 5B, the alignment was adjusted so that the centers of the through-holes were located at 0.05 mm intervals along the center line of the wiring of M1 from 3 mm to 57 mm on the Y axis, and the substrate was exposed, developed, and cured to form an interlayer insulating film L1 with a thickness of 8 μm having (54 / 0.05+1) × (54 / 0.05+1) through-holes LL1 (5 μm × 5 μm squares).

[0217] (15-3) Formation of conductive wiring layer M2 and through wiring MM1 As shown in Figure 5C, a copper conductive wiring layer M2 with a width of 10 μm and copper through wiring MM1 were simultaneously formed on the L1 layer, so that the center lines of the wiring were positioned parallel to the X-axis of the substrate at intervals of 0.05 mm, from 3 mm to 57 mm along the Y-axis of the substrate. At this time, the alignment of M2 was finely adjusted so that it made contact with M1 via LL1.

[0218] (15-4) Formation of interlayer insulating film L2 Resin compositions 4, 5, 23-26, and 36-39 were applied to the entire substrate to cover M2 and pre-baked. The alignment was adjusted so that the centers of the through-holes were located at 0.05 mm intervals along the center line of the wiring of M2 from 3 mm to 57 mm in the X-axis, as shown in Figure 5D. Exposure and development were performed to cure the film, forming an interlayer insulating film L2 with a thickness of 8 μm and having (54 / 0.05+1) × (54 / 0.05+1) through-holes LL2 (5 μm × 5 μm squares).

[0219] (15-5) Formation of conductive wiring layer M3 and through-wiring MM2 As shown in Figure 5A, a copper conductive wiring layer M3 with a width of 10 μm and copper through-wiring MM2 were simultaneously formed on the L2 layer in the same pattern as in (15-1). At this time, the alignment of M3 was finely adjusted so that it made contact with M2 via LL2.

[0220] (15-6) Formation of interlayer insulating film L3 Resin compositions 4, 5, 23-26, and 36-39 were applied to the entire substrate so as to cover M3, and pre-baked to form an interlayer insulating film L3 with a thickness of 8 μm having through-holes LL3 (5 μm x 5 μm squares) in the same pattern as in (15-2), as shown in Figure 5B.

[0221] (15-7) Formation of conductive wiring layer M4 and through-wiring MM3 As shown in Figure 5C, a copper conductive wiring layer M4 with a width of 10 μm and copper through-wiring MM3 were simultaneously formed on the L3 layer in the same pattern as in (15-3). At this time, the alignment of M4 was finely adjusted so that it made contact with M3 via LL3.

[0222] (15-8) Formation of interlayer insulating film L4 Resin compositions 4, 5, 23-26, and 36-39 were applied to the entire substrate so as to cover M4, and pre-baked to form an interlayer insulating film L4 with a thickness of 8 μm having through-holes LL4 (5 μm x 5 μm squares) in the same pattern as in (15-4), as shown in Figure 5D.

[0223] (15-9) Formation of conductive wiring layer M5 and through-wiring MM4 As shown in Figure 5A, a copper conductive wiring layer M5 with a width of 10 μm and copper through-wiring MM4 were simultaneously formed on the L4 layer in the same pattern as in (15-1). At this time, the alignment of M5 was finely adjusted so that it made contact with M4 via LL4.

[0224] (15-10) Formation of the outermost layer film L5 Resin compositions 4, 5, 23-26, and 36-39 were applied to the entire substrate so as to cover the M5 layer, and pre-baked. As shown in Figure 5E, an interlayer insulating film L5 was formed by processing through holes LL5 (30 μm x 30 μm squares) for forming electrode pads M6 for bonding semiconductor elements C1 and C2 at the following positions.

[0225] (15-10-1) Through-hole for semiconductor element C1 junction: Along the X-axis, the Y-axis is positioned at 0.1 mm intervals from (60 / 2)-15 mm to 60 / 2+15 mm along the center line of the (54 / 0.1) + 2 × X5 + 1)th wiring (where X5 is an integer from -220 to -20).

[0226] (15-10-2) Through-hole for semiconductor element C2 junction: Along the X-axis, the Y-axis is positioned at 0.1 mm intervals from (60 / 2)-7.5 mm to 60 / 2+7.5 mm along the center line of the (54 / 0.1) + 2 × X6 + 1)th wiring (where X6 is an integer from 20 to 170).

[0227] (15-11) A copper electrode pad M6 was formed on LL5 as shown in Figure 6. At this time, the alignment of M6 was finely adjusted so that the center of LL5 and the center of M6 coincided.

[0228] (15-12) The support substrate 50 and the L1 layer were separated by a laser to obtain substrates K1 to K10 containing a multilayer wiring structure.

[0229] (16) Fabrication of semiconductor devices H1 to H10 After step (15-11), semiconductor elements C1 and C2 were bonded to the M6 ​​layer without laser peeling and sealed with molding resin 30. Then, peeling was performed in the same manner as in (15-12) above to obtain semiconductor devices H1 to H10 having a substrate including a multilayer wiring structure.

[0230] Synthesis Example 1 Under a stream of dry nitrogen, 14.0 g (0.07 mol) of diaminodiphenyl ether and 3.24 g (0.03 mol) of metaphenylenediamine were dissolved in 104 g of N-methyl-2-pyrrolidone (NMP). To this, 12.6 g (0.06 mol) of trimellitic anhydride chloride and 8.12 g (0.04 mol) of terephthalic acid chloride were added together with 10.0 g of NMP, and the mixture was reacted at a temperature of 5°C or lower for 6 hours. After the reaction was complete, the solution was added to 2 L of pure water to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 200°C for 24 hours to obtain a copolymer of polyamide and polyamide-imide (PA01).

[0231] Under a stream of dry nitrogen, 6.35 g (0.02 mol) of PA01 and 3.42 g (0.028 mol) of 4-dimethylaminopyridine (DMAP) were dissolved in 40 g of NMP, and 6.11 g (0.028 mol) of di-t-butyl dicarbonate (DTBC) was added. The mixture was reacted at room temperature for 16 hours. After the reaction was complete, 16.8 g of acetic acid was added, and the solution was added to 1 L of pure water to 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 polymer (PA01-tBOC) in which the amide group of PA01 was protected by the t-butoxycarbonyl group. At this time, according to the evaluation in (1), the protection rate of the amide group was 96%.

[0232] Synthesis Example 2 Under a stream of dry nitrogen, 17.5 g (0.07 mol) of diphenylmethane diisocyanate and 5.22 g (0.03 mol) of 2,4-tolylene diisocyanate were dissolved in 113 g of NMP. To this, 18.3 g (0.095 mol) of trimellitic anhydride was added along with 10.0 g of NMP, and the mixture was reacted at 120°C for 4 hours, 140°C for 2 hours, and 160°C for 2 hours. After cooling to room temperature, the solution was added to 2 L of pure water to 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 polyamide-imide copolymer (PAI01).

[0233] Under a stream of dry nitrogen, 6.53 g (0.02 mol) of PAI01 and 2.44 g (0.02 mol) of DMAP were dissolved in 40 g of NMP, and 4.37 g (0.02 mol) of DTBC was added. The mixture was reacted at room temperature for 16 hours. After the reaction was complete, 12 g of acetic acid was added, and the solution was poured into 1 L of pure water to 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 polymer (PAI01-tBOC) in which the amide group of PAI01 was protected by t-butoxycarbonyl groups. At this time, according to the evaluation in (1), the protection rate of the amide group was 92%.

[0234] Synthesis Example 3 Under a stream of dry nitrogen, 34.8 g (0.1 mol) of 9,9-bis(4-aminophenyl)fluorene was dissolved in 149 g of NMP. 17.3 g (0.085 mol) of isophthalic acid chloride was added together with 10.0 g of NMP, and the mixture was reacted at a temperature below 5°C for 4 hours. Then, 4.22 g (0.03 mol) of benzoyl chloride was added together with 10.0 g of NMP, and the mixture was reacted for another 2 hours at a temperature below 5°C, followed by a reaction at room temperature for 4 hours. After the reaction was complete, the solution was added to 2 L of pure water to 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 polyamide (PA02).

[0235] Under a stream of dry nitrogen, 9.80 g (0.02 mol) of PA02 and 9.77 g (0.04 mol) of DMAP were dissolved in 80 g of NMP, and 17.5 g (0.04 mol) of DTBC was added. The mixture was reacted at room temperature for 16 hours. After the reaction was complete, 24 g of acetic acid was added, and the solution was poured into 1 L of pure water to 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 polymer (PA02-tBOC) in which the amide group of PA02 was protected by t-butoxycarbonyl groups. At this time, according to the evaluation in (1), the protection rate of the amide group was 95%.

[0236] Synthesis Example 4 Under a stream of dry nitrogen, 24.5 g (0.095 mol) of bis(3-amino-4-hydroxy)propane and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were dissolved in 121 g of NMP. 17.3 g (0.085 mol) of isophthalic acid chloride was added together with 10.0 g of NMP, and the mixture was reacted at a temperature below 5°C for 4 hours. Then, 4.22 g (0.03 mol) of benzoyl chloride was added together with 10.0 g of NMP, and the mixture was reacted for a further 2 hours at a temperature below 5°C, followed by 4 hours of reaction at room temperature. After the reaction was complete, the solution was added to 2 L of pure water to 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 polyamide (PA03) containing hydroxyl groups.

[0237] Under a stream of dry nitrogen, 7.99 g (0.02 mol) of PA03 and 9.77 g (0.08 mol) of DMAP were dissolved in 80 g of NMP, and 17.5 g (0.08 mol) of DTBC was added. The mixture was reacted at room temperature for 16 hours. After the reaction was complete, 48 g of acetic acid was added, and the solution was poured into 1 L of pure water to 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 polymer (PA03-tBOC) in which the amide and hydroxyl groups of PA03 were protected with t-butoxycarbonyl groups. At this time, according to the evaluation in (1), the protection rate of the amide group was 90%, and the protection rate of the hydroxyl group was 98%.

[0238] Synthesis Example 5 Under a stream of dry nitrogen, 29.4 g (0.1 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 9.21 g (0.2 mol) of ethanol were added to 200 g of NMP. 20.2 g (0.2 mol) of triethylamine was slowly added dropwise over 1 hour at room temperature, and the mixture was then stirred at room temperature for 12 hours. 10.8 g (0.1 mol) of paraphenylenediamine was then added, followed by 75.9 g (0.2 mol) of 1-[bis(dimethylamino)methylene]-1H-benzotriazolium 3-oxidehexafluorophosphate and 176 g of NMP. The mixture was stirred at room temperature for 24 hours. After the reaction was complete, 60 g of acetic acid was added, and the solution was added to 2 L of pure water to precipitate the 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 (PI01) in which ethyl groups were bonded to the carboxylic acid side chains.

[0239] Under a stream of dry nitrogen, 9.16 g (0.02 mol) of PI01 and 9.77 g (0.04 mol) of DMAP were dissolved in 80 g of NMP, and 17.5 g (0.04 mol) of DTBC was added. The mixture was reacted at room temperature for 16 hours. After the reaction was complete, 24 g of acetic acid was added, and the solution was poured into 1 L of pure water to 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 polymer (PI01-tBOC) in which the amide group of PI01 was protected by t-butoxycarbonyl groups. At this time, according to the evaluation in (1), the protection rate of the amide group was 90%.

[0240] Synthesis Example 6 Under a stream of dry nitrogen, 9.80 g (0.02 mol) of PA02 was dissolved in 52.0 g of NMP, and 1.92 g (0.08 mol) of sodium hydride was added. The mixture was reacted at room temperature for 40 minutes. 7.36 g (0.04 mol) of 1-iodo-2-methylpropane was added, and the mixture was reacted at room temperature for another hour. After the reaction was complete, the solution was added to 1 L of pure water to 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 polymer (PA02-iBu) in which the hydrogen atoms bonded to the nitrogen atoms in the amide bonds of PA02 were replaced with isobutyl groups. At this time, NMR evaluation in the same manner as in (1) was performed, and it was found that 96% of the amide groups were replaced with isobutyl groups.

[0241] Synthesis Example 7 Under a stream of dry nitrogen, 34.8 g (0.1 mol) of 9,9-bis(4-aminophenyl)fluorene was dissolved in 165 g of NMP. 22.7 g (0.085 mol) of dodecanediol dichloride was added together with 10.0 g of NMP, and the mixture was reacted at a temperature below 5°C for 4 hours. Then, 4.22 g (0.03 mol) of benzoyl chloride was added together with 10.0 g of NMP, and the mixture was reacted for another 2 hours at a temperature below 5°C, followed by a reaction at room temperature for 4 hours. After the reaction was complete, the solution was added to 2 L of pure water to 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 polyamide (PA04).

[0242] Synthesis Example 8 Polyamide PA05 was obtained in the same manner as in Synthesis Example 3, except that 17.3 g (0.085 mol) of isophthalic acid chloride was replaced with 19.7 g (0.085 mol) of 1,3-phenylene diacetate chloride. Furthermore, the polymer (PA05-tBOC) was obtained in the same manner as in Synthesis Example 3, except that 9.80 g (0.02 mol) of PA02 was replaced with 10.1 g (0.02 mol) of PA05. At this time, according to the evaluation in (1), the protection rate of the amide groups of PA05-tBOC was 92%.

[0243] Synthesis Example 9 A polyimide precursor PI02 was obtained in which a methacryloxyethyl group was bonded to the carboxylic acid side chain by the same method as in Synthesis Example 5, except that 9.21 g (0.2 mol) of ethanol was replaced with 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate. Furthermore, a polymer (PI02-tBOC) was obtained by the same method as in Synthesis Example 5, except that 9.16 g (0.02 mol) of PI01 was replaced with 12.5 g (0.02 mol) of PI02. At this time, according to the evaluation in (1), the protection rate of the amide group of PI02-tBOC was 93%.

[0244] Synthesis Example 10 A polyimide precursor PI03 was obtained in the same manner as in Synthesis Example 5, except that 29.4 g (0.1 mol) of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride was replaced with 31.0 g (0.1 mol) of 3,3',4,4'-diphenyl ethertetracarboxylic acid dianhydride, 10.8 g (0.1 mol) of paraphenylenediamine was replaced with 20.0 g (0.1 mol) of 4,4'-diaminodiphenyl ether, and 9.21 g (0.2 mol) of ethanol was replaced with 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate. Furthermore, a polymer (PI03-tBOC) was obtained in the same manner as in Synthesis Example 5, except that 9.16 g (0.02 mol) of PI01 was replaced with 14.7 g (0.02 mol) of PI03. At this time, based on the evaluation in (1), the protection rate of the amide group of PI03-tBOC was 90%.

[0245] Synthesis Example 11 A polyimide precursor PI04, in which an ethyl group was bonded to the carboxylic acid side chain, was obtained by the same method as in Synthesis Example 5, except that 29.4 g (0.1 mol) of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride was replaced with 31.0 g (0.1 mol) of 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, and 10.8 g (0.1 mol) of paraphenylenediamine was replaced with 20.0 g (0.1 mol) of 4,4'-diaminodiphenyl ether. Furthermore, a polymer (PI04-tBOC) was obtained by the same method as in Synthesis Example 5, except that 9.16 g (0.02 mol) of PI01 was replaced with 11.3 g (0.02 mol) of PI04. At this time, according to the evaluation in (1), the protection rate of the amide group of PI04-tBOC was 90%.

[0246] Synthesis Example 12 A polyimide precursor PI05 was obtained in the same manner as in Synthesis Example 5, except that 29.4 g (0.1 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was replaced with 30.0 g (0.1 mol) of 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, and 10.8 g (0.1 mol) of paraphenylenediamine was replaced with 20.0 g (0.1 mol) of 4,4'-diaminodiphenyl ether. Furthermore, a polymer (PI05-tBOC) was obtained in the same manner as in Synthesis Example 5, except that 9.16 g (0.02 mol) of PI01 was replaced with 11.1 g (0.02 mol) of PI05. At this time, based on the evaluation in (1), the protection rate of the amide group of PI05-tBOC was 94%.

[0247] Synthesis Example 13 Under a stream of dry nitrogen, 34.8 g (0.1 mol) of 9,9-bis(4-aminophenyl)fluorene was dissolved in 149 g of NMP. To this, 8.63 g (0.0425 mol) of isophthalic acid chloride and 12.8 g (0.0425 mol) of 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione were added along with 10.0 g of NMP, and the mixture was reacted at a temperature of 5°C or lower for 4 hours, followed by reaction at room temperature for 4 hours. After the reaction was complete, the solution was added to 2 L of pure water to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 200°C for 24 hours to obtain a polymer of polyamide and polyimide (PA06).

[0248] Under a stream of dry nitrogen, 10.3 g (0.02 mol) of PA06 and 4.89 g (0.02 mol) of DMAP were dissolved in 80 g of NMP, and 8.75 g (0.02 mol) of DTBC was added. The mixture was reacted at room temperature for 16 hours. After the reaction was complete, 24 g of acetic acid was added, and the solution was poured into 1 L of pure water to 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 polymer (PA06-tBOC) in which the amide group of PA06 was protected by t-butoxycarbonyl groups. At this time, according to the evaluation in (1), the protection rate of the amide group was 98%.

[0249] Synthesis Example 14 Under a stream of dry nitrogen, 34.8 g (0.1 mol) of 9,9-bis(4-aminophenyl)fluorene was dissolved in 149 g of NMP. To this, 10.3 g (0.051 mol) of isophthalic acid chloride and 10.2 g (0.034 mol) of 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione were added along with 10.0 g of NMP, and the mixture was reacted at a temperature of 5°C or lower for 4 hours, followed by reaction at room temperature for 4 hours. After the reaction was complete, the solution was added to 2 L of pure water to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 200°C for 24 hours to obtain a copolymer of polyamide and polyimide (PA07).

[0250] Under a stream of dry nitrogen, 10.1 g (0.02 mol) of PA07 and 5.87 g (0.024 mol) of DMAP were dissolved in 80 g of NMP, and 10.5 g (0.024 mol) of DTBC was added. The mixture was reacted at room temperature for 16 hours. After the reaction was complete, 24 g of acetic acid was added, and the solution was poured into 1 L of pure water to 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 polymer (PA07-tBOC) in which the amide group of PA07 was protected by t-butoxycarbonyl groups. At this time, according to the evaluation in (1), the protection rate of the amide group was 96%.

[0251] Table 1-1 shows the diamine compounds, acid compounds, terminal compounds, and organic groups ester-bonded to carboxylic acid side chains used in polymer polymerization before amide and hydroxyl group protection of the polymer ((A) resin). Table 1-2 shows the protecting groups for the amide and hydroxyl groups of the polymer after amide and hydroxyl group protection ((A) resin), the protection rate of the amide and hydroxyl groups, which of the general formulas (1) to (5) it corresponds to, and the proportion of structural units of (a-1) and (a-2) described in claim 6.

[0252] Resin compositions 1 to 39 were prepared by blending the polymers obtained in synthesis examples 1 to 14, (B) solvent, (C) thermal acid generator, and (D) photoacid generator in the types and amounts shown in Table 2-1. Furthermore, (E) other additives (polymerization initiator, polymerizable compound, rust inhibitor, adhesion improver) were blended in the types and amounts shown in Table 2-2.

[0253] The abbreviations for the solvents in Table 2 are as follows: PGMEA: Propylene glycol monomethyl ether acetate CHN: Cyclohexanone CPN: Cyclopentanone PGME: Propylene glycol monomethyl ether NMP: N-methyl-2-pyrrolidone GBL: Gamma butyrolactone.

[0254] Furthermore, in Table 2, V1 to V7 represent the following compounds: V1: Benzyl-4-hydroxyphenylmethylsulfonium V2: Benzeneacetonitrile, 2-methyl-α-[[(4-methylphenyl)oxy]imino]-3(2H)-thienylidene V3: 1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime) V4: N-phenyldiethanolamine V5: Tetraethylene glycol dimethacrylate V6: Benzotriazole V7: 3-Glycidoxypropyltrimethoxysilane.

[0255] Table 3 shows the tensile modulus of resin compositions 1-5, 18, 19, 22-28, and 36-39, and the absorbance of resin (A) used in the preparation of resin compositions 1-5, 18, 19, 22-28, and 36-39 before and after heat treatment.

[0256] Furthermore, Table 4 shows the sensitivity measurement results for resin compositions 4, 5, 23-26, and 36-39.

[0257] For Examples 1 to 18 and Comparative Examples 1 to 21, and resin compositions 1 to 39, (2) solvent solubility and (3) film thickness retention rate (T2 / T1) were evaluated. The results are shown in Table 5.

[0258] Examples 19-28: Thermal cycle tests were performed on substrates K1-K10 containing multilayer wiring structures, and the minimum number of cycles at which cracks and delamination were observed was measured. The results are shown in Table 6-1.

[0259] Examples 29-38: Thermal cycle tests were performed on semiconductor devices H1-H10, and the minimum number of cycles at which cracks and delamination were observed was measured. The results are shown in Table 6-2.

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269] 1 Semiconductor device 10 Substrate containing a multilayer wiring structure 10A Side of the substrate containing the multilayer wiring structure on the semiconductor element side 10B Side of the substrate containing the multilayer wiring structure on the support substrate side 30 Molding resin 301 Side of the molding resin opposite to the substrate containing the multilayer wiring structure 10 302 Side of the molding resin on the substrate containing the multilayer wiring structure 10 50 Support substrate 61 Interlayer insulating film or support substrate 62 Conductive wiring layer 63 Interlayer insulating film 64 Through-holes in the interlayer insulating film 65 Ti layer 66 Cu layer 67 Photoresist layer 68 Through-holes in the photoresist 69 Cu plating layer C1, C2 Semiconductor element C11 Side of the semiconductor element without bump M7 C12 Side of the semiconductor element with bump M7 C13 Side of the semiconductor element L1-L4 Interlayer insulating film L5 Outermost layer film LL1-LL5 Through-holes formed in the interlayer insulating films L1-L4 and the outermost layer film L5: M1-M5 Conductive wiring layers: MM1-MM5 Through-holes: M6 Electrode pads: M7 Bumps

Claims

A resin having amide bonds in the structural units of the polymer main chain, wherein some or all of the amide bonds are protected by acid-dissociable groups (hereinafter referred to as "(A) resin"). 　 The resin according to claim 1, wherein the (A) resin is a resin selected from the group consisting of polyamides, polyamide-imides, polyimide precursors, and copolymers thereof. 　 The resin according to claim 1, wherein the acid-dissociable group has an oxycarbonyl group. 　 The resin according to claim 2, wherein the resin (A) has one or more structural units selected from formulas (1) to (5). (In formula (1), R １ and R ２ Each of these independently represents a hydrogen atom or an acid-dissociable group having 1 to 50 carbon atoms, R １ and R ２ At least one of them represents an acid-dissociable group having 1 to 50 carbon atoms. １ This represents a divalent organic group with 2 to 50 carbon atoms, X １ (This represents a divalent organic group with 1 to 50 carbon atoms.) (In formula (2), R ３ represents an acid dissociable group having 1 to 50 carbon atoms, Y ２ represents a divalent organic group having 2 to 50 carbon atoms, and X ２ represents a trivalent organic group having 3 to 50 carbon atoms.) (In formula (3), R ４ and R ５ Each of these independently represents a hydrogen atom or an acid-dissociable group having 1 to 50 carbon atoms, R ４ and R ５ At least one of them represents an acid-dissociable group having 1 to 50 carbon atoms. ６ and R ７ Each of these independently represents a hydrogen atom or an acid-dissociable group having 1 to 50 carbon atoms. ３ This represents a tetravalent organic group with 4 to 50 carbon atoms, X ３ (This represents a divalent organic group with 1 to 50 carbon atoms.) (In formula (4), R ８ and R ９ Each of these independently represents a hydrogen atom or an acid-dissociable group having 1 to 50 carbon atoms, R ８ and R ９ At least one of them represents an acid-dissociable group having 1 to 50 carbon atoms. １０ and R １１ Each of these independently represents a monovalent organic group having 1 to 10 carbon atoms. ４ represents a divalent organic group with 2 to 50 carbon atoms, X ４ (This represents a tetravalent organic group with 4 to 50 carbon atoms.) (In formula (5), R １２ and R １３ Each of these independently represents a hydrogen atom or an acid-dissociable group having 1 to 50 carbon atoms, R １２ and R １３ At least one of them represents an acid-dissociable group having 1 to 50 carbon atoms. １４ and R １５ Each of these independently represents a hydrogen atom or an acid-dissociable group having 1 to 50 carbon atoms. １６ and R １７ Each of these independently represents a monovalent organic group having 1 to 10 carbon atoms. ５ represents a tetravalent organic group with 4 to 50 carbon atoms, X ５ (This represents a tetravalent organic group with 4 to 50 carbon atoms.) 　 In equations (1) to (5) above, X １ ~X ５ The resin according to claim 4, wherein Y1 is an organic group that does not contain an amide bond. 　 The resin according to claim 4, wherein the structural units of (a-1) and (a-2) described below constitute 60 mol% or more of the total structural units of the resin (A) described above. (a-1) Structural units of equations (1) to (5) (a-2) In equations (1) to (5), R １ ~R ５ , R ８ , R ９ , R １２ , and R １３ A structural unit in which all are hydrogen atoms In the above formula (1), X １ This is an organic group having an aromatic ring, -NR １ -CO- group and -NR ２ The aromatic ring is directly bonded to the carbonyl group of the -CO- group, and Y １ This is an organic group having an aromatic ring, -NR １ -CO- group and -NR ２ The resin according to claim 4, wherein the aromatic ring is directly bonded to the nitrogen atom of the -CO- group. 　 The absorbance A1 per 1 μm of film thickness of the film obtained by applying the resin (A) in a solution dissolved in a solvent to a substrate and drying it at 100°C for 2 minutes using a hot plate, and the absorbance A2 per 1 μm of film thickness of the film obtained by heat-treating the film at 250°C for 1 hour using an oven after drying, are 0.003 < A1 < 0.3 and A2 ≥ 0.3 The resin according to claim 1. 　 A resin composition comprising (A) the resin and (B) the solvent according to claim 1. 　 The resin composition according to claim 9, wherein the tensile modulus of the film heat-treated at 250°C for 1 hour is 3.5 GPa or more and 20 GPa or less. 　 When the total amount of solvent (B) is 100% by mass, the Hansen solubility parameter is 22.5 (MPa). １／２ The resin composition according to claim 9, wherein the solvent less than 50% by mass of the total solvent. 　 The resin composition according to claim 9, further comprising (C) a thermal acid generator. 　 Furthermore, the resin composition according to claim 9, further comprising (D) a photoacid generator. 　 A cured product of the resin composition according to any one of claims 9 to 13. 　 A method for producing the (A) resin according to claim 1, comprising the step of reacting a resin having an amide bond in the structural unit of the polymer main chain with a compound represented by formula (11). (In formula (11), R ２８ and R ２９ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms. 　 A substrate comprising a multilayer wiring structure, wherein the interlayer insulating film in the multilayer wiring structure is made of the cured product described in claim 14. 　 A semiconductor device having the cured product described in claim 14. 　 A semiconductor device comprising a substrate including a multilayer wiring structure and a semiconductor element bonded to the substrate, wherein the interlayer insulating film in the multilayer wiring structure is made of the cured product described in claim 14. 　 Furthermore, the semiconductor device according to claim 18, wherein the printed circuit board is further comprising a printed circuit board, and the side of the printed circuit board that is not bonded to the semiconductor elements of the substrate including the multilayer wiring structure is directly bonded to the printed circuit board without the use of another organic substrate. A communication device comprising the semiconductor device described in claim 18. A communication device comprising the semiconductor device described in claim 19. 　 A display device having the cured product according to claim 14. 　 A secondary battery having the cured product described in claim 14. 　 A capacitor having the cured product according to claim 14.

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