JP2023115093A - Resin composition, and method for producing cured film - Google Patents

Abstract

To provide a resin composition that gives a cured film that adheres to copper after a cure process and causes no steps with the exposed copper surface after polishing, and a method for producing a cured film using the resin composition, and a semiconductor device.SOLUTION: A resin composition contains (A) 100 pts.mass of resin that has a neutral functional group as a substituted body of an acidic functional group or a basic functional group in a side chain, and is at least one selected from the group consisting of a polyimide precursor as polyamide acid and/or polyamide acid ester, a polyoxazole precursor as polyhydroxy amide, polyamino amide, polyamide, polyamide imide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole, and (B) 1-50 pts.mass of a compound having an aromatic sulfonic acid ester structure.SELECTED DRAWING: None

Description

The present invention relates to, for example, an insulating material for electronic parts, a resin composition used for forming a passivation film, a buffer coat film and an interlayer insulating film in a semiconductor device, and a method for producing a cured film using the resin composition.

BACKGROUND ART Conventionally, polyimide resins, which have excellent heat resistance, electrical properties and mechanical properties, have been used as insulating materials for electronic parts, passivation films, surface protective films, interlayer insulating films, etc. for semiconductor devices. Polyimide resins, which are excellent in heat resistance and mechanical properties, are poor in heat melting and solubility in solvents, and poor in workability. Therefore, such a polyimide resin uses a liquid resin composition in which a polyimide precursor resin having excellent solvent solubility is dissolved in a solvent, is applied, and after drying, the polyimide precursor is ring-closed by a high-temperature curing step. It is common to carry out processing in a step of obtaining a cured film of a polyimide resin.

In recent semiconductor devices, before a large number of semiconductor chips formed on a wafer are cut into individual pieces, wiring portions for electrically connecting the semiconductor chips and a circuit board on which the semiconductor devices are mounted are formed on the surface of the semiconductor chips. There is a so-called wafer level chip size package (hereinafter referred to as WLCSP) in which an electrode portion is formed and an insulating portion for sealing the wiring portion and the electrode portion is formed. In this WLCSP, since the wiring part, the electrode part and the insulating part are formed so as not to protrude from the side surface of the semiconductor chip, it is attracting attention as a method for realizing a reduction in size and weight of the semiconductor device.

As an interlayer insulating film layer for such a WLCSP, a technique for forming high-density wiring using polyimide and chemical mechanical polishing has been disclosed (see Non-Patent Document 1).

Since polyimide resins have poor adhesion to copper, a method has been proposed for improving the adhesion of copper or copper alloys by adding triazole or a derivative thereof to a composition containing a polyimide precursor (Patent Document 1. reference).

Also, a method of providing good adhesion of copper to polyimide by introducing an unsaturated heterocyclic group or the like to the terminal of polyimide has been proposed (see Patent Document 2).

Japanese Patent Application Laid-Open No. 2005-010360 JP-A-6-106678

Proceedings of the Conference of the Japan Institute of Electronics Packaging Volume: 22nd Page: 65-66

However, when the composition described in Patent Document 2 is applied to a semiconductor device having copper wiring, there is a problem that peeling occurs at the interface between copper and polyimide after the curing process, and polyimide does not adhere to copper. Further, when a polyimide film formed on a substrate having copper wiring is polished, there is a problem that a step occurs between the exposed copper and the polyimide film. Therefore, the present invention provides a resin composition that adheres to copper after a curing step and gives a cured film that does not cause a step on the exposed copper surface after polishing, a method for producing a cured film using the resin composition, and a semiconductor device. intended to provide

The present inventors have found that a compound having an aromatic sulfonate ester structure is combined with a resin having a neutral functional group, which is a substitute for an acidic functional group or a basic functional group, in the side chain, thereby reducing the copper content after the curing step. The present inventors have found that a resin composition can be obtained that adheres well to the surface of the copper and gives a cured film that does not cause a difference in level with the exposed copper surface after polishing, thereby completing the present invention. That is, the present invention is as follows.

[1] (A) Polyimide precursors and polyhydroxyamides that are polyamic acids and/or polyamic acid esters and have neutral functional groups in side chains that are substitutions of acidic or basic functional groups. At least one resin selected from the group consisting of polyoxazole precursors, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, polybenzimidazoles, and polybenzthiazoles: 100 parts by mass, and (B) fragrance A resin composition containing 1 to 50 parts by mass of a compound having a group sulfonate structure.
[2] The resin composition according to Aspect 1, wherein the neutral functional group is one or more groups selected from the group consisting of methacryl groups, acryl groups, and styryl groups.
[3] The resin (A) has the following general formula (1):
{wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently In, a hydrogen atom, or the following general formula (1a):
(wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10). It is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. }, the following general formula (2):
{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and has the same structure, or a plurality of wherein R ₆ is an organic group having at least one radically polymerizable unsaturated bond group of 3-20 carbon atoms, and n ₂ is an integer of 1-1000. } and the following general formula (3):
{wherein X ₅ is a 4- to 14-valent organic group, Y ₅ is a 2- to 12-valent organic group, and R ₇ and R ₈ are each independently a phenolic hydroxyl group and a sulfonic acid group; or a structure in which a group selected from a thiol group is substituted with an organic group having at least one selected from the group consisting of a methacryl group, an acryl group and a styryl group, n ₅ is an integer of 3 to 200, and m ₂ and m ₃ represent integers from 0 to 10; } The resin composition according to aspect 1 or 2 above, which is at least one resin selected from the group consisting of polyimides having a structure represented by:
[4] X ₁ in the general formula (1) is represented by the following formula:
The resin composition according to aspect 3 above, comprising at least one structure selected from the group consisting of structures represented by:
[5] The resin composition according to any one of the above aspects 1 to 4, wherein (B) the compound having an aromatic sulfonate structure is a quinonediazide compound.
[6] The resin composition according to aspect 5, wherein the quinonediazide compound has an average of 2.4 or more quinonediazide structures in the molecule.
[7] The compound (B) having an aromatic sulfonate structure is represented by the following general formulas (4) to (8):
{In Formula (4), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms, and X ₃ and X ₄ each independently represent a hydrogen atom or a carbon represents a monovalent organic group of numbers 1 to 60, r1, r2, r3 and r4 are each independently an integer of 0 to 5, and at least one of r3 and r4 is an integer of 1 to 5 , r1+r3=5 and r2+r4=5. }
{In formula (5), Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X ₅ , X ₆ , X ₇ and X ₈ each independently represent a monovalent organic group having 1 to 30 carbon atoms. represents an organic group, r6 is an integer of 0 or 1, r5, r7, r8 and r9 are each independently an integer of 0 to 3, r10, r11, r12 and r13 are each independently is an integer from 0 to 2, and at least one of r10, r11, r12 and r13 is 1 or 2; }
{In formula (6), r14 represents an integer of 1 to 5, r15 is an integer of 3 to 8, and (r14 × r15) L are each independently 1 having 1 to 20 carbon atoms represents a valent organic group, (r15) T are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and (r15) S are each independently hydrogen represents an atom or a monovalent organic group having 1 to 20 carbon atoms; }
{In formula (7), A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group. }
{In formula (8), r17, r18, r19 and r20 are each independently an integer of 0 to 2, at least one of r17, r18, r19 and r20 is 1 or 2, and X10 to X19 each independently represents at least one monovalent group selected from the group _consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group and an _{acyl group} ; , each independently a single bond, -O-, -S-, -SO-, -SO2-, -CO-, -CO2-, cyclopentylidene, cyclohexylidene, phenylene and divalent having 1 to 20 carbon atoms represents at least one divalent group selected from the group consisting of organic groups of } is a 1,2-naphthoquinonediazide-4-sulfonic acid ester and/or a 1,2-naphthoquinonediazide-5-sulfonic acid ester of at least one compound selected from the group consisting of hydroxy compounds represented by The resin composition according to any one of aspects 1 to 6 above.
[8] The hydroxy compound represented by the general formula (4) is represented by the following general formula (4a):
{In formula (4a), each r16 is independently an integer of 0 to 2, and each _X9 independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. } The resin composition according to aspect 7 above, which is a compound represented by:
[9] In the general formula (5), Z is the following formula:
The resin composition according to aspect 7 or 8 above, which is at least one group selected from the group consisting of tetravalent groups represented by:
[10] The resin composition according to any one of the above aspects 1 to 9, further comprising (C) a photopolymerization initiator.
[11] The photopolymerization initiator (C) has the following general formula (10):
{In Formula (10), R ₁ , R ₂ and R ₃ each represent a monovalent organic group, and R ₁ and R ₂ may be linked together to form a ring structure} 11. The resin composition according to aspect 10 above, which is an oxime ester compound.
[12] The resin composition according to any one of the above aspects 1 to 11, further comprising (D) a photopolymerizable compound.
[13] (1) A step of forming a resin film on a substrate by applying the resin composition according to any one of the above aspects 1 to 12 onto the substrate;
(2) forming a cured film by heat-treating the resin film;
(3) flattening the cured film by polishing;
A method for producing a cured film, comprising:

According to the present invention, a compound having an aromatic sulfonate ester structure is combined with a resin having a neutral functional group, which is a substitute for an acidic functional group or a basic functional group, in a side chain, thereby reducing the copper content after the curing step. It is possible to obtain a resin composition that adheres well to and gives a cured film that does not cause a step difference with the exposed copper surface after polishing, and a method for producing a cured film using the resin composition, and a semiconductor device. can be provided.

Illustrative embodiments of the invention are specifically described below. Throughout the present specification, structures represented by the same reference numerals in general formulas may be the same or different when a plurality of structures are present in a molecule.

<Resin composition>
One aspect of the present invention provides a resin composition comprising (A) resin: 100 parts by mass and (B) a compound having an aromatic sulfonate structure: 1 to 50 parts by mass as essential components. (A) The resin has, in a side chain, a neutral functional group that is a substitute for an acidic functional group or a basic functional group. (A) resin is a polyimide precursor polyamic acid and / or polyamic acid ester, a polyoxazole precursor polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and poly at least one resin selected from the group consisting of benzthiazoles; The resin composition may be photosensitive or non-photosensitive, but in one aspect, the resin composition includes (A) a resin having a photopolymerizable group (for example, a radically polymerizable unsaturated bond such as an olefinic double bond) and , (B) a compound having an aromatic sulfonate structure, (C) a photopolymerization initiator, and optionally (D) a photopolymerizable compound.

(A) resin (A) resin has a neutral functional group that is a substitute for an acidic functional group or a basic functional group in a side chain, and is a polyimide precursor polyamic acid, polyamic acid ester, polyoxazole precursor At least one resin selected from the group consisting of polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, polybenzimidazoles, and polybenzothiazoles. The resin component contained in the resin composition is mainly composed of the resin (A). Here, the main component means that the (A) resin is contained in an amount of 60% by mass or more, preferably 80% by mass or more, and in one embodiment, 100% by mass. In one aspect, the resin composition may optionally contain an additional resin other than the (A) resin, and the additional resin may be a polyimide precursor polyamic acid, a polyamic acid ester, a polyoxazole precursor. Polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, polybenzimidazoles, and polybenzthiazoles other than (A) resins, as well as novolac resins, polyhydroxystyrenes, and acrylic resins. , epoxy resin, silicon resin, elastomer, and the like.

The weight-average molecular weight of the resin (A) is preferably 1,000 or more, more preferably 5,000 or more, in terms of polystyrene conversion by gel permeation chromatography, from the viewpoint of heat resistance and mechanical properties after heat treatment. The upper limit is preferably 100,000 or less. 9,000 to 50,000 is more preferable from the viewpoint of the solubility in the solvent of the resin composition and the viewpoint of physical properties.

(A) The resin has a neutral functional group side chain which is a substitute of an acidic functional group or a basic functional group. In the present disclosure, the acidic functional group is an electron pair acceptor group with an acid dissociation constant pKa of 10 or less, the basic functional group is an electron pair donor group, and the neutral functional group is the above acidic functional group and basic It means a group that is not one of the functional groups. Using a resin having a neutral functional group in its side chain in combination with (B) a compound having an aromatic sulfonate structure contributes to achieving good adhesion between copper and the resin. Examples of acidic functional groups include acid groups (carboxylic acid groups, sulfonic acid groups, etc.), acid anhydride groups, phenolic hydroxyl groups, thiol groups, and the like. An amino group etc. are mentioned as a basic functional group. A neutral functional group is an acidic functional group or a basic functional group that forms an ester bond, amide bond, urea bond, urethane bond, ionic bond, etc. is substituted for the neutral structure of Examples of neutral functional groups include alkyl groups, alkenyl groups, alkenyl groups, allyl groups, and aryl groups, and they may have structures such as methacryl groups, acryl groups, and styryl groups. In one aspect, the (A) resin has an acidic functional group or a basic functional group remaining. (A) The presence and amount of neutral functional groups, acidic functional groups and basic functional groups in the resin can be confirmed by ¹ H-NMR. (A) A preferred example of the abundance of the neutral functional group in the resin is 50 mol% or more, preferably 90 mol, with respect to 100 mol% of the total of the acidic functional group, basic functional group and neutral functional group. % is more preferred, and 100 mol % is most preferred. (A) Resins are polyimide precursors such as polyamic acid and polyamic acid ester, and polyoxazole precursors such as polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzthiazole. selected from the group consisting of They are advantageous in heat resistance and mechanical properties. Among them, polyimide precursors, polyamides, polybenzoxazole precursors, and polyimides are preferably used because the resins after heat treatment are excellent in heat resistance and mechanical properties.

[Polyimide precursor]
In the resin composition of the present invention, one example of the (A) resin, which is preferable from the viewpoint of heat resistance and film properties (especially elongation), is represented by the following general formula (1):
{wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently , a hydrogen atom, or the general formula (1a):
(wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10). It is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. } is a polyimide precursor having a structure represented by. A polyimide precursor is converted to a polyimide by subjecting it to a heating (for example, 200° C. or higher) cyclization treatment.

In the above general formula (1), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably , -COOR ₁ group and -COOR ₂ group and -CONH- group are aromatic groups or alicyclic groups in the ortho position to each other. The tetravalent organic group represented by X ₁ is preferably an aromatic ring-containing organic group having 6 to 40 carbon atoms, more preferably the following formula (1b):
Examples include, but are not limited to, structures represented by: Further, the structure of _X1 may be one type or a combination of two or more types within a molecule or between molecules. By combining two or more types of structures of _X1 , a resin having excellent film physical properties can be obtained. The X ₁ group having the structure represented by formula (1b) above is particularly preferable in terms of achieving both heat resistance and film physical properties. Among these, in particular, X ₁ has the following formula:
From the viewpoint of adhesion between copper and resin and in-plane uniformity after polishing, it is preferable to include at least one structure selected from the group consisting of structures represented by:

In general formula (1) above, the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive properties. Formula (1c) below:
and the following formula (1d):
{wherein R ₂₃ and R ₂₄ are each independently a methyl group (--CH ₃ ), an ethyl group (--C ₂ H ₅ ), a propyl group (--C ₃ H ₇ ) or a butyl group (--C ₄ H ₉ ). }, but not limited thereto. Further, the structure of Y ₁ may be one type or a combination of two or more types in the molecule or in the molecule. By combining two or more types of structures of _Y1 , a resin having excellent film physical properties can be obtained. A Y ₁ group having a structure represented by formulas (1c) and/or (1d) above is particularly preferable in terms of achieving both heat resistance and film physical properties. Among these, in particular, Y ₁ is expressed by the following formula from the viewpoint of elongation:
It is preferably at least one structure selected from the group consisting of structures represented by

Regarding R ₁ and R ₂ , R ₃ in general formula (1a) above is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are preferably hydrogen atoms from the viewpoint of photosensitive properties. In addition, _m1 is an integer of 2 or more and 10 or less, preferably 2 or more and 4 or less, from the viewpoint of film thickness uniformity of the coating film.

(A) When a polyimide precursor is used as the resin, methods for substituting an acidic functional group with a neutral functional group include an ester bond type and an ionic bond type. The former is a method of introducing a compound having a photopolymerizable group, i.e., an olefinic double bond, into the side chain of the polyimide precursor via an ester bond, and the latter is a method of introducing a carboxyl group of the polyimide precursor and an amino group ( In this method, the amino group of the meth)acrylic compound is bonded via an ionic bond to impart a photopolymerizable group.

The above-mentioned ester bond type polyimide precursor is first composed of a tetracarboxylic dianhydride containing the above-mentioned tetravalent organic group X ₁ , an alcohol having a photopolymerizable unsaturated double bond, and optionally a carbon number of 1. After preparing a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester form) by reacting it with a saturated aliphatic alcohol of 1 to 4, this is combined with the above-mentioned divalent organic group Y ₁ It is obtained by amide polycondensation with diamines containing.

(Preparation of acid/ester form)
Examples of tetracarboxylic dianhydrides containing a tetravalent organic group X ₁ that are suitably used in the present invention for preparing an ester bond type polyimide precursor include pyromellitic anhydride, diphenyl ether-3, 3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride anhydride, diphenylsulfone-3,3′,4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3′,4,4′-tetracarboxylic dianhydride, 2,2-bis(3, 4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane and the like, but are not limited to these. not something. Moreover, these may be used alone, or two or more of them may be mixed and used.

In the present invention, alcohols having a photopolymerizable unsaturated double bond that are suitably used for preparing an ester bond type polyimide precursor include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy -3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxy Propyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3- Propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate , 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.

A saturated aliphatic alcohol having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc., can be partially mixed with the above alcohols.

dissolving the above tetracarboxylic dianhydride suitable for the present invention and the above alcohol in the presence of a basic catalyst such as pyridine in an appropriate reaction solvent at a temperature of 20 to 50° C. for 4 to 10 hours with stirring; By mixing, the esterification reaction of the acid anhydride proceeds and the desired acid/ester can be obtained.

The reaction solvent preferably dissolves completely the acid/ester and the polyimide precursor which is the amide polycondensation product of this and a diamine component. -dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gamma-butyrolactone and the like.

Other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, Ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene etc. These may be used alone or in combination of two or more as needed.

(Preparation of polyimide precursor)
To the above acid/ester form (typically a solution in the above reaction solvent), under ice cooling, a suitable dehydration condensation agent such as dicyclocarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline , 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. are added and mixed to convert the acid/ester form into a polyanhydride, which is then Then, a diamine containing a divalent organic group Y ₁ preferably used in the present invention is separately dissolved or dispersed in a solvent and added dropwise, and amide polycondensation is performed to obtain the desired polyimide precursor. can be done.

Examples of diamines containing a divalent organic group _Y1 preferably used in the present invention include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3, 3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone , 3,3′-diaminodiphenyl sulfone, 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis (4-aminophenoxy)benzene,

1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-amino phenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis (4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2 - bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolysine sulfone, 9,9-bis(4-aminophenyl)fluorene, and some of the hydrogen atoms on their benzene rings are methyl groups, ethyl group, hydroxymethyl group, hydroxyethyl group, those substituted with halogen, etc., such as 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'- Examples include, but are not limited to, dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

In addition, for the purpose of improving the adhesion between the resin layer formed on the substrate and various substrates by applying the resin composition of the present invention on the substrate, 1,3-bis ( Diaminosiloxanes such as 3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized.

After the completion of the amide polycondensation reaction, water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution are optionally filtered off, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is It is added to the obtained polymer component, the polymer component is precipitated, and the polymer is purified by repeating redissolution, reprecipitation, etc., and vacuum drying to obtain the desired polyimide precursor. release. In order to improve the degree of purification, the polymer solution may be passed through a column packed with anion and/or cation exchange resins swollen with a suitable organic solvent to remove ionic impurities.

On the other hand, the ionic bond type polyimide precursor is typically obtained by reacting a tetracarboxylic dianhydride with a diamine. In this case, at least one of the structures of the sites corresponding to R ₁ and R ₂ in the general formula (1) of the tetracarboxylic dianhydride used is a hydrogen atom.

The tetracarboxylic dianhydride is preferably a tetracarboxylic anhydride having the structure of formula (1b) above, and the diamine is preferably a diamine having the structure of formula (1c) or (1d) above. By adding a (meth)acrylic compound having an amino group, which will be described later, to the obtained polyamide precursor, a photopolymerizable group is imparted by an ionic bond between the carboxyl group and the amino group.

The molecular weight of the ester bond type and the ion bond type polyimide precursor is preferably 8,000 to 150,000, preferably 9,000, when measured by polystyrene-equivalent weight average molecular weight by gel permeation chromatography. More preferably ~50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in a solvent is good and the resin composition can be easily applied. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Also, the weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko.

[polyamide]
Another example of the preferred (A) resin in the resin composition of the present invention is represented by the following general formula (2):
{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and has the same structure, or a plurality of wherein R ₆ is an organic group having at least one radically polymerizable unsaturated bond group having 3-20 carbon atoms, and n ₂ is an integer of 1-1000. } is a polyamide having a structure represented by

In the above general formula (2), the group represented by R ₆ includes the following general formula (2a),
{In the formula, R ₂₅ is an organic group having at least one radically polymerizable unsaturated bond group having 2 to 19 carbon atoms. } is preferably a group represented by .

In general formula (2) above, the trivalent organic group represented by X ₂ is preferably a trivalent organic group having 6 to 15 carbon atoms, such as the following formula (2b):
It is preferably an aromatic group selected from groups represented by the following, and more preferably an aromatic group obtained by removing a carboxyl group and an amino group from an amino group-substituted isophthalic acid structure.

In the above general formula (2), the divalent organic group represented by Y ₂ is preferably an organic group having 6 to 35 carbon atoms, and an optionally substituted aromatic or aliphatic ring. is more preferably a cyclic organic group having 1 to 4 or an aliphatic group or a siloxane group having no cyclic structure. The divalent organic group represented by Y ₂ includes the following general formulas (2c) to (2e):
{wherein R ₂₆ and R ₂₇ are each independently a hydroxyl group, a methyl group (--CH ₃ ), an ethyl group (--C ₂ H ₅ ), a propyl group (--C ₃ H ₇ ) and a butyl group (--C ₄ H ₉ ), and the propyl and butyl groups include various isomers. }
{wherein m ₄ is an integer of 0 to 8, m ₅ and m ₆ are each independently an integer of 0 to 3, m ₇ and m ₈ are each independently an integer of 0 to 10 is an integer and R ₂₈ and R ₂₉ are a methyl group (--CH ₃ ), an ethyl group (--C ₂ H ₅ ), a propyl group (--C ₃ H ₇ ), a butyl group (--C ₄ H ₉ ) or isomers of these. } is mentioned.

As the aliphatic group or siloxane group having no cyclic structure, the following general formula (2f):
{wherein m ₉ is an integer of 2 to 12, m ₁₀ is an integer of 1 to 3, m ₁₁ is an integer of 1 to 20, and R ₃₀ , R ₃₁ , R ₃₂ and Each R ₃₃ is independently an alkyl group having 1 to 3 carbon atoms or an optionally substituted phenyl group. } are preferred.

(A) A polyamide as a resin can be synthesized, for example, as follows.
(Synthesis of phthalate compound encapsulant)
First, a compound having a trivalent aromatic group X ₂ , such as selected from the group consisting of amino-substituted phthalic acid, amino-substituted isophthalic acid, and amino-substituted terephthalic acid. 1 mol of at least one or more compounds (hereinafter referred to as "phthalic acid compound") are reacted with 1 mol of a compound that reacts with an amino group, and the amino group of the phthalic acid compound is subjected to the radically polymerizable compound described later. A compound modified and blocked with a group containing an unsaturated bond (hereinafter referred to as a “blocked phthalate compound”) is synthesized. These may be used alone or in combination.

The group containing a radically polymerizable unsaturated bond is preferably an organic group having a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and a group containing a methacryloyl group or an acryloyl group is particularly preferable.

The above-mentioned phthalate compound encapsulant is obtained by reacting the amino group of the phthalate compound with an acid chloride, isocyanate, epoxy compound, or the like having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms. can be obtained with

Suitable acid chlorides include (meth)acryloyl chloride, 2-[(meth)acryloyloxy]acetyl chloride, 3-[(meth)acryloyloxy]propionyl chloride, 2-[(meth)acryloyloxy]ethyl chloroformate , 3-[(meth)acryloyloxypropyl]chloroformate, and the like. Suitable isocyanates include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate, 2-[2-(meth)acryloyloxyethoxy]ethyl isocyanate, and the like. . Suitable epoxy compounds include glycidyl (meth)acrylate and the like. These may be used alone or in combination, but it is particularly preferred to use methacryloyl chloride and/or 2-(methacryloyloxy)ethyl isocyanate.

Furthermore, as for these phthalic acid compound sealing bodies, those in which the phthalic acid compound is 5-aminoisophthalic acid are excellent in photosensitivity, and at the same time, a polyamide having excellent film properties after heat curing can be obtained. preferred.

The above sealing reaction is carried out by dissolving and mixing the phthalic acid compound and the sealing agent in a solvent with stirring in the presence of a basic catalyst such as pyridine or a tin-based catalyst such as di-n-butyltin dilaurate. can be done.

The reaction solvent is preferably one that completely dissolves the phthalate compound-encapsulated product, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide. , tetramethylurea, gamma-butyrolactone, and the like.

Other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene and the like. These solvents can be used singly or in combination, if necessary.

Depending on the type of sealing agent such as acid chloride, hydrogen chloride may be produced as a by-product in the process of the sealing reaction. In this case, from the viewpoint of preventing contamination in subsequent steps, it is preferable to carry out appropriate purification such as reprecipitation with water, washing with water and drying, or removing and reducing ion components through a column filled with an ion exchange resin. .

(Synthesis of Polyamide) The above phthalic acid compound capped product and a diamine compound having a divalent organic group _Y2 are mixed in a suitable solvent in the presence of a basic catalyst such as pyridine or triethylamine to effect amide polycondensation. Thus, the polyamide of the present invention can be obtained.

As the amide polycondensation method, the phthalate compound-capped product is converted to a symmetrical polyacid anhydride using a dehydration condensation agent and then mixed with a diamine compound, or the phthalic compound-capped product is converted to an acid chloride by a known method. and a method of reacting a dicarboxylic acid component and an active esterifying agent in the presence of a dehydration condensing agent to effect active esterification, followed by mixing with a diamine compound.

Dehydration condensation agents include, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1′-carbonyldioxy-di-1,2,3-benzotriazole, N,N '-Disuccinimidyl carbonate and the like are preferred.

Examples of the chlorinating agent include thionyl chloride.

Active esterification agents include N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic imide, 2-hydroxyimino-2-ethyl cyanoacetate, 2-hydroxyimino- 2-cyanoacetamide and the like.

The diamine compound having an organic group _Y2 is at least one diamine selected from the group consisting of aromatic diamine compounds, aromatic bisaminophenol compounds, alicyclic diamine compounds, linear aliphatic diamine compounds, and siloxane diamine compounds. Compounds are preferred, and a plurality of them can be used in combination if desired.

The aromatic diamine compounds include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'- Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane , 3,4′-diaminodiphenylmethane,

3,3′-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4 -(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy ) biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis( 4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2, 2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene , ortho-tolysine sulfone, 9,9-bis(4-aminophenyl)fluorene, and some of the hydrogen atoms on their benzene rings are methyl, ethyl, hydroxymethyl, hydroxyethyl, and halogen atoms. diamine compounds substituted with one or more groups selected from the group consisting of

Examples of diamine compounds in which hydrogen atoms on the benzene ring are substituted include 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro- 4,4'-diaminobiphenyl and the like.

Examples of aromatic bisaminophenol compounds include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenylsulfone, bis- (3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(3-hydroxy-4-aminophenyl)hexafluoropropane, bis-(3-hydroxy-4-aminophenyl)methane, 2,2-bis-(3-hydroxy-4-aminophenyl) Propane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5 -dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4-(α-methylbenzylidene)-bis(2-amino phenol) and the like.

Alicyclic diamine compounds include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, 1,5 -diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2 ,5-diethylcyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2-(3-aminocyclopentyl)-2-propylamine, menzenediamine, isophoronediamine, norbornane diamine, 1-cycloheptene-3,7-diamine, 4,4′-methylenebis(cyclohexylamine), 4,4′-methylenebis(2-methylcyclohexylamine), 1,4-bis(3-aminopropyl)piperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-[5,5]-undecane and the like.

Linear aliphatic diamine compounds include 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane. or alkylene oxide diamines such as 2-(2-aminoethoxy)ethylamine, 2,2'-(ethylenedioxy)diethylamine, bis[2-(2-aminoethoxy)ethyl]ether, etc. is mentioned.

Examples of the siloxane diamine compound include dimethyl(poly)siloxane diamine, such as trade names PAM-E, KF-8010 and X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.

The reaction solvent is preferably a solvent that completely dissolves the resulting polymer, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gamma-butyrolactone. etc.

In addition, ketones, esters, lactones, ethers, hydrocarbons, and halogenated hydrocarbons may be used as reaction solvents in some cases. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloro butane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like.

After completion of the amide polycondensation reaction, precipitates derived from the dehydration condensing agent deposited in the reaction solution are separated by filtration, if necessary. Next, a poor solvent for polyamide such as water, lower aliphatic alcohol, or a mixture thereof is introduced into the reaction solution to precipitate polyamide. Further, the precipitated polyamide is redissolved in a solvent, purified by repeating the reprecipitation procedure, and vacuum-dried to isolate the target polyamide. In order to further improve the degree of purification, the polyamide solution may be passed through a column filled with an ion exchange resin to remove ionic impurities.

Polystyrene equivalent weight average molecular weight of polyamide measured by gel permeation chromatography (hereinafter referred to as "GPC") is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. If the polystyrene equivalent weight average molecular weight is 7,000 or more, the basic physical properties of the cured relief pattern are ensured. Further, if the polystyrene-equivalent weight average molecular weight is 70,000 or less, development solubility when forming a relief pattern is ensured.

Tetrahydrofuran or N-methyl-2-pyrrolidone are recommended as eluents for GPC. Also, the weight average molecular weight value is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko.

[Polyimide]
Another example of the preferred (A) resin in the resin composition of the present invention is the general formula (3):
{Wherein, X ₅ is a 4- to 14-valent organic group, Y ₅ is a 2- to 12-valent organic group, R ₇ and R ₈ are groups selected from a phenolic hydroxyl group, a sulfonic acid group and a thiol group. represents a structure substituted with an organic group having at least one methacrylic group, acrylic group and styryl group, and may be the same or different, n ₅ is an integer of 3 to 200, and m ₂ and _m3 is an integer from 0 to 10; } is a polyimide having a structure represented by Here, the resin represented by the general formula (3) is particularly preferable in that it is suitable for treatment at a lower temperature because it does not require a chemical change in the heat treatment process in order to develop sufficient film properties.
X ₅ in the structural unit represented by the above general formula (3) is preferably a tetravalent to 14valent organic group having 4 to 40 carbon atoms, in terms of achieving both heat resistance and photosensitive properties. , an aromatic ring- or aliphatic ring-containing organic group having 5 to 40 carbon atoms is more preferred.

The polyimide represented by the general formula (3) can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride, or the like with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine. can. Polyimide is generally obtained by dehydrating and ring-closing polyamic acid, which is one of the polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, by heating or chemical treatment with an acid or base.

Suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'- Benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1- Bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis (2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluoric dianhydride,

9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluoric dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine Aromatic tetracarboxylic acids such as tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride dianhydrides, or aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,3′,4,4′ - diphenylsulfonetetracarboxylic dianhydride and the following general formula (3a):
{wherein R ₃₅ represents a group selected from an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₃₆ and R ₃₇ are the same or different; and represents a group selected from a hydrogen atom, a hydroxyl group and a thiol group. } is exemplified.

Among these, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,2′,3,3′- biphenyltetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis( 3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride , 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride,

Bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluoric dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluoric dianhydride and The following general formula (3b):
{wherein R ₃₈ represents a group selected from an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₃₉ and R ₄₀ are the same or different; and represents a group selected from a hydrogen atom, a hydroxyl group and a thiol group. } is preferable. These are used alone or in combination of two or more.

Y ₅ in the above general formula (3) represents a structural component of a diamine, and this diamine represents a divalent to 12-valent organic group containing an aromatic ring or an aliphatic ring, especially ~40 organic groups are preferred.

Specific examples of diamines 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, benzine, m-phenylenediamine, p-phenylene Diamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-( 4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diamino biphenyl, 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, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, or an alkyl group or halogen on the aromatic ring thereof Atom-substituted compounds or aliphatic cyclohexyldiamines, methylenebiscyclohexylamines, and the following general formula (3c):
{wherein R ₄₁ represents a group selected from an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₄₂ to R ₄₅ are the same or different; and represents a group selected from a hydrogen atom, a hydroxyl group and a thiol group. } and the like having a structure represented by .

Among these, 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, m-phenylenediamine, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis (4-aminophenyl)fluorene and the following general formula (3d):
{wherein R ₄₆ represents a group selected from an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₄₇ to R ₅₀ are the same or different; and represents a group selected from a hydrogen atom, a hydroxyl group and a thiol group. } is preferred.

Among these, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenyl sulfone, 4,4′- diaminodiphenylsulfone, 1,4-bis(4-aminophenoxy)benzene, and the following general formula (3e):
{wherein R ₅₁ represents a group selected from an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₅₂ and R ₅₃ are the same or different; and represents a group selected from a hydrogen atom, a hydroxyl group and a thiol group. } is particularly preferred. These are used alone or in combination of two or more.

R ₇ and R ₈ in general formula (3) represent a structure in which a phenolic hydroxyl group, a sulfonic acid group, or a thiol group is substituted with an organic group having at least one of a methacryl group, an acryl group, and a styryl group. there is In the present invention, unsubstituted phenolic hydroxyl groups, sulfonic acid groups and/or thiol groups may be present. is desirable, more preferably 90 mol % or more, most preferably 100 mol %. The substitution rate can be confirmed by ¹ HNMR.

Furthermore, in order to improve adhesion to the substrate, aliphatic groups having a siloxane structure may be copolymerized as X ₅ and Y ₅ within a range that does not reduce the heat resistance. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-amino-phenyl)octamethylpentasiloxane, etc. may be copolymerized in an amount of 1 to 10 mol %.

The above-mentioned polyimide is produced by, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a terminal blocker that is a monoamine) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially A method of reacting a diamine compound with an acid anhydride or a monoacid chloride compound or a monoactive ester compound as a terminal blocking agent, a method of reacting a diamine compound with a tetracarboxylic dianhydride and an alcohol to obtain a diester, and then a diamine (partially A method of reacting with a monoamine terminal blocker) in the presence of a condensing agent, a diester is obtained by tetracarboxylic dianhydride and alcohol, then the remaining dicarboxylic acid is acid chloride, diamine (partially A polyimide precursor is obtained using a method such as a method of reacting with a monoamine terminal blocker), and this is completely imidized using a known imidization reaction method, or in the middle Synthesis using a method of stopping the imidization reaction and partially introducing an imide structure, or a method of partially introducing an imide structure by blending a completely imidized polymer with its polyimide precursor. be able to.

It is preferable that the polyimide has an imidization rate of 15% or more with respect to the entire polymer constituting the resin composition. More preferably, it is 20% or more. Here, the imidization rate refers to the imidization rate present in the entire polymer constituting the resin composition. If the imidization rate is less than 15%, the amount of shrinkage during thermosetting will increase, making it unsuitable for producing thick films.

The imidization rate can be easily calculated by the following method. First, the infrared absorption spectrum of the polymer is measured to confirm the presence of absorption peaks (near 1780 cm ⁻¹ and 1377 cm ⁻¹ ) of the imide structure due to polyimide. Next, the polymer was heat-treated at 350° C. for 1 hour, the infrared absorption spectrum after the heat treatment was measured, and the peak intensity near 1377 cm ⁻¹ was compared with the intensity before the heat treatment to determine the imidization in the polymer before the heat treatment. Calculate the rate.

The molecular weight of the polyimide is preferably 3,000 to 200,000, more preferably 5,000 to 50,000, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight. When the weight average molecular weight is 3,000 or more, the mechanical properties are good, and when it is 50,000 or less, the dispersibility in a developer is good and the relief pattern resolution performance is good.

Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Also, the molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko.

(B) Compound Having Aromatic Sulfonate Structure The (B) compound having an aromatic sulfonate structure used in the present invention is a compound in which an aromatic compound is linked with a sulfonate ester. (B) By using a compound having an aromatic sulfonate ester structure, the adhesion between copper and resin can be improved, and the step between the copper surface and the resin after polishing can be reduced. The mechanism by which the adhesion between copper and resin is excellent is not clear, but the aromatic sulfonate structure interacts with copper, and (A) the resin and the aromatic sulfonate structure are also hydrogen-bonded. It is presumed that the interaction between copper and the resin develops adhesiveness.

(B) Specific examples of the compound having an aromatic sulfonate structure include phenyl p-toluenesulfonate, 2-naphthyl p-toluenesulfonate, 2-bromophenyl p-toluenesulfonate, and derivatives thereof. . Also, a compound composed of a condensate of any phenol compound and any aromatic sulfonyl chloride may be used.

The compound (B) having an aromatic sulfonate structure is preferably a compound (B') having a quinonediazide group (hereinafter also referred to as "(B') quinonediazide compound"). (B') Examples of the quinonediazide compound include compounds having a 1,2-benzoquinonediazide structure and compounds having a 1,2-naphthoquinonediazide structure. The quinonediazide compound may be a substance described in U.S. Pat. Nos. 2,772,972, 2,797,213, and 3,669,658. good. The quinonediazide compound (B′) is preferably a naphthoquinonediazide sulfonic acid ester of a hydroxy compound (hereinafter also referred to as “NQD compound”) in that it has a good effect of improving the adhesion between copper and resin. , 1,2-naphthoquinonediazide-4-sulfonate of a hydroxy compound having a specific structure detailed below, and 1,2-naphthoquinonediazide-5-sulfonate of the hydroxy compound. More preferably, it is at least one kind of compound.

The NQD compound is prepared by converting a naphthoquinonediazide sulfonic acid compound into a sulfonyl chloride with chlorosulfonic acid or thionyl chloride according to a conventional method, and condensing the obtained naphthoquinonediazide sulfonyl chloride with a hydroxy compound (for example, a polyhydroxy compound). can get. For example, a predetermined amount of a hydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride is dissolved in a solvent such as dioxane, acetone, or tetrahydrofuran with a basic catalyst such as triethylamine. It can be obtained by reacting in the presence of to effect esterification, washing the resulting product with water, and drying it.

In one embodiment, (B') a compound having a quinonediazide group has the following general formulas (4) to (8):
{In Formula (4), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms), and X ₃ and X ₄ each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms); is an integer and at least one of r3 and r4 is an integer from 1 to 5, r1+r3=5 and r2+r4=5. }
{In formula (5), Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X ₅ , X ₆ , X ₇ and X ₈ each independently represent a monovalent organic group having 1 to 30 carbon atoms. represents an organic group, r6 is an integer of 0 or 1, r5, r7, r8 and r9 are each independently an integer of 0 to 3, r10, r11, r12 and r13 are each independently It is an integer between 0 and 2, and r10, r11, r12 and r13 cannot all be zero. }
{In formula (6), r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, (r14 × r15) L are each independently 1 having 1 to 20 carbon atoms represents a valent organic group, (r15) T are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and (r15) S are each independently hydrogen represents an atom or a monovalent organic group having 1 to 20 carbon atoms; }
{In formula (7), A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group, preferably represented by the following chemical formula:
represents at least one divalent group selected from the three groups represented by }
{In formula (8), r17, r18, r19 and r20 are each independently an integer of 0 to 2, at least one of r17, r18, r19 and r20 is 1 or 2, and X ₁₀ to Each X ₁₉ independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group and an acyl group, and Y ₁ to Y ₃ each independently represents a single bond, —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO ₂ —, cyclopentylidene, cyclohexylidene, phenylene and 1 to represents at least one divalent group selected from the group consisting of 20 divalent organic groups; } is preferably a 1,2-naphthoquinonediazide-4-sulfonate ester and/or a 1,2-naphthoquinonediazide-5-sulfonate ester compound of a hydroxy compound represented by }.

In a further embodiment, in general formula (8) above, Y ₁ to Y ₃ each independently represent the following general formula:
{Wherein, X ₂₀ and X ₂₁ each independently represent at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and a substituted aryl group, and X ₂₂ , X ₂₃ , X ₂₄ and X ₂₅ each independently represent a hydrogen atom or an alkyl group, r21 is an integer of 1 to 5, and X ₂₆ , X ₂₇ , X ₂₈ and X ₂₉ each independently represents a hydrogen atom or an alkyl group. is preferably at least one selected from three divalent organic groups represented by }.

As the compound represented by the general formula (4), the following formulas (4a) to (4e):
{In formula (4a), r16 is each independently an integer of 0 to 2, and _X9 is each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and _X9 When a plurality of X 9 are present, the plurality of X ₉ may be the same or different, and X ₉ has the following chemical formula:
(wherein r18 is an integer of 0 to 2, _X31 represents at least one monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group, and a cycloalkyl group, and r18 is 2, two X ₃₁ may be the same or different from each other.) is preferably a monovalent organic group represented by . }
{In formula (4b), X ₃₂ is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms. represents one monovalent organic group. }

{In formula (4c), r19 is each independently an integer of 0 to 2, and X ₃₃ is each independently a hydrogen atom or the following general formula:
(Wherein, r20 is an integer of 0 to 2, _X35 represents at least one selected from the group consisting of a hydrogen atom, an alkyl group and a cycloalkyl group, and when r20 is 2 , two X ₃₅ may be the same or different), and X ₃₄ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon represents at least one selected from the group consisting of 3 to 20 cycloalkyl groups; }
and hydroxy compounds (p-cumylphenol) represented by.

As the compound represented by the above formula (4a), the following formulas (4a-1) to (4a-3):
The hydroxy compound represented by is preferable because it has high sensitivity when converted into an NQD compound and has low precipitation in the resin composition (NQD of a polyhydroxy compound described in JP-A-2004-109849 It is a monster.).

As the compound represented by the above formula (4b), the following formula (4b-1):
The hydroxy compound represented by is preferable because it has high sensitivity when made into an NQD compound and has low precipitation in the resin composition (NQD of a polyhydroxy compound described in JP-A-2001-356475 It is a monster.).

As the compound represented by (4c) above, the following formulas (4c-1) to (4c-3):
The hydroxy compound represented by is preferable because it has high sensitivity when converted into an NQD compound and has low precipitation in the resin composition (NQD of a polyhydroxy compound described in JP-A-2005-8626 It is a monster.).

In the above general formula (5), Z is not particularly limited as long as it is a tetravalent organic group having 1 to 20 carbon atoms, but from the viewpoint of sensitivity, the following formula:
A tetravalent group having a structure represented by is preferred.

Among the compounds represented by the general formula (5), the following formulas (5a) to (5d):
The hydroxy compound represented by is preferable because it has high sensitivity when made into an NQD compound and has low precipitation in the resin composition (NQD of a polyhydroxy compound described in JP-A-2001-92138 It is a monster.).

As the compound represented by the general formula (6), the following formula (6a):
{Wherein, each r40 is independently an integer of 0 to 9. } is preferable because it has high sensitivity when made into an NQD compound and has low precipitation in the resin composition (of the polyhydroxy compound described in JP-A-2004-347902, It is an NQD compound.).

As the compound represented by the general formula (7), the following formulas (7a) and (7b):
The hydroxy compound represented by is preferable because it has high sensitivity when converted into an NQD compound and has low precipitation in the resin composition.

Specific examples of the compound represented by the general formula (8) include NQD compounds of polyhydroxy compounds described in JP-A-2001-109149. Among those compounds, the following formula (8a):
The NQD compound of the polyhydroxy compound represented by is preferable because of its high sensitivity and low deposition property in the resin composition.

(B') In the quinonediazide compound, the 1,2-naphthoquinonediazide sulfonyl group is either a 1,2-naphthoquinonediazide-5-sulfonyl group or a 1,2-naphthoquinonediazide-4-sulfonyl group, However, the 1,2-naphthoquinonediazide-5-sulfonyl group has more excellent adhesiveness.

In embodiments, it is preferred to select one or both of a 1,2-naphthoquinonediazide-4-sulfonate compound and a 1,2-naphthoquinonediazide-5-sulfonate compound. A 1,2-naphthoquinonediazide sulfonic acid ester compound having a 1,2-naphthoquinonediazide-4-sulfonyl group and a 1,2-naphthoquinonediazide-5-sulfonyl group in the same molecule can also be used. A mixture of a 2-naphthoquinonediazide-4-sulfonate compound and a 1,2-naphthoquinonediazide-5-sulfonate compound can also be used.

In the quinonediazide compound (B′), the average esterification rate of the naphthoquinonediazide sulfonyl ester of the hydroxy compound is preferably 10% to 100%, more preferably 20% to 100%, from the viewpoint of adhesion between copper and resin. More preferred. The average esterification rate can be confirmed by ¹ H NMR.

The (B') quinonediazide compound according to the present embodiment is not limited as long as it has one or more quinonediazide sites. From the viewpoint of adhesion and elongation between copper and resin, the average number of quinonediazide moieties in the compound is preferably 2.4 or more, more preferably 2.5 or more. From the viewpoint of elongation, the average number of quinonediazide moieties in the compound is preferably 5 or less, more preferably 4 or less.

In one embodiment, the amount of (B) the compound having an aromatic sulfonate structure in the resin composition is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the (A) resin, preferably 3 to 30 parts by mass, more preferably 5 to 10 parts by mass. When the amount is 1 part by mass or more, good adhesiveness between copper and the resin can be obtained.

(C) Photoinitiator In one aspect, the resin composition contains (C) a photoinitiator. (C) Photopolymerization initiators include, for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, benzophenone derivatives such as fluorenone, and 2,2′-diethoxyacetophenone. , 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives, benzyl, benzyl dimethyl ketal, benzyl- Benzyl derivatives such as β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione -2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl) Oximes such as oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N such as N-phenylglycine - arylglycines, peroxides such as benzoyl perchloride, and aromatic biimidazoles are preferred, but not limited thereto. Moreover, in using these, they may be used singly or as a mixture of two or more.

Among the above photoinitiators, the following general formula (9):
{In formula (9), Z is a sulfur or oxygen atom, R12a represents a methyl group, a phenyl group or a divalent organic group, R13a to R15a each independently represents a hydrogen atom or a monovalent organic group represents } An oxime compound represented by is more preferably used. Among them, the following formulas (9a), (9b), (9c) or (9d) are particularly preferred:
A compound represented by or a mixture thereof. Formula (9a) is TR-PBG-305 manufactured by Changzhou Power New Electronic Materials Co., Ltd., Formula (9b) is TR-PBG-3057 manufactured by Changzhou Power New Electronic Materials Co., Ltd., Formula (9c) is Irgacure OXE- manufactured by BASF. 01 commercially available.

In a preferred embodiment, (C) the photopolymerization initiator has the following general formula (10):
{In Formula (10), R ₁ , R ₂ and R ₃ each represent a monovalent organic group, and R ₁ and R ₂ may be linked to each other to form a ring structure} including oxime ester compounds.

(C) The amount of the photopolymerization initiator in the resin composition is preferably 0.1 to 50 parts by mass, more preferably 0.5 parts by mass to 100 parts by mass of the resin (A). 20 parts by mass, more preferably 1 to 7 parts by mass. When the blending amount is 0.1 parts by mass or more, the elongation of the cured film is excellent.

(D) Photopolymerizable compound In one aspect, the resin composition contains (D) a photopolymerizable compound. (D) The photopolymerizable compound is a monomer having a photopolymerizable unsaturated bond, and such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator, particularly Ethylene glycol or polyethylene glycol mono- or diacrylates and methacrylates, propylene glycol or polypropylene glycol mono- or diacrylates and methacrylates, glycerol mono-, such as, but not limited to, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate. , di- or triacrylates and methacrylates, cyclohexane diacrylates and dimethacrylates, diacrylates and dimethacrylates of 1,4-butanediol, diacrylates and dimethacrylates of 1,6-hexanediol, diacrylates and dimethacrylates of neopentyl glycol , mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol di- or triacrylates and methacrylates, Compounds such as di-, tri-, or tetraacrylates and methacrylates of pentaerythritol and ethylene oxide or propylene oxide adducts of these compounds may be mentioned.

When the resin composition contains a monomer having a photopolymerizable unsaturated bond, the amount of the monomer having a photopolymerizable unsaturated bond is (A) 1 to 50 parts by mass per 100 parts by mass of the resin. It is preferable that it is a part. When the amount is 1 part by mass or more, the adhesion between copper and the resin is excellent, and when the amount is 50 parts by mass or less, the in-plane uniformity of the coating film is excellent.

(E) Organic Titanium Compound The resin composition of the present invention may contain (E) an organic titanium compound. By including (E) an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature of about 250° C. or lower.

(E) Compounds that can be used as the organotitanium compound include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

Specific examples of (E) organotitanium compounds are shown below in I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable because the storage stability of the resin composition and a favorable pattern can be obtained, and a specific example is titanium bis(triethanolamine ) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate, titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedio acid), titanium diisopropoxide bis(ethylacetoacetate), and the like.

II) Tetraalkoxytitanium compounds: for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide. , titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl) butoxide}] and the like.

III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η ⁵ - and 2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide and the like.

V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.

VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate.

VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, (E) the organotitanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, which results in better resistance. It is preferable from the viewpoint of exhibiting chemical properties. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-( 1H-pyrrol-1-yl)phenyl)titanium is preferred.

When the organic titanium compound (E) is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the resin (A). . When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, and when the amount is 10 parts by mass or less, the storage stability is excellent.

(F) Other Components The resin composition of the present invention may further contain components other than the above components (A) to (E). Since the resin composition of the present invention is typically used as a varnish-like resin composition by dissolving each of the above components and optionally further optional components in a solvent, (F) other components A solvent can be mentioned as a solvent. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the (A) resin. Specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α -Acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like, and these can be used alone or in combination of two or more.

The solvent is, for example, in the range of 30 to 1500 parts by mass, preferably in the range of 100 to 1000 parts by mass, with respect to 100 parts by mass of the resin (A), depending on the desired coating thickness and viscosity of the resin composition. can be done.

Furthermore, solvents containing alcohols are preferable from the viewpoint of improving the storage stability of the resin composition. Alcohols that can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond. Specific examples include methyl alcohol, ethyl alcohol, n- Alkyl alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and tert-butyl alcohol, lactic acid esters such as ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol Propylene glycol monoalkyl ethers such as 1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, propylene glycol-2-(n-propyl) ether, ethylene glycol methyl ether , ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, and other monoalcohols, 2-hydroxyisobutyric acid esters, ethylene glycol, and propylene glycol, and other dialcohols. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferred, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether are more preferred.

When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, more preferably It is preferably 10 to 30% by mass. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the resin composition is improved, and when it is 50% by weight or less, the solubility of the (A) resin is improved. Become.

The resin composition of the present invention may contain a cross-linking agent. The cross-linking agent may be a cross-linking agent capable of cross-linking the (A) resin or capable of forming a cross-linked network by itself when the resin composition of the present invention is heat-cured. The cross-linking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the resin composition.

Examples of cross-linking agents having one thermal cross-linkable group include ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, and ML-TBC (trade names of Honshu Kagaku Kogyo Co., Ltd.), Pa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc. DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (trade name, Asahi Yu Kizai Kogyo Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, Dimethylol- Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP ( Above, product name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (product name, manufactured by Sanwa Chemical Co., Ltd.),

Ba type benzoxazine, Bm type benzoxazine (both trade names, manufactured by Shikoku Kasei Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p- Cresol, 2,6-diacetoxymethyl-p-cresol, etc. TriML-P, TriML-35XL, TriML-TrisCR-HAP (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), etc., and 4 TM-BIP-A (trade name, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (trade names, Honshu Chemical Industry Co., Ltd.), Nicalac MX-280, Nicalac MX-270 (the above are product names, manufactured by Sanwa Chemical Co., Ltd.), etc. HML-TPPHBA and HML-TPHAP (the above are products name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicalac MW-390, and Nicalac MW-100LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

Among these, those containing at least two thermally crosslinkable groups are preferred in the present invention, and particularly preferred are 46DMOC, 46DMOEP (trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-MBPC, DML- MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, Trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (above, trade name, Shikoku Kasei Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc., TriML-P, TriML- 35XL (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc., TM-BIP-A (trade name, manufactured by Asahi Organic Chemical Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (trade names, manufactured by Sanwa Chemical Co., Ltd.), etc., HML-TPPHBA , HML-TPHAP (both trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and the like. Still more preferably, Nicalac MX-290, Nicalac MX-280, Nicalac MX-270 (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (the above , trade name, manufactured by Shikoku Kasei Co., Ltd.), Nicalac MW-390, and Nicalac MW-100LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

In consideration of various properties other than heat resistance and chemical resistance, when the resin composition contains a cross-linking agent, the blending amount is 0.5 to 20 parts by mass per 100 parts by mass of the (A) resin. is preferred, more preferably 2 to 10 parts by mass. When the amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are exhibited, and when it is 20 parts by mass or less, the storage stability is excellent.

(Nitrogen-containing heterocyclic compound)
A nitrogen-containing heterocyclic compound such as an azole compound or a purine derivative can be arbitrarily blended into the resin composition of the present invention in order to suppress discoloration on copper. Examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl- 5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxy Phenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5 -bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl- 2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxy phenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl -1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like. Particularly preferred is one or more selected from tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used singly or as a mixture of two or more.

Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl) guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine and derivatives thereof.

When the resin composition contains the nitrogen-containing heterocyclic compound, which is the azole compound or purine derivative, the amount of the nitrogen-containing heterocyclic compound is 0.1 to 20 parts by mass based on 100 parts by mass of the (A) resin. and more preferably 0.5 to 5 parts by mass from the viewpoint of storage stability of the resin composition. When the amount of the nitrogen-containing heterocyclic compound compounded with respect to 100 parts by mass of the resin (A) is 0.1 parts by mass or more, when the resin composition of the present invention is formed on copper or a copper alloy, copper or copper Discoloration of the alloy surface is suppressed, and on the other hand, when the content is 20 parts by mass or less, the storage stability of the resin composition is excellent.

Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. Moreover, these azole compounds may be used singly or as a mixture of two or more.

In addition, a hindered phenol compound can optionally be blended to suppress discoloration on the copper surface. Hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4, 4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t -butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio -diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrosine namamide), 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2,2′-methylene-bis(4-ethyl-6-t-butylphenol),

pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl -4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2 ,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2 ,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3- hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,

1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 , 3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3 ,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 , 3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H) -trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H, 5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-( 1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione,

1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1, 3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1, 3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like are mentioned, but are not limited to these. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione and the like are particularly preferred.

The amount of the hindered phenol compound compounded is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and from the viewpoint of the degree of polymerization of the compound having an unsaturated bond, it is 0.5 to 10 parts by mass. Part is more preferred. When the amount of the hindered phenol compound added to 100 parts by mass of resin (A) is 0.1 parts by mass or more, for example, when the resin composition of the present invention is formed on copper or copper alloy, copper or copper alloy On the other hand, when it is 20 parts by mass or less, the degree of polymerization of the compound having an unsaturated bond is excellent.

(sensitizer)
A sensitizer may optionally be added to the resin composition of the present invention. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal). ) cyclohexanone, 2,6-bis(4′-diethylaminobenzal)-4-methylcyclohexanone, 4,4′-bis(dimethylamino)chalcone, 4,4′-bis(diethylamino)chalcone, p-dimethylamino thinner mylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)acetone, 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylamino) styryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene and the like. These can be used singly or in combination, for example of 2 to 5 types.

When the resin composition contains the sensitizer, the amount of the sensitizer is preferably 0.1 to 25 parts by mass per 100 parts by mass of the resin (A).

(adhesion aid)
In addition, an adhesion aid can be arbitrarily blended in order to improve the adhesion between the film formed using the resin composition of the present invention and the substrate. Adhesion aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide , N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3′-bis(N-[3-triethoxysilyl]propylamide)-4,4′-dicarboxylic acid, benzene-1, 4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyl Silane coupling agents such as trimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, and aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethyl Examples thereof include aluminum-based adhesion promoters such as acetoacetate aluminum diisopropylate.

Among these adhesion aids, the silane coupling agent is more preferable from the point of adhesion. When the resin composition contains an adhesion promoter, the content of the adhesion promoter is preferably in the range of 0.5 to 25 parts by weight per 100 parts by weight of the resin (A).

(Thermal polymerization inhibitor)
In addition, a thermal polymerization inhibitor can be arbitrarily blended in order to improve the stability of the viscosity of the resin composition during storage, particularly in the state of a solution containing a solvent. Thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6 -Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N- sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like are used.

The amount of the thermal polymerization inhibitor to be added to the resin composition is preferably in the range of 0.005 to 12 parts by weight per 100 parts by weight of the resin (A).

<Method for producing cured film and semiconductor device>
In addition, the present invention
(1) forming a resin film on a substrate by applying a resin composition onto the substrate;
(2) forming a cured film by heat-treating the resin film;
(3) A method for producing a cured film, comprising the step of flattening the cured film by polishing. Typical aspects of each step are described below.

(1) Step of forming a resin film on a substrate by applying a resin composition onto the substrate In this step, the resin composition of the present invention is applied onto a substrate, and then dried if necessary. A resin layer is formed. Examples of the coating method include a method of coating with a spin coater, bar coater, blade coater, curtain coater, screen printer, etc., and a method of spray coating with a spray coater.

If necessary, the coating film made of the resin composition can be dried. As a drying method, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are used. Specifically, when air drying or heat drying is performed, drying can be performed at 20° C. to 140° C. for 1 minute to 1 hour. A resin layer can be formed on the substrate by the above procedure.

(2) Step of forming a cured film by heat-treating the resin film In this step, the coating film obtained in (1) above is converted into a cured film by heating. As the heat curing method, various methods such as a method using a hot plate, a method using an oven, and a method using a heating oven capable of setting a temperature program can be selected. Heating can be performed, for example, at 180° C. to 400° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas for heat curing, or an inert gas such as nitrogen or argon may be used.

(3) Step of flattening the cured film by polishing In this step, the cured film obtained in (2) above is polished to expose the electrodes and the like formed on the substrate from the cured film. Polishing methods include grinding, chemical mechanical polishing (CMP), and the like.

Further, when the resin composition is a photosensitive resin composition, after the step of (1) coating the resin composition on a substrate to form a resin film on the substrate, the resin film is coated with a contact aligner, An exposure apparatus such as a mirror projection, stepper, or the like may be used to expose to an ultraviolet light source or the like directly or through a photomask or reticle having a pattern. When exposed to light, the degree of polymerization of the compound having an unsaturated bond in the resin film is improved, and a cured film having excellent mechanical properties can be obtained.

Also, if necessary, a post-exposure bake (PEB) may be applied at any combination of temperature and time. The range of baking conditions is preferably a temperature of 40 to 120° C. and a time of 10 to 240 seconds. do not have.

<Semiconductor device>
The present invention also provides a semiconductor device obtained by the above-described method for producing a cured film of the present invention. The present invention also provides a semiconductor device comprising a base material which is a semiconductor element and a cured resin film formed on the base material by the above-described method for producing a cured film. The present invention can also be applied to a semiconductor device manufacturing method that uses a semiconductor element as a base material and includes the above-described cured film manufacturing method as a part of the process. The semiconductor device of the present invention is a semiconductor device having a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a bump structure. It can be manufactured by forming it as a protective film or the like and combining it with a known method for manufacturing a semiconductor device.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these. In Examples, Comparative Examples and Production Examples, the physical properties of the resin compositions were measured and evaluated according to the following methods.

(1) Weight Average Molecular Weight The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (converted to standard polystyrene). The column used for the measurement is the trade name "Shodex 805M/806M Series" manufactured by Showa Denko K.K. , the developing solvent was N-methyl-2-pyrrolidone (NMP), and the detector used was trade name "Shodex RI-930" manufactured by Showa Denko KK.

(2) Adhesion to Copper A substrate having a copper plating pattern of 25 μm in height on a 6-inch silicon wafer was produced with reference to JP-A-2006-19316. Note that the method for producing the copper plating pattern is not limited to this, and any pattern made of copper may be used. The resin composition was spin-coated on the substrate, dried to form a coating film with a thickness of 35 μm as a resin layer, and then using a temperature-rising programmable curing furnace (VF-2000, manufactured by Koyo Lindbergh Co., Ltd.), nitrogen. A cured resin coating film was obtained by heat treatment (curing) at 200° C. for 2 hours in an atmosphere. The copper pattern in this cured film was cleaved at 10 points on the substrate using a focused ion beam processing observation device (JIB-4000 type, manufactured by JEOL Ltd.). A SIM image was obtained from the cross section of the cleaved copper pattern using a focused ion beam processing observation device to observe the adhesion between the cured film and copper.
"⊚+": Peeling was not observed between the cured film and the copper in all 10 copper patterns.
"A": No peeling was observed between the cured film and copper at 9 out of 10 copper patterns.
"○+": No peeling was observed between the cured film and the copper at 8 out of 10 copper patterns.
"◯": No peeling was observed between the cured film and the copper at 7 of the 10 copper patterns.
"Δ": No peeling was observed between the cured film and the copper at 6 out of 10 copper patterns.
"X": Peeling was observed between the cured film and the copper at 5 or more of the 10 copper patterns.
“Whole surface peeling”: The entire cured film is peeled off from the copper at 10 locations out of 10 copper patterns.

(3) Elongation On a 6-inch silicon wafer, the resin composition was spin-coated and dried so that the film thickness after curing was about 8 μm. ) under a nitrogen atmosphere at 200° C. for 2 hours to obtain a cured film. After cutting the resulting polyimide coating film into strips with a width of 3 mm using a dicing saw (DAD3350 type, manufactured by DISCO), a silicon wafer was used with 46% hydrofluoric acid to form a cured film on the silicon wafer. was peeled off to obtain 10 polyimide tapes. The elongation of the obtained polyimide tape was measured according to ASTM D882-09 using a tensile tester (UTM-II-20 type, manufactured by Orientec).
"◎ +": The average elongation of 10 polyimide tapes is 50% or more, and the elongation of 9 or more out of 10 polyimide tapes is 50% or more "◎": The average elongation of 10 polyimide tapes is 50% or more, and the elongation of 8 or less out of 10 polyimide tapes is 50% or more. In this book, the elongation of 7 or more is 40% or more "○": The average elongation of 10 polyimide tapes is 40% or more and less than 50%, and the elongation of 6 or less out of 10 polyimide tapes 40% or more "△": The average elongation of 10 polyimide tapes is 30% or more and less than 40%, and the elongation of 5 or more out of 10 polyimide tapes is 30% or more "X": The average elongation of 10 polyimide tapes is less than 30%

(4) In-plane uniformity after polishing A cured resin coating film formed on a silicon wafer substrate having a copper pattern was obtained in the same manner as in (2) above. The cured film-coated substrate film formed using a chemical mechanical polishing apparatus (Reflexion LK CMP type, manufactured by Applied Materials) was polished using a polishing slurry and a polishing pad at a rotational speed of 150 rpm while applying a pressure of 4.8 psi. It was polished for 1 minute to expose the copper pattern portion. A silica sol type polishing slurry (silica concentration: 13% by mass, primary particle size: 30 nm, pH = 10.8 (ammonia)) was used. A foamed polyurethane pad (about 1.8 mm thick) was used as the polishing pad. After polishing, the cured film portion and the copper pattern portion were measured with a contact-type profilometer (P-15 type, manufactured by KLA-Tencor) to measure the height difference between the cured film portion and the copper pattern portion.
"⊚+": The height difference between the cured film and the copper pattern portion is less than 5 nm.
"A": The height difference between the cured film and the copper pattern portion is 5 nm or more and less than 10 nm.
"○+": The height difference between the cured film and the copper pattern portion is 10 nm or more and less than 20 nm.
"◯": The height difference between the cured film and the copper pattern portion is 20 nm or more and less than 40 nm.
"Δ": The height difference between the cured film and the copper pattern portion is 40 nm or more and less than 100 nm.
"X": The height difference between the cured film and the copper pattern portion is 100 nm or more.

<Production Example 1> ((A) Synthesis of polymer A in which the acidic functional group in the side chain of the resin is alkyl-esterified)
155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, 46.5 g of ethanol and 400 ml of γ-butyrolactone were added, and the mixture was stirred at room temperature. 5 g was added to obtain a reaction mixture. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture with stirring over 40 minutes, followed by 4,4′-diaminodiphenyl ether (DADPE). A suspension of 93.0 g in 350 ml of γ-butyrolactone was added with stirring over 60 minutes. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The resulting reaction mixture was added to 3 liters of ethyl alcohol to form a precipitate consisting of crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polymer A). When the molecular weight of polymer A was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 34,000.

<Production Example 2> ((A) Synthesis of polymer B in which the acidic functional group in the side chain of the resin is esterified with a methacrylic group)
Except for using 131.2 g of 2-hydroxyethyl methacrylate (HEMA) instead of 46.5 g of ethanol in Production Example 1, the reaction was carried out in the same manner as in Production Example 1 to obtain Polymer B. Ta. When the molecular weight of polymer B was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 20,000.

<Production Example 3> ((A) Synthesis of polymer C in which the acidic functional group in the side chain of the resin is esterified with a methacrylic group)
Instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 2, 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for this, the reaction was carried out in the same manner as in Production Example 2 above to obtain Polymer C. When the molecular weight of Polymer C was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 22,000.

<Production Example 4> ((A) Synthesis of polymer D in which the basic functional group in the side chain of the resin is ureated with a methacrylic group) (Synthesis of phthalate compound-sealed AIPA-MO)
5-aminoisophthalic acid (hereinafter abbreviated as AIPA) is placed in a 5-liter separable flask. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50° C. in a water bath. To this, 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise from a dropping funnel, and the mixture was stirred at 50° C. for about 2 hours.

Completion of the reaction (disappearance of 5-aminoisophthalic acid) was measured by low-molecular-weight gel permeation chromatography {hereinafter referred to as low-molecular-weight GPC. }, the reaction mixture was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product crystallized and precipitated, the reaction mixture was separated by filtration, washed with water as needed, and vacuumed at 40°C for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate acted was obtained. The obtained AIPA-MO had a low molecular weight GPC purity of about 100%.

(Synthesis of polymer D)
100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added to a 2-liter separable flask, mixed, and cooled to 5°C in an ice bath. did. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise over about 20 minutes under ice cooling, followed by 4,4′-bis(4-aminophenoxy ) Biphenyl {hereinafter referred to as BAPB. } A solution of 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, followed by stirring in an ice bath for 3 hours while maintaining the temperature below 5°C, then removing the ice bath and stirring at room temperature for 5 hours. did. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The resulting crude polymer solution was dropped into 5 liters of water to precipitate the polymer, and the obtained precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polymer D). When the molecular weight of polymer D was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 34,700.

<Production Example 5> ((A) Synthesis of polymer E in which the acidic functional group in the side chain of the resin is esterified with a methacrylic group)
A condenser with a Dean-Stark trap was attached to a four-neck glass separable flask equipped with a Teflon (registered trademark) anchor stirrer. The flask was placed in a silicone oil bath and stirred while nitrogen gas was passed through.

32.96 g (90 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added, 196 g of NMP and 40 g of toluene were added, and the mixture was stirred at room temperature. 31.02 g (100 millimoles) of oxydiphthalic dianhydride (ODPA) was added and stirred at room temperature for 2 hours, then heated and stirred at 180° C. and 180 rpm for 3 hours. After the imidization reaction was completed, the temperature was returned to room temperature.

After that, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and deposit the polymer, which was collected, washed with water as appropriate, dehydrated, and vacuum-dried, and measured by gel permeation chromatography (GPC). A crude polyimide having a weight average molecular weight of 23,000 (converted to polystyrene) was obtained.

30 g of the above crude polyimide was dissolved in 200 g of NMP in a 2 L separable flask equipped with an anchor stirrer, and the reaction vessel was immersed in a container containing methanol and dry ice to cool to -15°C. After that, 5.1 g of methacryloyl chloride was added dropwise, and 5.5 g of pyridine was subsequently added dropwise while maintaining the reaction system at -15 to 0°C. Thereafter, the above reaction solution was dropped into 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, and vacuum-dried to obtain Polymer E. Analysis of this polymer E by ¹ H NMR revealed that 50% of the phenolic hydroxyl group side chains in the resin were substituted with methacrylic ester structures.

<Production Example 6> ((A) Synthesis of polymer F in which the acidic functional group in the side chain of the resin is esterified with a methacrylic group)
Except for using 10 g of methacryloyl chloride instead of 5.1 g of methacryloyl chloride in Production Example 5, the reaction was carried out in the same manner as in Production Example 5 to obtain Polymer F. Analysis of this polymer F by ¹ H NMR revealed that 100% of the phenol hydroxyl side chains in the resin were substituted with methacrylic ester structures.

<Production Example 7> (Synthesis of polymer G having an acidic functional group in the side chain)
93.0 g of 4,4′-diaminodiphenyl ether (DADPE) was placed in a 2-liter separable flask, 400 ml of γ-butyrolactone was added, and the mixture was stirred at room temperature to dissolve. 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was added and stirred at room temperature for 2 hours. The resulting crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polymer G). When the molecular weight of polymer G was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 30,000.

<Production Example 8> (Synthesis of polymer H having an acidic functional group in the side chain)
A condenser with a Dean-Stark trap was attached to a four-neck glass separable flask equipped with a Teflon (registered trademark) anchor stirrer. The flask was placed in a silicone oil bath and stirred while nitrogen gas was passed through.

32.96 g (90 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added, 196 g of NMP and 40 g of toluene were added, and the mixture was stirred at room temperature. 31.02 g (100 millimoles) of oxydiphthalic dianhydride (ODPA) was added and stirred at room temperature for 2 hours, then heated and stirred at 180° C. and 180 rpm for 3 hours. After the imidization reaction was completed, the temperature was returned to room temperature.

After that, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and deposit the polymer, which was collected, washed with water as appropriate, dehydrated, and vacuum-dried, and measured by gel permeation chromatography (GPC). A polymer H having a weight average molecular weight of 23,000 (converted to polystyrene) was obtained.

<Production Example 9>
Described in Production Example 2 above, except that 109.1 g of pyromellitic dianhydride (PMDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 2. A polymer I was obtained by performing a reaction in the same manner as in . When the molecular weight of polymer I was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 22,000.

<Production Example 10>
Instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 2, 161.1 g of benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA) Polymer J was obtained by carrying out the reaction in the same manner as in Production Example 2, except that the polymer was used. When the molecular weight of Polymer J was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 21,000.

[Synthesis Example 1]
<Synthesis of diazonaphthoquinone compound B-3, which is a compound having an aromatic sulfonate structure>
A 1 L separable flask equipped with a stirrer, a dropping funnel and a thermometer was charged with the following formula (b3) as a hydroxy compound:
Using 30 g (0.141 mol) of p-cumylphenol (manufactured by Mitsui Chemicals Fine Co., Ltd.) having a structure represented by, 1,2-naphthoquinonediazide-5- in an amount corresponding to 100 mol% of the OH groups After dissolving 37.9 g (0.141 mol) of sulfonyl chloride in 300 g of acetone with stirring, the flask was adjusted to 30° C. in a constant temperature bath. Next, 17.9 g of triethylamine was dissolved in 18 g of acetone, charged into a dropping funnel, and dropped into the flask over 30 minutes. After the dropwise addition was completed, the stirring was continued for an additional 30 minutes, then hydrochloric acid was added dropwise, and the reaction was completed by further stirring for 30 minutes. The reaction was then filtered to remove triethylamine hydrochloride. 1640 g of pure water and 30 g of hydrochloric acid were mixed and stirred in a 3 L beaker, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. The precipitate was washed with water, filtered and dried at 40° C. under reduced pressure for 48 hours to obtain a photosensitive diazonaphthoquinone (B-3).

[Synthesis Example 2]
<Synthesis of diazonaphthoquinone compound B-4, which is a compound having an aromatic sulfonate structure>
A 1 L separable flask equipped with a stirrer, a dropping funnel and a thermometer was charged with the following formula (b4) as a hydroxy compound:
30 g (0.0707 mol) of 4,4′-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (trade name Tris-PA manufactured by Honshu Chemical Industry Co., Ltd.) represented by was used to dissolve 47.49 g (0.177 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride in an amount corresponding to 83.3 mol % of the OH groups in 300 g of acetone with stirring. The temperature was adjusted to 30°C in the bath. Next, 17.9 g of triethylamine was dissolved in 18 g of acetone, charged into a dropping funnel, and dropped into the flask over 30 minutes. After the dropwise addition was completed, the stirring was continued for an additional 30 minutes, then hydrochloric acid was added dropwise, and the reaction was completed by further stirring for 30 minutes. The reaction was then filtered to remove triethylamine hydrochloride. 1640 g of pure water and 30 g of hydrochloric acid were mixed and stirred in a 3 L beaker, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. The precipitate was washed with water, filtered and dried at 40° C. under reduced pressure for 48 hours to obtain a photosensitive diazonaphthoquinone (B-4).

[Synthesis Example 3]
<Synthesis of diazonaphthoquinone compound B-5, which is a compound having an aromatic sulfonate structure>
4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl) represented by the above formula (21) as a hydroxy compound was placed in a 1 L separable flask equipped with a stirrer, dropping funnel and thermometer. Using 30 g (0.0707 mol) of phenyl) ethylidene) bisphenol (trade name Tris-PA manufactured by Honshu Chemical Industry Co., Ltd.), 1,2-naphthoquinonediazide-4- in an amount corresponding to 83.3 mol% of the OH groups After dissolving 47.49 g (0.177 mol) of sulfonyl chloride in 300 g of acetone with stirring, the flask was adjusted to 30° C. in a constant temperature bath. Next, 17.9 g of triethylamine was dissolved in 18 g of acetone, charged into a dropping funnel, and dropped into the flask over 30 minutes. After the dropwise addition was completed, stirring was continued for an additional 30 minutes, after which hydrochloric acid was added dropwise and stirring was continued for an additional 30 minutes to terminate the reaction. The reaction was then filtered to remove triethylamine hydrochloride. 1640 g of pure water and 30 g of hydrochloric acid were mixed and stirred in a 3 L beaker, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. This precipitate was washed with water, filtered, and dried at 40° C. under reduced pressure for 48 hours to obtain a photosensitive diazonaphthoquinone (B-5).

[Synthesis Example 4]
<Synthesis of diazonaphthoquinone compound B-6, which is a compound having an aromatic sulfonate structure>
A 1 L separable flask equipped with a stirrer, a dropping funnel and a thermometer was charged with the following formula (b6) as a hydroxy compound:
Using 30 g (0.0474 mol) of the compound represented by (trade name Tekoc-4HBPA, manufactured by Honshu Chemical Industry Co., Ltd.), an amount corresponding to 80 mol% of the OH groups of 1,2-naphthoquinonediazide-4-sulfonic acid After stirring and dissolving 40.76 g (0.152 mol) of chloride in 300 g of acetone, the flask was adjusted to 30° C. in a constant temperature bath. Next, 15.4 g of triethylamine was dissolved in 15 g of acetone, charged into a dropping funnel, and dropped into the flask over 30 minutes. After the dropwise addition was completed, the stirring was continued for an additional 30 minutes, then hydrochloric acid was added dropwise, and the reaction was completed by further stirring for 30 minutes. The reaction was then filtered to remove triethylamine hydrochloride. 1640 g of pure water and 22 g of hydrochloric acid were mixed and stirred in a 3 L beaker, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. The precipitate was washed with water, filtered and dried at 40° C. under reduced pressure for 48 hours to obtain a photosensitive diazonaphthoquinone (B-6).

<Preparation of resin composition>
(A) The polymers of Production Examples 1 to 7 were used as the resin.
(B) The following compounds (B-1) to (B-6) were used as compounds having an aromatic sulfonate structure.
(B-1): p-toluenesulfonic acid phenyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-2): p-toluenesulfonic acid naphthyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-3): Diazonaphthoquinone compound (B-4) of [Synthesis Example 1]: Diazonaphthoquinone compound (B-5) of [Synthesis Example 2]: Diazonaphthoquinone compound (B-6) of [Synthesis Example 3] : As the diazonaphthoquinone compound (C) photopolymerization initiator of [Synthesis Example 4], the following (C-1) to (C-4) were used.
(C-1): Benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)
(C-2): 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.)
(C-3): (1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)) (trade name: IRGACURE-OXE-01, manufactured by BASF)
(C-4): 1-Phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime (D) The following (D-1) was used as the photopolymerizable compound.
(D-1) Tetraethylene glycol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Example 1>
100 g of polymer A (corresponding to resin (A)) was dissolved in a mixed solvent of 80 g of NMP and 20 g of ethyl lactate together with 10 g of B-1 and 0.05 g of 2-nitroso-1-naphthol. The viscosity of the resulting solution was adjusted to about 45 poise by further adding a small amount of the mixed solvent, and filtered through a polyethylene filter with a pore size of 0.2 μm to obtain a resin composition.

The resin composition was evaluated according to the method described above. Table 1 shows the evaluation results.

<Example 2>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 1, to 10 g of B-3. was evaluated. Table 1 shows the evaluation results.

<Example 3>
A resin composition was prepared in the same manner as in Example 1 except that 100 g of polymer A, which is the resin (A) in Example 1, was changed to 100 g of polymer B, and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

<Example 4>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 3, to 10 g of B-2. was evaluated. Table 1 shows the evaluation results.

<Example 5>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 3, to 10 g of B-3. was evaluated. Table 1 shows the evaluation results.

<Example 6>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 3, to 1 g of B-4. was evaluated. Table 1 shows the evaluation results.

<Example 7>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 3, to 3 g of B-4. was evaluated. Table 1 shows the evaluation results.

<Example 8>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 3, to 5 g of B-4. was evaluated. Table 1 shows the evaluation results.

<Example 9>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 3, to 10 g of B-4. was evaluated. Table 1 shows the evaluation results.

<Example 10>
10 g of B-1, which is a compound having an aromatic sulfonic acid ester structure in Example 3, was changed to 15 g of B-4, and a mixed solvent of 80 g of NMP and 20 g of ethyl lactate was replaced with a mixed solvent of 85 g of GBL and 15 g of dimethyl sulfoxide. A resin composition was prepared in the same manner as in Example 1 by changing to , and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

<Example 11>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 3, to 30 g of B-4. was evaluated. Table 1 shows the evaluation results.

<Example 12>
A resin composition was prepared in the same manner as in Example 1 except that 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 3, was changed to 50 g of B-4. was evaluated. Table 1 shows the evaluation results.

<Example 13>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 3, to 10 g of B-5. was evaluated. Table 1 shows the evaluation results.

<Example 14>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-1, which is a compound having an aromatic sulfonate structure (B) in Example 3, to 10 g of B-6. was evaluated. Table 1 shows the evaluation results.

<Example 15>
A resin composition was prepared in the same manner as in Example 1 except that 100 g of polymer B, which is the resin (A) in Example 9, was changed to 100 g of polymer C, and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

<Example 16>
A resin composition was prepared in the same manner as in Example 1 except that 100 g of polymer B, which is the resin (A) in Example 9, was changed to 50 g of polymer B and 50 g of polymer C, and the same evaluation as in example 1 was performed. Table 1 shows the evaluation results.

<Example 17>
A resin composition was prepared in the same manner as in Example 1 except that 100 g of polymer A, which is the resin (A) in Example 1, was changed to 100 g of polymer D, and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

<Example 18>
A resin composition was prepared in the same manner as in Example 1 except that 100 g of polymer A, which is the resin (A) in Example 1, was changed to 100 g of polymer E, and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

<Example 19>
A resin composition was prepared in the same manner as in Example 1 except that 100 g of Polymer A, which is the resin (A) in Example 1, was changed to 100 g of Polymer F, and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

<Example 20>
100 g of polymer B, 10 g of B-4, 3 g of C-1 and 0.05 g of 2-nitroso-1-naphthol were all dissolved in a mixed solvent of 80 g of NMP and 20 g of ethyl lactate. The viscosity of the resulting solution was adjusted to about 45 poise by further adding a small amount of the mixed solvent, and filtered through a polyethylene filter with a pore size of 0.2 μm to obtain a resin composition. Each was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

<Example 21>
A resin composition was prepared in the same manner as in Example 20 by changing 3 g of C-1, which is the photopolymerization initiator (C) in Example 20, to 3 g of C-2, and the same evaluation as in Example 1 was performed. . Table 1 shows the evaluation results.

<Example 22>
A resin composition was prepared in the same manner as in Example 20 by changing 3 g of C-1, which is the (C) photopolymerization initiator of Example 20, to 0.1 g of C-3, and the same evaluation as in Example 1 was performed. went. Table 1 shows the evaluation results.

<Example 23>
A resin composition was prepared in the same manner as in Example 20 by changing 3 g of C-1, which is the (C) photopolymerization initiator of Example 20, to 1 g of C-3, and the same evaluation as in Example 1 was performed. . Table 1 shows the evaluation results.

<Example 24>
A resin composition was prepared in the same manner as in Example 20 by changing 3 g of C-1, which is the (C) photopolymerization initiator of Example 20, to 3 g of C-3, and the same evaluation as in Example 1 was performed. . Table 1 shows the evaluation results.

<Example 25>
A resin composition was prepared in the same manner as in Example 20 by changing 3 g of C-1, which is the photopolymerization initiator (C) in Example 20, to 5 g of C-3, and the same evaluation as in Example 1 was performed. . Table 1 shows the evaluation results.

<Example 26>
A resin composition was prepared in the same manner as in Example 20 by changing 3 g of C-1, which is the photopolymerization initiator (C) in Example 20, to 10 g of C-3, and the same evaluation as in Example 1 was performed. . Table 1 shows the evaluation results.

<Example 27>
A resin composition was prepared in the same manner as in Example 20 by changing 3 g of C-1, which is the (C) photopolymerization initiator of Example 20, to 20 g of C-3, and the same evaluation as in Example 1 was performed. . Table 1 shows the evaluation results.

<Example 28>
A resin composition was prepared in the same manner as in Example 20 by changing 3 g of C-1, which is the (C) photopolymerization initiator of Example 20, to 3 g of C-4, and the same evaluation as in Example 1 was performed. . Table 1 shows the evaluation results.

<Example 29>
100 g of polymer B, 10 g of B-4, 3 g of C-3, 10 g of D-1 and 0.05 g of 2-nitroso-1-naphthol were all dissolved in a mixed solvent of 80 g of NMP and 20 g of ethyl lactate. The viscosity of the resulting solution was adjusted to about 45 poise by further adding a small amount of the mixed solvent, and filtered through a polyethylene filter with a pore size of 0.2 μm to obtain a resin composition. Each was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

<Example 30>
Example 1 and Example 1 were obtained by changing 100 g of polymer A, which is the resin of Example 1, to 100 g of polymer I, and 10 g of B-1, which is a compound having an aromatic sulfonate structure, to 10 g of B-3. A resin composition was prepared in the same manner and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

<Example 31>
In Example 1, 100 g of polymer A, which is the resin (A) in Example 1, was changed to 100 g of polymer J, and 10 g of B-1, which is a compound having an aromatic sulfonate structure (B), was changed to 10 g of B-3. A resin composition was prepared in the same manner and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

<Comparative Example 1>
A resin composition was prepared in the same manner as in Example 1 except that 100 g of Polymer B, which is the resin (A) in Example 9, was changed to 100 g of Polymer G, and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

<Comparative Example 2>
A resin composition was prepared in the same manner as in Example 1 except that 100 g of Polymer G, which is the resin (A) of Comparative Example 1, was changed to 100 g of Polymer H, and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

<Comparative Example 3>
100 g of polymer A and 0.05 g of 2-nitroso-1-naphthol were both dissolved in a mixed solvent of 80 g of NMP and 20 g of ethyl lactate. The viscosity of the resulting solution was adjusted to about 45 poise by further adding a small amount of the mixed solvent, and filtered through a polyethylene filter with a pore size of 0.2 μm to obtain a resin composition. Each was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

<Comparative Example 4>
A resin composition was prepared in the same manner as in Comparative Example 3 except that 100 g of Polymer A, which is the resin (A) of Comparative Example 3, was changed to 100 g of Polymer B, and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

<Comparative Example 5>
A resin composition was prepared in the same manner as in Example 1 by changing 10 g of B-3, which is a compound having an aromatic sulfonate structure (B) in Example 2, to 0.1 g of B-3. performed the same evaluation. Table 1 shows the evaluation results.

<Comparative Example 6>
A resin composition was prepared in the same manner as in Comparative Example 6 by changing 0.1 g of B-3, which is a compound having an aromatic sulfonate structure (B) in Comparative Example 5, to 100 g of B-3. performed the same evaluation. Table 1 shows the evaluation results.

<Comparative Example 7>
100 g of polymer B, 3 g of C-3, 10 g of D-1 and 0.05 g of 2-nitroso-1-naphthol were all dissolved in a mixed solvent of 80 g of NMP and 20 g of ethyl lactate. The viscosity of the resulting solution was adjusted to about 45 poise by further adding a small amount of the mixed solvent, and filtered through a polyethylene filter with a pore size of 0.2 μm to obtain a resin composition. Each was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can be suitably used as, for example, a semiconductor device having a copper pattern, a surface protective film of a multilayer wiring board, an interlayer insulating film, an insulating film for rewiring, a cover coat, and a solder resist film.

Claims (13)

(A) A polyimide precursor that is a polyamic acid and/or a polyamic acid ester, and a polyoxazole precursor that is a polyhydroxyamide, having a neutral functional group that is a substitute of an acidic functional group or a basic functional group in a side chain Polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and at least one resin selected from the group consisting of polybenzthiazole: 100 parts by mass, and (B) aromatic sulfonic acid A resin composition containing 1 to 50 parts by mass of a compound having an ester structure. 2. The resin composition according to claim 1, wherein said neutral functional group is one or more groups selected from the group consisting of methacryl groups, acryl groups and styryl groups. The (A) resin has the following general formula (1):
{wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently In, a hydrogen atom, or the following general formula (1a):
(wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10). It is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. }, the following general formula (2):
{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and has the same structure, or a plurality of wherein R ₆ is an organic group having at least one radically polymerizable unsaturated bond group of 3-20 carbon atoms, and n ₂ is an integer of 1-1000. } and the following general formula (3):
{wherein X ₅ is a 4- to 14-valent organic group, Y ₅ is a 2- to 12-valent organic group, and R ₇ and R ₈ are each independently a phenolic hydroxyl group and a sulfonic acid group; or a structure in which a group selected from a thiol group is substituted with an organic group having at least one selected from the group consisting of a methacryl group, an acryl group and a styryl group, n ₅ is an integer of 3 to 200, and m ₂ and m ₃ represent integers from 0 to 10; 3. The resin composition according to claim 1 or 2, which is at least one resin selected from the group consisting of polyimides having a structure represented by }. X ₁ in the above general formula (1) is represented by the following formula:
The resin composition according to claim 3, comprising at least one structure selected from the group consisting of structures represented by The resin composition according to any one of claims 1 to 4, wherein (B) the compound having an aromatic sulfonate structure is a quinonediazide compound. 6. The resin composition according to claim 5, wherein the quinonediazide compound has an average of 2.4 or more quinonediazide structures in the molecule. The (B) compound having an aromatic sulfonate structure is represented by the following general formulas (4) to (8):
{In Formula (4), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms, and X ₃ and X ₄ each independently represent a hydrogen atom or a carbon represents a monovalent organic group of numbers 1 to 60, r1, r2, r3 and r4 are each independently an integer of 0 to 5, and at least one of r3 and r4 is an integer of 1 to 5 , r1+r3=5 and r2+r4=5. }
{In formula (5), Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X ₅ , X ₆ , X ₇ and X ₈ each independently represent a monovalent organic group having 1 to 30 carbon atoms. represents an organic group, r6 is an integer of 0 or 1, r5, r7, r8 and r9 are each independently an integer of 0 to 3, r10, r11, r12 and r13 are each independently is an integer from 0 to 2, and at least one of r10, r11, r12 and r13 is 1 or 2; }
{In formula (6), r14 represents an integer of 1 to 5, r15 is an integer of 3 to 8, and (r14 × r15) L are each independently 1 having 1 to 20 carbon atoms represents a valent organic group, (r15) T are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and (r15) S are each independently hydrogen represents an atom or a monovalent organic group having 1 to 20 carbon atoms; }
{In formula (7), A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group. }
{In formula (8), r17, r18, r19 and r20 are each independently an integer of 0 to 2, at least one of r17, r18, r19 and r20 is 1 or 2, and X10 to X19 each independently represents at least one monovalent group selected from the group _consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group and an _{acyl group} ; , each independently a single bond, -O-, -S-, -SO-, -SO2-, -CO-, -CO2-, cyclopentylidene, cyclohexylidene, phenylene and divalent having 1 to 20 carbon atoms represents at least one divalent group selected from the group consisting of organic groups of } is a 1,2-naphthoquinonediazide-4-sulfonic acid ester and/or a 1,2-naphthoquinonediazide-5-sulfonic acid ester of at least one compound selected from the group consisting of hydroxy compounds represented by The resin composition according to any one of claims 1-6. The hydroxy compound represented by the general formula (4) is represented by the following general formula (4a):
{In formula (4a), each r16 is independently an integer of 0 to 2, and each _X9 independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The resin composition according to claim 7, which is a compound represented by }. In the general formula (5), Z is the following formula:
The resin composition according to claim 7 or 8, which is at least one group selected from the group consisting of tetravalent groups represented by. (C) The resin composition according to any one of claims 1 to 9, further comprising a photopolymerization initiator. The (C) photopolymerization initiator has the following general formula (10):
{In Formula (10), R ₁ , R ₂ and R ₃ each represent a monovalent organic group, and R ₁ and R ₂ may be linked together to form a ring structure} The resin composition according to claim 10, which is an oxime ester compound. (D) The resin composition according to any one of claims 1 to 11, further comprising a photopolymerizable compound. (1) forming a resin film on a substrate by coating the resin composition according to any one of claims 1 to 12 on the substrate;
(2) forming a cured film by heat-treating the resin film;
(3) flattening the cured film by polishing;
A method for producing a cured film, comprising: