WO2015178074A1 - Photosensitive resin composition and use of same - Google Patents

Abstract

[Problem] To provide a photosensitive resin composition which is capable of forming a cured film having a small internal stress. [Solution] A photosensitive resin composition which contains (A) a polymer having a structural unit represented by formula (A1), (B) a photosensitive acid generator, and (C) a crosslinking agent. (In formula (A1), a hydroxyl group is a substituent that is bonded to the naphthalene ring; R¹ represents a substituent that is bonded to the naphthalene ring, said substituent being a halogen atom or an alkyl group having 1-10 carbon atoms, and in cases where a plurality of R¹ moieties are present, the plurality of R¹ moieties may be the same as or different from each other; a represents an integer of 1-6, b represents an integer of 0-4, and a and b satisfy 1 ≤ a + b ≤ 6; and bonding bands *1 and *2 may be bonded to the same benzene nucleus contained in the naphthalene ring or to different benzene nuclei.)

Description

Photosensitive resin composition and use thereof

The present invention relates to a photosensitive resin composition suitably used for the formation of a surface protective film, an interlayer insulating film and the like possessed by an electronic component, etc., and further a resin coating film, a cured film formed from the composition, and a method for producing the same And an electronic component having the cured film.

The semiconductor element that constitutes the electronic component includes an insulating film. Conventionally, various photosensitive resin compositions have been proposed as resin compositions used when forming this insulating film (see, for example, Patent Documents 1 to 3).

The insulating film is usually formed on the substrate using a composition containing a cross-linking agent in order to impart insulation, chemical resistance and heat resistance thereto. However, when a resin coating film is formed using such a composition and this coating film is dried and cured to form an insulating film (cured film), the coating film shrinks due to the crosslinking agent. As a result, internal stress remains in the insulating film. If the internal stress of the insulating film is large, the substrate may be warped after the insulating film is formed, or the insulating film may be cracked by an impact when the electronic device is dropped.

Patent Document 4 discloses a positive photosensitive resin composition containing polynaphthylene and a compound that generates an acid by light. However, since the composition does not contain a crosslinking agent, there is no mention of shrinkage of the resin coating film caused by the crosslinking agent.

JP 2006-154780 A JP 2007-056109 A JP 2013-209607 A JP 2002-341542 A

A cured film formed using a conventional photosensitive resin composition has a problem that internal stress is large. An object of the present invention is to provide a photosensitive resin composition capable of forming a cured film having a small internal stress.

The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-described problems can be solved by using a photosensitive resin composition having the following configuration, and the present invention has been completed.

The present invention includes, for example, the following [1] to [12].
[1] A photosensitive resin composition comprising (A) a polymer having a structural unit represented by formula (A1), (B) a photosensitive acid generator, and (C) a crosslinking agent.

Wherein (A1), a hydroxyl group is a substituted group bonded to a naphthalene ring; R ¹ is a substituent bonded to the naphthalene ring, a halogen atom or an alkyl group having 1 to 10 carbon atoms, R ¹ May be the same as or different from each other when a plurality is present; a is an integer of 1 to 6, b is an integer of 0 to 4, and 1 ≦ a + b ≦ 6; * 2 may be bonded to the same benzene nucleus contained in the naphthalene ring, or may be bonded to different benzene nuclei. ]

[2] The photosensitive resin composition according to [1], wherein in the structural unit represented by the formula (A1), the bonds * 1 and * 2 are bonded to different benzene nuclei contained in the naphthalene ring.
[3] The photosensitive resin composition according to [1] or [2], wherein the structural unit represented by the formula (A1) is a structural unit represented by the formula (A1-1).

[4] The above [1] to [3], wherein the polymer (A) has a weight average molecular weight (Mw) measured by a gel permeation chromatography method of more than 10,000 and not more than 200,000 in terms of polystyrene. ] The photosensitive resin composition of any one of these.

[5] The crosslinking agent (C1) in which the crosslinking agent (C) has at least two groups represented by —CH ₂ OR (where R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acetyl group) The photosensitive resin composition according to any one of the above [1] to [4], comprising:

[6] The photosensitive property according to any one of [1] to [5], wherein the content of the crosslinking agent (C) is 5 to 50 parts by mass with respect to 100 parts by mass of the polymer (A). Resin composition.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the photosensitive acid generator (B) includes a compound containing a haloalkyl group and a triazine skeleton.

[8] A cured film obtained from the photosensitive resin composition according to any one of [1] to [7].
[9] A resin coating film containing a polymer (A) having a structural unit represented by the formula (A1).

[10] A step of forming a resin coating film of the photosensitive resin composition according to any one of [1] to [7] on a substrate having metal, a step of exposing the resin coating film, The manufacturing method of the patterned cured film which has the process of developing the resin coating film after the said exposure with alkaline developing solution.

[11] An electronic component having the cured film according to [8].
[12] An electronic component having a substrate, a metal wiring, and a rewiring layer including the cured film according to [8].

According to the present invention, a photosensitive resin composition capable of forming a cured film with low internal stress can be provided. For this reason, the curvature of the board | substrate after cured film formation can be suppressed, and generation | occurrence | production of a crack can be suppressed in a cured film when an electronic device falls.

FIG. 1 is a top view of a base material for electrical insulation evaluation.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described including preferred embodiments.
[Photosensitive resin composition]
The photosensitive resin composition of this invention contains the polymer (A) demonstrated below, the photosensitive acid generator (B), and a crosslinking agent (C). The photosensitive resin composition of the present invention is also referred to as “the composition of the present invention”.

<Polymer (A)>
The polymer (A) has a structural unit represented by the formula (A1). The structural unit represented by the formula (A1) is also referred to as “structural unit (A1)”. Since the polymer (A1) has the structural unit (A1), the resin coating film formed from the composition of the present invention has a poly (hydroxynaphthylene) structure. Thus, since the cured film obtained even after the crosslinking reaction in the resin coating film has a rigid polynaphthylene skeleton, it is presumed that a cured film having a small internal stress was obtained.

In the formula (A1), details of each symbol are as follows.

A hydroxyl group is a substituent bonded to the naphthalene ring. R ¹ is a substituent bonded to the naphthalene ring, and is a halogen atom or an alkyl group having 1 to 10 carbon atoms. When a plurality of R ¹ are present, they may be the same as or different from each other.

The “substituent bonded to the naphthalene ring” may be bonded to any of the two benzene nuclei contained in the naphthalene ring. A plurality of hydroxyl groups may be bonded to the same benzene nucleus contained in the naphthalene ring or may be bonded to different benzene nuclei. When a plurality of R ¹ are present, they may be bonded to the same benzene nucleus contained in the naphthalene ring or may be bonded to different benzene nuclei.

Examples of the halogen atom include fluorine, chlorine, and iodine.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms.

A is an integer of 1 to 6, b is an integer of 0 to 4, and 1 ≦ a + b ≦ 6. a is preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and still more preferably 2. b is preferably an integer of 0 to 2, and more preferably 0. a + b is preferably 2 to 6.

In the structural unit (A1), the bonds * 1 and * 2 may be bonded to the same benzene nucleus contained in the naphthalene ring (for example, 1 below) or may be bonded to different benzene nuclei ( For example, the following 2).

Examples of the bonding site of the bond * 1 and * 2 in the structural unit (A1) include the 1,2-position, 1,3-position, 1,4-position, 1,5-position, 1,6-position, and 1,7-position. 1,8th, 2,3th, 2,4th, 2,5th, 2,6th, 2,7th, 2,8th, 3,4th, 3,5th, 3,6th 3, 7th, 3, 8th, 4,5th, 4,6th, 4,7th, 4th, 8th.

The structural unit (A1) is preferably a structural unit in which the bonds * 1 and * 2 are bonded to different benzene nuclei contained in the naphthalene ring. In this case, a cured film having a small internal stress tends to be obtained.

The structural unit (A1) is particularly preferably a structural unit represented by the formula (A1-1). The structural unit represented by the formula (A1-1) is also referred to as “structural unit (A1-1)”. In this case, a cured film having a smaller internal stress tends to be obtained.

Content of a structural unit (A1) is 80 mass% or more normally in 100 mass% of polymers (A), Preferably it is 90 mass% or more, More preferably, it is 99 mass% or more. When the content is in the above range, a cured film having a small internal stress tends to be obtained.

The weight average molecular weight (Mw) measured by the gel permeation chromatography method of the polymer (A) is usually more than 10,000 and not more than 200,000, preferably 15,000 to 100,000 in terms of polystyrene. More preferably, it is 20,000 to 60,000.

When Mw is in the above range, a cured film having high resolution, low internal stress, and high crack resistance can be formed. Details of the method for measuring Mw are as described in the examples. Mw can be adjusted by changing the kind and amount of the one-electron oxidizing agent and reaction solvent described later.

The polymer (A) is preferably a resin that dissolves 0.001 mg / ml or more in a 2.38% by mass tetramethylammonium hydroxide aqueous solution (23 ° C.).
The content of the polymer (A) is usually 50 to 95% by mass, preferably 60 to 90% by mass, and more preferably 70 to 85% by mass in 100% by mass of the solid content contained in the composition of the present invention. . The solid content usually means all components other than the solvent (F) contained in the composition of the present invention. When the content of the polymer (A) is in the above range, a composition capable of forming a cured film with high resolution tends to be obtained.

Examples of the method for synthesizing the polymer (A) include the methods described in paragraphs [0027] to [0035] of JP-A-2008-65081. Specifically, as a monomer, a naphthalene derivative corresponding to the structural unit (A1) is used, and if necessary, another copolymerizable monomer is used and a coupling reaction is performed. ) Can be obtained.

From the viewpoint of molecular weight control, a coupling reaction using a one-electron oxidant is preferable. The coupling reaction using a one-electron oxidant can be performed by dissolving a naphthalene derivative in a reaction solvent. The phenomenon of oxidizing the oxide by taking one electron from the oxide is called one-electron oxidation, and the component that receives one electron at this time is called one-electron oxidant.
As a naphthalene derivative, the derivative represented by a formula (a1) is mentioned, for example.

In formula (a1), R ¹ , a and b are synonymous with the same symbols in formula (A1). Further, each of the hydroxyl group and R ¹ may be bonded to the same benzene nucleus contained in the naphthalene ring, or may be bonded to different benzene nuclei.

Examples of the naphthalene derivative include derivatives where a = 2 in the formula (a1), and specifically include 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5- Examples thereof include dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene and 3-methyl-2,6-dihydroxynaphthalene.

A naphthalene derivative may be used individually by 1 type and may use 2 or more types together.
Examples of other copolymerizable monomers include phenol, p-isopropenylphenol, ethynylstyrene, propargylic acid, 6-hexynoic acid, 2-propyn-1-ol, 1-butyn-3-ol, 3 -Butyn-3-ol, 1-pentyn-3-ol, 4-pentyn-1-ol, 3-ethynylaniline, 4-ethynylaniline and phenylacetylene.

Other copolymerizable monomers may be used alone or in combination of two or more.
Examples of the one-electron oxidant include organometallic compounds, peracids or peroxides, diazo compounds, halogens or halogen acids, ozone, and enzymes described in JP-A-2008-65081 described above. These may be used alone or in combination of two or more.

Among the one-electron oxidizers, organometallic compounds are preferable in view of reaction results, and copper (II) compounds and iron (III) compounds are preferable. Specifically, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′ , N′-Tetramethylpropylenediamine) copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetraethylethylenediamine) copper (II)] chloride, di-μ-hydroxo -Bis [(N, N, N ′, N′-tetraethylethylenediamine) copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethyl-1,6- Hexanediamine) copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethyl-1,8-naphthalenediamine) copper (II)] chloride, di-μ- Hydroxo-bis [(N, N, N ′, N′-tetramethylethylenedi Amine) titanium (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) cerium (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) iron] chloride is preferred.
Further, examples of the one-electron oxidizing agent include iron (II) compounds such as N, N′-bis (salicylidene) ethylenediamine iron (II).

Also, when using a combination of a plurality of one-electron oxidants [for example, a combination of an organic metal compound such as a copper (II) compound and a peracid or peroxide] and when using a one-electron oxidant alone In comparison, the oxidation rate can be greatly improved. Examples of the peracid include peracetic acid and m-chloroperbenzoic acid. Examples of the peroxide include hydrogen peroxide and t-butyl hydroperoxide.

The amount of the one-electron oxidizing agent used is preferably 0.0001 to 10 mol, more preferably 0.01 to 5 mol, and still more preferably 0.1 to 1 mol, with respect to 1 mol of the naphthalene derivative. .

The reaction solvent used in the coupling reaction is preferably a monomer that forms a polymer, a one-electron oxidant, and a solvent that dissolves the resulting polymer, such as methanol, 2-methoxyethanol, 2-ethoxyethanol, Examples include 3-methoxypropanol, 3-ethoxypropanol, ethyl lactate, propane lactic acid, butyl lactate, and N, N-dimethylformamide.

The reaction conditions for the coupling reaction are, for example, 10 to 100 ° C. and 0.1 to 10 hours. After completion of the coupling reaction, the reaction solution contains impurities other than the polymer (A) such as a catalyst residue. For this reason, after completion | finish of reaction, it is preferable to refine | purify by a well-known purification method, for example, a reprecipitation method and a liquid washing method.

<Photosensitive acid generator (B)>
The composition of the present invention contains a photosensitive acid generator (B). The photosensitive acid generator (B) is a compound that generates an acid by a treatment including light irradiation. By the process including the exposure process for the resin coating film formed from the composition of the present invention, an acid is generated in the exposed part based on the photosensitive acid generator (B), and an alkaline aqueous solution in the exposed part is formed based on the action of this acid. Solubility changes.

The composition of the present invention may be either a negative type or a positive type. The kind of the photosensitive acid generator (B) can be appropriately selected according to the negative composition or the positive composition. Among these, a negative composition is preferable from the viewpoints of insulation, chemical resistance, and heat resistance.

Examples of the photosensitive acid generator (B) include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, and compounds having a quinonediazide group. Hereinafter, the compound having a quinonediazide group is also referred to as “quinonediazide compound (B2)”, and the other exemplified photosensitive acid generators are also referred to as “acid generator (B1)”.

The acid generator (B1) is a compound that forms an acid when irradiated with light. When the resin coating film obtained from the composition containing the acid generator (B1) is irradiated with light, the generated acid acts on the polymer (A), the cross-linking agent (C) and the like to form a cross-linked structure. This is a film that is hardly soluble in alkali. A negative pattern is formed by utilizing the fact that the film changes from a readily alkaline soluble state to a hardly alkaline soluble state by light irradiation.

The quinonediazide compound (B2) is a compound in which a quinonediazide group is decomposed to generate a carboxyl group by light irradiation and contact treatment with water. The resin coating film obtained from the composition containing the quinonediazide compound (B2) is a film that is hardly soluble in an alkaline developer. A positive pattern is formed by utilizing the fact that the film is changed from a hardly alkali-soluble state to an easily alkali-soluble state by light irradiation.

<< Acid generator (B1) >>
The acid generator (B1) is at least one selected from, for example, an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound.

Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Specific examples of preferred onium salts include iodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate; L-methanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7- Di-n-butoxynaphthyltetrahydrothiofe Um trifluoromethanesulfonate, 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, etc. A sulfonium salt is mentioned.

Examples of the halogen-containing compound include a haloalkyl group-containing heterocyclic compound and a haloalkyl group-containing hydrocarbon compound. Specific examples of preferred halogen-containing compounds include compounds containing a haloalkyl group and a triazine skeleton; 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane Can be mentioned.

As the photosensitive acid generator (B), a compound containing a haloalkyl group and a triazine skeleton is particularly preferable. Hereinafter, this compound is also referred to as “triazine skeleton-containing compound”. When a triazine skeleton-containing compound is used, a cured film having excellent resolution and low internal stress tends to be obtained.

The triazine skeleton-containing compound is, for example, a photosensitive acid generator represented by the formula (B-1). The photosensitive acid generator represented by the formula (B-1) is also referred to as “photosensitive acid generator (B-1)”.

In formula (B-1), R ^B1 each independently represents an aryl group, an alkoxy group-substituted aryl group, an aryl group-substituted alkenyl group, a heterocyclic group-substituted alkenyl group, or a haloalkyl group, and at least one R ^B1 represents a haloalkyl group It is a group. Two R ^B1 are preferably a haloalkyl group, and the other R ^B1 is preferably an aryl group, an alkoxy group-substituted aryl group, an aryl group-substituted alkenyl group or a heterocyclic group-substituted alkenyl group.

Examples of the aryl group include groups having 6 to 20 carbon atoms, and specific examples include a phenyl group and a naphthyl group. An alkoxy group-substituted aryl group is a group formed by substituting at least one hydrogen atom bonded to an aromatic ring in an aryl group with an alkoxy group, and includes a group having 7 to 30 carbon atoms. A phenyl group etc. are mentioned.

The aryl group or heterocyclic group-substituted alkenyl group is a group formed by substituting at least one hydrogen atom of an alkenyl group with an aryl group or a heterocyclic group. Examples of the aryl group-substituted alkenyl group include groups having 8 to 30 carbon atoms, and specifically include a styryl group. Examples of the heterocyclic group include groups having 4 to 20 carbon atoms, such as a furanyl group and a methylfuranyl group. Specific examples of the heterocyclic group-substituted alkenyl group include groups having 6 to 30 carbon atoms. Specific examples include 2- (5-methylfuran-2-yl) ethenyl group.

The haloalkyl group is a group formed by substituting at least one hydrogen atom of an alkyl group with a halogen atom, and includes a group having 1 to 10 carbon atoms, specifically, a trichloromethyl group and the like.

Examples of the photosensitive acid generator (B-1) include phenyl-bis (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl)- s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, etc. -Triazine derivatives.

Examples of sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples of preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenacylsulfonyl) methane.

Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, and o-nitrobenzyl p-toluene sulfonate.

Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy). ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide.

Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.
The acid generator (B1) may be used alone or in combination of two or more.

In the composition of the present invention, when the acid generator (B1) is used as the photosensitive acid generator (B), the content of the acid generator (B1) is preferably 100 parts by mass of the polymer (A). Is 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 5 parts by mass.

When the content of the acid generator (B1) is equal to or higher than the lower limit, the exposed area is sufficiently cured and the heat resistance is easily improved. When the content of the acid generator (B1) is not more than the above upper limit value, a patterned cured film having a high resolution is easily obtained without lowering the transparency to exposure light.

<< Quinonediazide compound (B2) >>
Examples of the quinonediazide compound (B2) include a naphthoquinonediazide compound, specifically, a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphtho Examples include ester compounds with quinonediazide-5-sulfonic acid.

Examples of the quinonediazide compound (B2) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2 , 3,4,2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [ 1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene and 1,1- (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-4-sulfonic acid or 1 , 2-naphthoquinonediazide-5-sulfonic acid ester compounds.
A quinonediazide compound (B2) may be used by 1 type, and may use 2 or more types together.

In the composition of the present invention, when the quinonediazide compound (B2) is used as the photosensitive acid generator (B), the content of the quinonediazide compound (B2) is preferably 5 with respect to 100 parts by mass of the polymer (A). -50 parts by mass, more preferably 10-30 parts by mass, still more preferably 15-30 parts by mass.

When the content of the quinonediazide compound (B2) is equal to or higher than the lower limit, the remaining film ratio in the unexposed area is improved and an image faithful to the mask pattern is easily obtained. When the content of the quinonediazide compound (B2) is not more than the above upper limit value, a cured film excellent in pattern shape is easily obtained, and foaming during film formation tends to be prevented.

<Crosslinking agent (C)>
The composition of the present invention contains a crosslinking agent (C). By using a crosslinking agent (C), the insulation of a cured film, chemical resistance, and heat resistance can be improved.

Examples of the crosslinking agent (C) include a crosslinking agent (C1) having at least two groups represented by —CH ₂ OR and other crosslinking agents (C2). In the above formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acetyl group. The (C1) is also referred to as “active methylene group-containing crosslinking agent (C1)”. Among these, the crosslinking agent (C1) is preferable because a cured film having a small internal stress can be formed.

In the composition of the present invention, the content of the crosslinking agent (C) is usually 5 to 50 parts by weight, preferably 10 to 40 parts by weight, and more preferably 15 to 30 parts by weight with respect to 100 parts by weight of the polymer (A). Part by mass. When the content of the crosslinking agent (C) is in the above range, a composition excellent in sensitivity and resolution is obtained, and a cured film excellent in insulation tends to be obtained.

<< Active methylene group-containing crosslinking agent (C1) >>
The active methylene group-containing crosslinking agent (C1) is a crosslinking agent having at least two groups represented by —CH ₂ OR. In the formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acetyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Here, since the group represented by —CH ₂ OR has an active methylene group, for example, in the case of the negative type, the active methylene group is converted into the polymer (A) based on the acid derived from the photosensitive acid generator (B). Nucleophilic reaction with the contained naphthalene ring causes the crosslinking reaction to proceed. Here, the “active methylene group” means a methylene group sandwiched between two electron donating groups.
Examples of the crosslinking agent (C1) include a compound having two or more groups represented by the formula (C1-1) and a compound having two or more groups represented by the formula (C1-2).

In the formulas (C1-1) and (C1-2), m is 1 or 2, n is 0 or 1, m + n is 2, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or An acetyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * is a bond.

Examples of the crosslinking agent (C1) include nitrogen compounds such as polymethylolated melamine, polymethylolated glycoluril, polymethylolated guanamine, and polymethylolated urea; active methylol groups in the nitrogen compounds (CH bonded to N atom) ₂ OH group) or all of a part thereof are alkyl etherified or acetoxylated. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be the same as or different from each other. Moreover, the active methylol group which is not alkyletherified or acetoxylated may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.

Examples of the crosslinking agent (C1) include crosslinking agents described in JP-A-6-180501, JP-A-2006-178059, and JP-A-2012-226297. Specifically, melamine-based crosslinking agents such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine; polymethylolated glycoluril, tetramethoxymethylglycoluril, tetrabutoxy Glycoluril-based crosslinking agents such as methylglycoluril; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [ 5,5] Undecane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetraoxospiro [5,5] undecane A compound obtained by methylolating guanamine, etc., and all of the active methylol groups in the compound Or guanamine-based crosslinking agent such as an alkyl etherified or acetoxylation the compounds of the part. Among these, a melamine type crosslinking agent and a guanamine type crosslinking agent are preferable.

Other examples of the crosslinking agent (C1) include a methylol group-containing phenol compound, an alkylmethylol group-containing phenol compound, and an acetoxymethyl group-containing phenol compound. Specific examples include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and compounds represented by the following formulae. It is done.

A crosslinking agent (C1) may be used by 1 type, and may use 2 or more types together.

<< Other cross-linking agent (C2) >>
Examples of the other crosslinking agent (C2) include an oxirane ring-containing compound, an oxetane ring-containing compound, an isocyanate group-containing compound (including a blocked one), an oxazoline ring-containing compound, and an aldehyde group-containing phenol compound. .

As the oxirane ring-containing compound, it is sufficient that an oxirane ring is contained in the molecule. For example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin Phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, and aliphatic epoxy resin.

Specific examples of the oxirane ring-containing compound include resorcinol diglycidyl ether, pentaerythritol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, phenyl glycidyl ether, neopentyl glycol diglycidyl ether, ethylene / polyethylene glycol diester. Examples thereof include glycidyl ether, propylene / polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether.
The other crosslinking agent (C2) may be used alone or in combination of two or more.

<Adhesion aid (D)>
In order to improve the adhesion between the cured film and the substrate, the composition of the present invention may further contain an adhesion assistant (D). As the adhesion assistant (D), a functional silane coupling agent is preferable, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, and an epoxy group. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate.

In the composition of the present invention, when the adhesion assistant (D) is used, the content of the adhesion assistant (D) is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polymer (A). More preferably, it is 0.5 to 20 parts by mass. When the content of the adhesion aid (D) is in the above range, the adhesion of the cured film to the substrate is further improved.

<Acid diffusion control agent (E)>
The acid diffusion inhibitor (E) can be used for suppressing diffusion of an acid generated from the photosensitive acid generator (B) upon exposure in the resin coating film. By suppressing the diffusion of the acid, the resolution of the photosensitive resin composition can be improved.

Examples of the acid diffusion inhibitor (E) include compounds usually used in resist compositions described in International Publication No. 2009/051088 pamphlet. Examples of the acid diffusion inhibitor (E) include tri (cyclo) alkylamines such as triethylamine, tri-n-propylamine and tri-n-butylamine; aromatic amines such as aniline, diphenylamine, triphenylamine and naphthylamine Quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetra-n-butylammonium hydroxide; nitrogen-containing heterocycles such as pyrazine, pyrazole and acridine; Nt-butoxycarbonyldi-n-octylamine Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxy Carbonyl-2-methylbenzimi Protecting group such as sol, Nt-butoxycarbonyl-2-phenylbenzimidazole, Nt-butoxycarbonyl-pyrrolidine, Nt-butoxycarbonyl-piperidine, Nt-butoxycarbonyl-4-hydroxy-piperidine The amine which has is mentioned. Among these, amines having a protecting group are preferable from the viewpoint of resolution.

In the composition of the present invention, when the acid diffusion inhibitor (E) is used, the content thereof is preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the photosensitive acid generator (B). Is 1 to 5 parts by mass.

<Solvent (F)>
The composition of the present invention preferably contains a solvent (F). By using the solvent (F), the handleability of the composition can be improved, and the viscosity and storage stability can be adjusted.

As the solvent (F), for example,
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; propylene glycol monomethyl ether , Propylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether Propylene glycol dialkyl ethers and the like; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol monobutyl ether acetate;
Carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-acetate Aliphatic carboxylic acid esters such as amyl, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Other esters such as ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactones such as γ-butyrolacun Aromatic hydrocarbons such as toluene and xylene;
Is mentioned.

Among these, lactic acid esters, propylene glycol monoalkyl ether acetates, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers are preferred; ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether Is more preferable.

A solvent (F) may be used by 1 type and may use 2 or more types together.
When the solvent (F) is used in the composition of the present invention, the amount of the solvent (F) used is usually 1 to 70% by mass, preferably 5 to 60% by mass, more preferably the solid content concentration in the composition. Is in the range of 10 to 50% by mass.

<Other additives>
In addition, the composition of the present invention contains various additives such as cross-linked fine particles, leveling agents, surfactants, sensitizers, inorganic fillers, quenchers, and the like as long as the object and characteristics of the present invention are not impaired. Can do.

<Method for preparing photosensitive resin composition>
The composition of this invention can be prepared by mixing each component uniformly. Moreover, in order to remove dust, after mixing each component uniformly, you may filter the obtained mixture with a filter.

[Resin coating film]
The resin coating film of the present invention contains a polymer (A) having a structural unit represented by the above formula (A1). This resin coating film can be formed using the above-described photosensitive resin composition of the present invention, for example, according to the following [1] coating film forming step.

[Curing film and method for producing the same]
The cured film of this invention is formed from the above-mentioned photosensitive resin composition, for example. By using the composition, a cured film having a low internal stress can be obtained. For example, according to the present invention, a cured film having an internal stress of usually 25 MPa or less, preferably 20 MPa or less, more preferably 15 MPa or less can be formed. This internal stress can be evaluated by the stress difference before and after the formation of the cured film on the substrate on which the cured film is formed. For this reason, the curvature of the board | substrate after cured film formation can be suppressed, and generation | occurrence | production of a crack can be suppressed in a cured film when an electronic device falls. Furthermore, a cured film having high heat resistance, chemical resistance and insulation, and a patterned cured film having high resolution can be produced.

Therefore, the composition of the present invention is used for a material for forming a surface protective film, an interlayer insulating film, a planarizing film, etc., and a high-density mounting substrate, which electronic parts such as a circuit board (semiconductor element), a semiconductor package or a display element have. It can be suitably used as an insulating film material.

Examples of production of the cured film of the present invention are shown below. This production example includes a step of forming a resin coating film of the composition of the present invention on a substrate having a metal (coating film forming step), a step of exposing the resin coating film (exposure step), and an alkaline developer. The process of developing the resin coating after exposure to form a desired pattern on the substrate by dissolving and removing the non-exposed part in the case of negative type and the exposed part in the case of positive type (developing process) Have The said manufacture example has the process (heating process) of heat-processing the said pattern as needed.

[1] Coating film forming step In the coating film forming step, for example, the composition is applied onto a substrate having a metal so that the finally obtained cured film has a thickness of, for example, 0.1 to 100 μm. . This is usually heated at 50 to 140 ° C. for 10 to 360 seconds using an oven or a hot plate. In this way, a resin coating film is formed on the substrate having metal.

Examples of the substrate include a silicon wafer, a compound semiconductor wafer, a glass substrate, a quartz substrate, a ceramic substrate, an aluminum substrate, and a substrate having a semiconductor chip on the surface of these substrates. As a board | substrate which has a metal, the board | substrate with which metal wiring, such as copper wiring, was formed is mentioned, for example.

Examples of the coating method of the composition include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an inkjet method.

[2] Exposure process In the exposure process, the resin coating film is exposed through a desired mask pattern using, for example, a contact aligner, a stepper, or a scanner. Examples of exposure light include ultraviolet light and visible light, and light with a wavelength of 200 to 500 nm (eg, i-line (365 nm)) is usually used. The irradiation amount of actinic rays varies depending on the type and content of each component in the photosensitive resin composition, the thickness of the resin coating film, etc., but when using i-line for exposure light, the exposure amount is usually 50-2. 1,000 mJ / m ² .

In the case of using a negative photosensitive resin composition, it is preferable to perform a heat treatment after exposure in order to further promote the crosslinking reaction. Hereinafter, this processing is also referred to as “PEB processing”. The PEB condition varies depending on the type and content of each component in the photosensitive resin composition and the thickness of the resin coating film, but is usually 70 to 150 ° C., preferably 80 to 120 ° C., for about 1 to 60 minutes. is there.

[3] Development process In the development process, the resin coating film is developed with an alkaline developer, and the metal is contained by dissolving and removing the non-exposed part in the case of the negative type and the exposed part in the case of the positive type. A desired pattern is formed on the substrate.

Examples of the development method include a shower development method, a spray development method, an immersion development method, and a paddle development method. The development conditions are usually about 20 to 40 ° C. for about 1 to 10 minutes.
Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, choline, etc. is dissolved in water so as to have a concentration of 1 to 10% by mass. Is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. In addition, after developing the resin coating film with an alkaline developer, it may be washed with water and dried.

[4] Heating step If necessary, the pattern is further cured by heating, for example, in order to sufficiently develop the characteristics as an insulating film. The heating conditions are not particularly limited, but for example, heating is performed at a temperature of 100 to 300 ° C. for about 30 minutes to 10 hours depending on the use of the cured film. In order to sufficiently advance the curing or to prevent the deformation of the pattern shape, heating can be performed in multiple stages.
As described above, a cured film can be obtained.

[Electronic parts]
When the photosensitive resin composition of the present invention is used, an electronic component having the above-described cured film, for example, a circuit board (semiconductor) having at least one cured film selected from a surface protective film, an interlayer insulating film, and a planarizing film. Element), a semiconductor package, or an electronic component such as a display element.

For example, an electronic component having a substrate and a rewiring layer including a metal wiring and the cured film may be mentioned. This rewiring layer is obtained by repeatedly filling a metal by plating or the like between the patterns of the patterned cured film formed in the above manufacturing example, and laminating the patterned cured film and filling the metal as necessary. Can be formed.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of Examples and the like, “part” is used to mean “part by mass” unless otherwise specified.

[1] Method for measuring physical properties [1-1] Method for measuring weight average molecular weight (Mw) of polymer Mw was measured by gel permeation chromatography under the following conditions.
Column: Tosoh column TSK-M and TSK2500 connected in series Developing solvent: Tetrahydrofuran Sample concentration: 0.01% by mass
・ Temperature: 40 ℃
・ Detection method: Refractive index method ・ Standard material: Polystyrene ・ GPC apparatus: manufactured by Tosoh Corporation, apparatus name “HLC-8220-GPC”

[1-2] Polymer Identification Method The polymer was identified by H-NMR and infrared spectroscopy.
Infrared spectroscopic analysis was performed by the following method. The polymer was dissolved in 2-methylethanol to prepare a solution having a solid concentration of 20% by mass. The solution was applied onto a substrate made of polyethylene terephthalate by a doctor blade method and heated at 70 ° C. for 30 minutes and 120 ° C. for 30 minutes to obtain a coating film. The coating film was peeled off from the substrate, and the coating film was fixed to a metal frame with an adhesive tape, followed by vacuum drying at 120 ° C. for 2 hours to obtain an infrared evaluation film having a thickness of 20 μm.

[2] Synthesis of Polymer [Synthesis Example 1] Synthesis of Polymer (A1) In a flask, 20.00 g (0.125 mol) of 2,6-dihydroxynaphthalene, 0.58 g (0.125 mmol) in a nitrogen atmosphere. ) Di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) copper (II)] chloride and 380 mL of 2-methoxyethanol were prepared. While stirring the mixed solution A at 25 ° C. in a nitrogen atmosphere, 13.7 g of 31 mass% hydrogen peroxide solution was dropped into the mixed solution A over 2 hours, and the mixture was stirred at 25 ° C. for 3 hours. Was prepared. Thereafter, 1000 ml of water was added to the mixed solution B. The precipitated solid was separated by filtration and the filtrate was vacuum dried at 80 ° C. to obtain a powdery polymer (A1). The weight average molecular weight of the polymer (A1) was 48,000. From H-NMR, the polymer (A1) was identified as polynaphthylene bonded to the adjacent naphthalene ring at the 1- and 5-positions of the naphthalene ring.

[Synthesis Example 2] Synthesis of polymer (A2) In a flask, 20.00 g (0.125 mol) of 2,3-dihydroxynaphthalene, 0.40 g (0.125 mmol) of N, N'- in a nitrogen atmosphere. A mixed solution C containing bis (salicylidene) ethylenediamine iron (II) and 180 mL of 2-methoxyethanol was prepared. While stirring the mixed solution C at 25 ° C. in a nitrogen atmosphere, 13.7 g of 31% by mass hydrogen peroxide was added dropwise to the mixed solution C over 1 hour, followed by stirring at 25 ° C. for 2 hours. Thereafter, 3.6 g of 31% by mass hydrogen peroxide solution was added dropwise over 15 minutes and stirred for 45 minutes at 25 ° C. four times to prepare a mixed solution D. Thereafter, 1000 ml of water was added to the mixed solution D. The precipitated solid was separated by filtration, and the filtrate was vacuum dried at 80 ° C. to obtain a powdery polymer (A2). The weight average molecular weight of the polymer (A2) was 20,000. From H-NMR, the polymer (A2) was identified as polynaphthylene bonded to the adjacent naphthalene ring at the 1- and 4-positions of the naphthalene ring.

Synthesis Example 3 Synthesis of Polymer (RA1) 70 parts of pt-butoxystyrene and 10 parts of styrene were dissolved in 150 parts of propylene glycol monomethyl ether, and the reaction temperature was maintained at 70 ° C. in a nitrogen atmosphere. For 10 hours using 4 parts of azobisisobutyronitrile. Thereafter, sulfuric acid was added to the reaction solution, and the reaction temperature was maintained at 90 ° C. for 10 hours, and the pt-butoxystyrene unit was deprotected and converted to the p-hydroxystyrene unit. Ethyl acetate was added to the obtained copolymer, washing with water was repeated 5 times, the ethyl acetate layer was separated, the solvent was removed, and a p-hydroxystyrene / styrene copolymer (RA1) was obtained. The weight average molecular weight of this polymer (RA1) was 9,000.

[3] Preparation of photosensitive resin composition [Example 1]
100 parts of the polymer (A1) of Synthesis Example 1, 3 parts of 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, methyl ether 20 parts of melamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-30M”), 2.5 parts of γ-glycidoxypropyltrimethoxysilane, 130 parts of propylene glycol monomethyl ether acetate, ethylene glycol monomethyl Ether was uniformly mixed in an amount of 50 parts, and foreign matters were removed with a membrane filter to prepare a photosensitive resin composition. Predetermined evaluation was performed using the obtained composition.

[Example 2]
100 parts of the polymer (A2) of Synthesis Example 2, 3 parts of 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, methyl ether 20 parts of melamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-30M”), 2.5 parts of γ-glycidoxypropyltrimethoxysilane, 130 parts of propylene glycol monomethyl ether acetate, ethylene glycol monomethyl Ether was uniformly mixed in an amount of 50 parts, and foreign matters were removed with a membrane filter to prepare a photosensitive resin composition. Predetermined evaluation was performed using the obtained composition.

[Examples 3 to 8, Comparative Example 1]
In Examples 3 to 8 and Comparative Example 1, photosensitive resin compositions were prepared in the same manner as in Example 1 except that the types and amounts of the ingredients were changed as shown in Table 1. Predetermined evaluation was performed using the obtained composition.
Details of each component in Table 1 are as follows.

<< Polymer (A) Other Polymers >>
Polymer (A1): Polymer obtained in Synthesis Example 1 Polymer (A2): Polymer obtained in Synthesis Example 2 Polymer (RA1): Polymer obtained in Synthesis Example 3
<< Photosensitive acid generator (B) >>
B1-1: 2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine B1-2: Phenylthiophenyldiphenylsulfonium salt Compound represented by 1)

B1-3: 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate

<< Crosslinking agent (C) >>
C1-1: Methyl ether melamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nikarak MW-30M”)
C1-2: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane methoxymethylolated compound (represented by the following formula 2) Compound)

C1-3: methoxymethylolated product of 1,1,1-tris (4-hydroxyphenyl) ethane (compound represented by the following formula 3)

C2-1: Trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name “Denacol EX321L”)

<< Adhesion aid (D) >>
D1: γ-glycidoxypropyltrimethoxysilane
<< Acid diffusion inhibitor (E) >>
E1: Nt-butoxycarbonyl-2-phenylbenzimidazole
<< Solvent (F) >>
・ F1: Propylene glycol monomethyl ether acetate ・ F2: Ethylene glycol monomethyl ether

[4] Evaluation The evaluation method of the photosensitive resin composition is as follows.
[4-1] A photosensitive resin composition is spin-coated on a 4-inch resolution silicon wafer, and then heated at 90 ° C. for 3 minutes using a hot plate to produce a uniform resin film having a thickness of 5 μm. did. Next, using an aligner (manufactured by Suss Microtec, device name “MA-100”), UV light from a high-pressure mercury lamp is applied through a pattern mask so that the exposure dose at a wavelength of 365 nm is 500 mJ / m ^2. The film was irradiated. Subsequently, the resin coating film was heated at 95 ° C. for 5 minutes using a hot plate (PEB treatment), and developed by immersion for 60 seconds at 23 ° C. using a 2.38 mass% aqueous tetramethylammonium hydroxide solution. . Next, the developed resin coating film was washed with ultrapure water for 60 seconds, air-dried with air, and then observed with a microscope (manufactured by Olympus Corporation, MHL110). Among the pattern dimensions of 10 to 100 μm, the minimum pattern dimension that can be resolved was evaluated as the resolution.

[4-2] A photosensitive resin composition was spin-coated on a silicon wafer having an internal stress of 8 inches, and then heated at 90 ° C. for 3 minutes using a hot plate to prepare a uniform resin film having a thickness of 5 μm. . Next, using an aligner (manufactured by Suss Microtec, apparatus name “MA-100”), the resin coating film was irradiated with ultraviolet rays from a high-pressure mercury lamp so that the exposure amount at a wavelength of 365 nm was 500 mJ / m ² . Next, the resin coating film was heated at 95 ° C. for 5 minutes using a hot plate (PEB treatment), and developed by immersion at 23 ° C. for 120 seconds using a 2.38 mass% aqueous tetramethylammonium hydroxide solution. . Subsequently, it heated at 260 degreeC for 1 hour using the convection-type oven, the resin coating film was hardened, and the cured film was formed. The stress difference between the silicon wafers before and after the formation of the cured film was measured with a stress measuring device (FLX-2320-s manufactured by TOHO Technology).

[4-3] The heat resistance of the heat-resistant cured film was evaluated at a thermal mass reduction temperature (° C.) of 5% by mass. The 5 mass% thermogravimetric decrease temperature was measured by a thermogravimetric analysis (TGA) under a nitrogen atmosphere at a heating rate of 10 ° C / min.

[4-4] Electrical Insulation As shown in FIG. 1, a photosensitive resin composition is applied to a base material 3 for electrical insulation evaluation having a substrate 1 and a patterned copper foil 2 formed on the substrate 1. Then, using a hot plate, it was heated at 110 ° C. for 5 minutes to prepare a substrate having a resin coating film having a thickness of 10 μm on the copper foil 2. Thereafter, the resin coating film was cured by heating in a convection oven at 120 ° C. for 30 minutes, then at 150 ° C. for 30 minutes, then at 200 ° C. for 1 hour to obtain a cured film. The obtained test substrate was put into a migration evaluation system (AEI, EHS-221MD manufactured by Tabai Espec Co., Ltd.), and the temperature was 121 ° C., the humidity was 85%, the pressure was 1.2 atm, and the applied voltage was 5 V for 100 hours. Processed. Thereafter, the resistance value (Ω) of the test substrate was measured to confirm the electrical insulation.

* The numerical values of each component in Table 1 indicate the blending amount (part by mass).

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Patterned copper foil, 3 ... Base material for electrical insulation evaluation

Claims (12)

1. (A) a polymer having a structural unit represented by the formula (A1);
   (B) a photosensitive acid generator;
   (C) The photosensitive resin composition containing a crosslinking agent.
   

   

   Wherein (A1), a hydroxyl group is a substituted group bonded to a naphthalene ring; R ¹ is a substituent bonded to the naphthalene ring, a halogen atom or an alkyl group having 1 to 10 carbon atoms, R ¹ May be the same as or different from each other when a plurality is present; a is an integer of 1 to 6, b is an integer of 0 to 4, and 1 ≦ a + b ≦ 6; * 2 may be bonded to the same benzene nucleus contained in the naphthalene ring, or may be bonded to different benzene nuclei. ]
2. The photosensitive resin composition according to claim 1, wherein in the structural unit represented by the formula (A1), the bond * 1 and * 2 are bonded to different benzene nuclei contained in the naphthalene ring.
3. The photosensitive resin composition according to claim 1 or 2, wherein the structural unit represented by the formula (A1) is a structural unit represented by the formula (A1-1).
   

   
4. The weight average molecular weight (Mw) measured by gel permeation chromatography of the polymer (A) is more than 10,000 and not more than 200,000 in terms of polystyrene. The photosensitive resin composition as described in 2.
5. The crosslinking agent (C) includes a crosslinking agent (C1) having at least two groups represented by —CH ₂ OR (where R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acetyl group). Item 5. The photosensitive resin composition according to any one of Items 1 to 4.
6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the content of the crosslinking agent (C) is 5 to 50 parts by mass with respect to 100 parts by mass of the polymer (A).
7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the photosensitive acid generator (B) comprises a compound containing a haloalkyl group and a triazine skeleton.
8. A cured film obtained from the photosensitive resin composition according to any one of claims 1 to 7.
9. The resin coating film containing the polymer (A) which has a structural unit represented by Formula (A1).
   

   

   Wherein (A1), a hydroxyl group is a substituted group bonded to a naphthalene ring; R ¹ is a substituent bonded to the naphthalene ring, a halogen atom or an alkyl group having 1 to 10 carbon atoms, R ¹ May be the same as or different from each other when a plurality is present; a is an integer of 1 to 6, b is an integer of 0 to 4, and 1 ≦ a + b ≦ 6; * 2 may be bonded to the same benzene nucleus contained in the naphthalene ring, or may be bonded to different benzene nuclei. ]
10. A step of forming a resin coating film of the photosensitive resin composition according to any one of claims 1 to 7, a step of exposing the resin coating film, and an exposure with an alkaline developer. The manufacturing method of a patterned cured film which has the process of developing the subsequent resin coating film.
11. An electronic component having the cured film according to claim 8.
12. A substrate,
    The electronic component which has a metal wiring and the rewiring layer containing the cured film of Claim 8.

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