JP4893527B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition used for an interlayer insulating film (passivation film), a surface protective film (overcoat film), an insulating film for a high-density mounting substrate, and the like of a semiconductor element. High solubility in g, good sensitivity to g-line and h-line, high-thickness coating and alkali development are possible, a pattern with high resolution can be formed, and a cured product with a high residual film ratio is obtained. The present invention relates to a photosensitive resin composition suitable for surface protective films, interlayer insulating films, and insulating film applications for high-density mounting substrates.

  Conventionally, polyimide-based resins having excellent heat resistance, mechanical properties, and the like have been widely used for surface protective layers, interlayer insulating films, and the like used in semiconductor devices of electronic devices. Also, various photosensitive polyimide-based resins imparted with photosensitivity for improving film formation accuracy due to high integration of semiconductor elements have been proposed, and side-chain polymerizable negative photosensitive polyimide is frequently used.

  For example, Patent Document 1 describes a photosensitive composition using an aromatic polyimide precursor having an acrylic side chain. However, this photosensitive composition has a problem that it is difficult to cope with a high film thickness due to a problem of light transmittance and a large residual stress after curing. Furthermore, there have been problems with the environment and safety due to solvent development. In addition, since it is necessary to use an organic solvent as a developing solution, development of an alkali development type radiation sensitive resin composition is desired.

  In order to solve these problems, many proposals have been conventionally made. For example, Patent Documents 2 and 3 propose a positive photosensitive polyimide composition that can be alkali-developed. However, the applicability of these photosensitive polyimide compositions is not necessarily good, and it has been difficult to cope with a high film pressure of, for example, 15 μm or more. Another problem is that it is difficult to obtain a sufficiently high resolution. For this reason, there is a problem that it is difficult to cope with the use of an interlayer insulating film, a surface protective film, and an insulating film for a high-density mounting substrate that require high film thickness coating and high resolution.

  Patent Document 4 proposes an alkali developing type negative photosensitive composition. However, the strength of the film (cured product) obtained by curing this negative photosensitive composition has not necessarily been sufficient. For this reason, there is a problem that it is still difficult to cope with the use of a surface protective layer, an interlayer insulating film, and an insulating film for a high-density mounting substrate that require toughness of the film. Many other patents have been filed, but it is difficult to sufficiently satisfy the required characteristics due to high integration and thinning of semiconductor elements.

JP 63-125510 A JP-A-3-204649 Japanese Patent Laid-Open No. 3-209478 JP 2000-26603 A

  The present invention has been made in view of such problems of the prior art, and the problem is that the sensitivity to g-line and h-line is good, and the solubility in general solvents is high. Photosensitivity suitable for interlayer insulating film, surface protective film, and insulating film application for high-density mounting substrate, which can be applied to high film thickness and alkali development, and can obtain a cured product with high resolution and mechanical strength. It is in providing a conductive resin composition.

  As a result of intensive studies to achieve the above-described problems, the present inventors have found that the above-described problems can be achieved by adopting the following configuration, and have completed the present invention.

  That is, according to the present invention, the following photosensitive resin composition is provided.

[1] A photosensitive resin composition containing (A) a polyimide resin having a hydroxyl group , (B) a photosensitive acid generator containing a compound represented by the following general formula (1), and (C) a crosslinking agent.

（前記一般式（１）において、Ｒ^１は水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシル基を示し、Ｘはハロゲン原子を示し、Ｙは酸素原子又は硫黄原子を示す。）

(In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms, X represents a halogen atom, and Y represents an oxygen atom or a sulfur atom. Show.)

(A) The photosensitive resin composition as described in [1] above, wherein the polyimide resin having a hydroxyl group contains a repeating unit represented by the following general formula (2).

（前記一般式（２）において、Ｚは４価の芳香族又は脂肪族炭化水素基を示し、Ａは水酸基を有する２価の基を示す。）

(In the general formula (2), Z represents a tetravalent aromatic or aliphatic hydrocarbon group, and A represents a divalent group having a hydroxyl group.)

  [3] The photosensitive resin composition according to [2], wherein Z in the general formula (2) is a tetravalent aliphatic hydrocarbon group.

  [4] The photosensitive resin composition according to [2] or [3], wherein A in the general formula (2) is a group represented by the following general formula (3).

（前記一般式（３）において、Ｒ^２は単結合、酸素原子、硫黄原子、スルホン基、カルボニル基、メチレン基、ジメチルメチレン基、及びビス（トリフルオロメチル）メチレン基からなる群より選択される少なくとも一種を示し、Ｒ^３は互いに独立して、水素原子、アシル基、又はアルキル基を示し、ｎ^１及びｎ^２は０〜２の整数を示し、ｎ^１とｎ^２の少なくとも一方は１以上であり、Ｒ^３の少なくとも一つは水素原子である。）

(In the general formula (3), R ² is selected from the group consisting of a single bond, oxygen atom, sulfur atom, sulfone group, carbonyl group, methylene group, dimethylmethylene group, and bis (trifluoromethyl) methylene group. At least one of them, R ³ independently of each other represents a hydrogen atom, an acyl group, or an alkyl group, n ¹ and n ² represent an integer of 0 to ² , and at least one of n ¹ and n ² is 1 or more. And at least one of R ³ is a hydrogen atom.)

(A) The photosensitive resin composition in any one of said [1]-[4] in which the polyimide resin which has a hydroxyl group contains the repeating unit shown by following General formula (4).

（前記一般式（４）において、Ｚは４価の芳香族又は脂肪族炭化水素基を示し、前記一般式（２）中のＺと同一でも異なってもよい。Ｂは炭素数２〜２０の置換若しくは無置換のアルキレン基、又は一般式（５）で示される２価の基を示す。）

(In the general formula (4), Z represents a tetravalent aromatic or aliphatic hydrocarbon group, and may be the same as or different from Z in the general formula (2). B has 2 to 20 carbon atoms. A substituted or unsubstituted alkylene group or a divalent group represented by the general formula (5) is shown.)

（前記一般式（５）において、Ｒ^４は炭素数２〜２０の置換又は無置換のアルキレン基を示す）

(In the general formula (5), R ⁴ represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms)

  [6] The photosensitive resin composition according to any one of [1] to [5], further including (D) a phenol resin having a phenolic hydroxyl group.

  Since the photosensitive resin composition of the present invention contains the compound represented by the general formula (1), the sensitivity to g-line and h-line is good, the solubility in general solvents is high, and the high film Surface protective film, interlayer insulating film, and high-density mounting substrate capable of thick coating and alkali development, capable of forming a pattern with excellent resolution, and capable of obtaining a cured product with high mechanical strength The effect suitable for the insulating film use is produced.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

The photosensitive resin composition of the present invention contains (A) a polyimide resin having a hydroxyl group , (B) a photosensitive acid generator containing a compound represented by the following general formula (1), and (C) a crosslinking agent. To do. The details will be described below.

In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms, X represents a halogen atom, and Y represents an oxygen atom or a sulfur atom. .

((A) Polyimide resin having a hydroxyl group )
The (A) hydroxyl group- containing polyimide resin (hereinafter also referred to as “(A) polymer”) contained in the photosensitive resin composition of the present invention is a polymer containing a polyimide skeleton having a hydroxyl group in its molecular structure ( Resin), it is not particularly limited, but is preferably an alkali-soluble resin. (A) Specific examples of the polyimide resin having a hydroxyl group include those containing a repeating unit represented by the general formula (2). Moreover, what contains the repeating unit shown by the said General formula (4) is preferable. Here, Z in the general formulas (2) and (4) is a tetravalent aromatic hydrocarbon group or a tetravalent aliphatic hydrocarbon group, preferably a tetravalent aliphatic hydrocarbon group. is there. Specific examples of the tetravalent aromatic hydrocarbon group include a tetravalent group in which four hydrogens in the mother skeleton of the aromatic hydrocarbon are substituted.

  As an aromatic hydrocarbon group, the group shown below can be mentioned, for example.

  Examples of the tetravalent aliphatic hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an alkyl alicyclic hydrocarbon group. More specifically, a tetravalent group in which four hydrogens in the base skeleton of a chain hydrocarbon group, an alicyclic hydrocarbon group, or an alkyl alicyclic hydrocarbon are substituted can be given. These tetravalent aliphatic hydrocarbon groups may contain an aromatic ring in at least a part of the structure. Here, examples of the chain hydrocarbon include ethane, n-propane, n-butane, n-pentane, n-hexane, n-octane, n-decane, and n-dodecane. Specific examples of the alicyclic hydrocarbon include a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, and a tricyclic or higher hydrocarbon.

Examples of monocyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclooctane and the like. Bicyclic hydrocarbons include bicyclo [2.2.1] heptane, bicyclo [3.1.1] heptane, bicyclo [3.1.1] hept-2-ene, bicyclo [2.2.2]. Examples include octane and bicyclo [2.2.2] oct-7-ene. Examples of the tricyclic or higher hydrocarbon include tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [5.2.1.0 ^2,6 ] dec-4-ene, adamantane, tetracyclo [ 6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane and the like.

  Examples of the alkyl alicyclic hydrocarbon include those obtained by replacing the alicyclic hydrocarbon with an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group. More specifically, methylcyclopentane, 3-ethyl-1-methyl-1-cyclohexene, 3-ethyl-1-cyclohexene and the like can be mentioned. The tetravalent aliphatic hydrocarbon group containing an aromatic ring in at least a part of the structure preferably has 3 or less aromatic rings in one molecule. It is particularly preferable that More specifically, 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-12,3,4-tetrahydronaphthalene and the like can be mentioned.

As a mother nucleus of a tetravalent group preferable as Z, n-butane, cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, bicyclo [2.2. 2] Oct-7-ene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane, methylcyclopentane and the like.

  More preferable as Z is

である。

It is.

    Particularly preferred as Z is

である。これらのＺは、一種単独で又は二種以上を組み合わせて用いることができる。

It is. These Z can be used individually by 1 type or in combination of 2 or more types.

A in the general formula (2) is a divalent group having a hydroxyl group. Preferred examples of the divalent group having a hydroxyl group include the group represented by the general formula (3). Here, R ² in the general formula (3) is selected from the group consisting of a single bond, an oxygen atom, a sulfur atom, a sulfone group, a carbonyl group, a methylene group, a dimethylmethylene group, and a bis (trifluoromethyl) methylene group. At least one group selected. Further, R ³ in the general formula (3) independently of one another, a hydrogen atom, an acyl group or an alkyl group. Preferred acyl groups include formyl group, acetyl group, propionyl group, butyroyl group, isobutyroyl group and the like. Preferred alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group and the like can be mentioned. Note that at least one of R ³ is a hydrogen atom. Further, ^{n 1} and ^{n 2} in formula (3) is an integer of 0 to 2, at least one of ^{n 1} and ^{n 2} is not less than.

  Furthermore, as A (divalent group having a hydroxyl group) in the general formula (2), specifically,

等の水酸基を一つ有する２価の基、

A divalent group having one hydroxyl group, such as

等の水酸基を二つ有する２価の基、

A divalent group having two hydroxyl groups, such as

等の水酸基を三つ有する２価の基、及び

A divalent group having three hydroxyl groups such as

等の水酸基を四つ有する２価の基等を挙げることができる。

And divalent groups having four hydroxyl groups.

  Of these, a divalent group having two hydroxyl groups is preferred,

が更に好ましい。

Is more preferable.

B in the general formula (4) is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a divalent group represented by the general formula (5). Here, R ⁴ in the general formula (5) represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms.

Specific examples of the substituted or unsubstituted alkylene group having 2 to 20 carbon atoms include a linear alkylene group, a branched alkylene group, and an alkylene group having an alicyclic structure. Here, as the linear alkylene group, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 1,8-octylene, 1,10-decylene, 1, Examples thereof include 12-dodecylene. Examples of the branched alkylene group include 1,2-propylene, 2-methyl-1,5-pentylene, 2,3,3-trimethyl-1,6-hexylene and the like. Furthermore, examples of the alkylene group having an alicyclic structure include 1,4-cyclohexylamine, 1,3-cyclohexylamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane. Hexane, 4,4-methylenebis (cyclohexylamine), 4,4-methylenebis (2-methylcyclohexylamine), isophoronediamine, 1,8-diamino-p-menthane, 3 (4), 8 (9),- bis (aminomethyl) tricyclo [5,2,1,0 ^2,6] decane, 2,5 (6) - bis (aminomethyl) bicyclo [2,2,1] heptane, 1,3-diamino-adamantane etc. Can be mentioned. These alkylene groups can be used individually by 1 type or in combination of 2 or more types.

Among these, an alkylene group containing an alicyclic structure is preferable, and an alkylene group containing a condensed alicyclic structure is more preferable. If the alkylene group has less than 2 carbon atoms, flexibility may not be sufficiently imparted. On the other hand, when the number of carbon atoms exceeds 20, the crosslink density may decrease and the mechanical strength may decrease. Moreover, as R < ⁴ > in the said General formula (5), the thing similar to B in the said General formula (4) is mentioned.

  (A) The polymer is usually a monomer represented by the following general formula (6) (hereinafter also referred to as “monomer (6)”) and a monomer represented by the following general formula (7) (hereinafter referred to as “monomer (7)”. ) ”) In a polymerization solvent to synthesize a polyamic acid, and further, an imidization reaction can be performed. The following two types of methods are generally known for synthesizing a polyamic acid, and any method may be used for synthesis. That is, (i) a method in which the monomer (7) is dissolved in the polymerization solvent and then the monomer (6) is reacted; (ii) the monomer (6) is dissolved in the polymerization solvent and then the monomer (7) is reacted. Is the method.

Z in the general formula (6) is synonymous with Z in the general formulas (2) and (4), and R ² , R ³ , n ¹ , and n ² in the general formula (7) are , Are the same as R ² , R ³ , n ¹ , and n ^{2 in the} general formula (2).

  In obtaining the polymer (A), a diamine compound other than the monomer (4) can be reacted as necessary within the range not impairing the effects of the present invention. Examples of the diamine compound that can be reacted include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4, 4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2 ' -Dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1, 3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzofe 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diamino Fluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5 5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl 1,4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethyl) Phenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octa Aromatic diamines such as fluorobiphenyl;

Metaxylylenediamine, paraxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 4 , 4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophorone diamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoin danylene dimethylene diamine , tricyclo [6.2.1.0 ^2,7] - undecylenate range methyl diamine, 4,4'-methylenebis aliphatic such as (cyclohexylamine) and alicyclic diamines; may be mentioned

  The following two types of methods are generally known for the synthesis procedure of the polyamic acid in the case of using the diamine compound described above, and the synthesis may be performed by any method. That is, (i) a method in which a monomer (7) and a diamine compound other than the monomer (7) are dissolved in a polymerization solvent and then the monomer (6) is reacted; (ii) the monomer (6) is dissolved in the polymerization solvent Thereafter, a diamine compound other than the monomer (7) is reacted, and the monomer (7) is further reacted.

  As a polymerization solvent, aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and dimethyl sulfoxide; used. If necessary, alcohol solvents such as methanol, ethanol, propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol; diglyme , Ether solvents such as triglyme; aromatic hydrocarbon solvents such as toluene and xylene may be added.

  As the imidization reaction, a heating imidization reaction and a chemical imidation reaction are generally known, but it is preferable to synthesize a polymer (A) by a heating imidization reaction. The heating imidization reaction is usually performed by heating a synthesis solution of polyamic acid at 120 to 210 ° C. for 1 to 16 hours. If necessary, the reaction may be performed while removing water in the system using an azeotropic solvent such as toluene or xylene.

  (A) The polystyrene-converted weight average molecular weight (hereinafter also referred to as “Mw”) of the polymer measured by gel permeation chromatography (GPC) is usually about 2,000 to 500,000, preferably 3, It is about 000-300,000. If Mw is less than 2,000, sufficient mechanical properties as an insulating film may not be obtained. On the other hand, when Mw exceeds 500,000, the solubility of the photosensitive resin composition obtained by using the polymer (A) in a solvent or a developer may be poor.

  (A) All monomers of the polymer (monomer (6) + monomer (7) (provided that a diamine compound other than monomer (7) is further contained, monomer (6) + monomer (7) + monomer (7 The proportion of the monomer (6) in the diamine compound other than) is usually 40 to 60 mol%, preferably 45 to 55 mol%, and the proportion of the monomer (6) in all monomers is less than 40 mol%. When the diamine compound is used, the monomer (7) and the diamine compound in terms of the total amount of the diamine compound ( The proportion of 7) is usually from 1 to 99 mol%, preferably from 20 to 95 mol%, more preferably from 30 to 90 mol%.

(Other resins)
The photosensitive resin composition of the present invention may further contain other resins other than the above-mentioned (A) polyimide resin having a hydroxyl group , as required, within a range not impairing the effects of the present invention. The “other resin” that can be contained is not particularly limited, but is preferably alkali-soluble, and further contains an alkali-soluble resin having a phenolic hydroxyl group (hereinafter also referred to as “phenol resin”). This is more preferable because the resolution is further improved.

  Examples of the phenol resin that can be contained include novolak resin, polyhydroxystyrene and copolymers thereof, phenol-xylylene glycol dimethyl ether condensation resin, cresol-xylylene glycol dimethyl ether condensation resin, phenol-dicyclopentadiene condensation resin, and the like. be able to.

  Specific examples of the novolak resin include a phenol / formaldehyde condensed novolak resin, a cresol / formaldehyde condensed novolak resin, and a phenol-naphthol / formaldehyde condensed novolak resin.

  The novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst. Examples of the phenols used in this case include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3 , 4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

  Monomers other than hydroxystyrene constituting the copolymer of polyhydroxystyrene are not particularly limited. Specifically, styrene, indene, p-methoxystyrene, p-butoxystyrene, p-acetoxystyrene, p-hydroxy- Styrene derivatives such as α-methylstyrene; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec -(Meth) acrylic acid derivatives such as butyl (meth) acrylate and t-butyl (meth) acrylate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether and t-butyl vinyl ether; maleic anhydride, italy anhydride It can be exemplified acid anhydride derivatives such as phosphate.

The content ratio of the phenol resin is preferably 5 to 90 parts by mass, more preferably 5 to 80 parts by mass with respect to (A) a total of 100 parts by mass of the polyimide resin having a hydroxyl group and the phenol resin. It is especially preferable to set it as 10-70 mass parts. If it is less than 5 parts by mass, the effect of containing this phenol resin may be difficult to be exhibited. On the other hand, if it exceeds 90 parts by mass, the mechanical strength of the film may decrease.

  Furthermore, the photosensitive resin composition of the present invention may contain a low molecular compound having a phenolic hydroxyl group (hereinafter also referred to as a phenolic low molecular compound) in addition to the above-described phenol resin. Specific examples of the phenolic low molecular weight compound that can be contained include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy). Phenyl) -1-phenylethane, tris (4-hydroxyphenyl) ethane, 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, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2- Tiger (4-hydroxyphenyl) ethane and the like.

The content ratio of the phenolic low molecular weight compound is (A) 100 parts by mass of a polyimide resin having a hydroxyl group (provided that (A) other polymer other than the polymer (A) is further contained, (A) a polyimide having a hydroxyl group. 1 to 100 parts by mass, more preferably 1 to 60 parts by mass, and particularly preferably 5 to 40 parts by mass with respect to 100 parts by mass of the resin and the other polymer. . If it is less than 1 part by mass, the effect of containing this phenolic low molecular weight compound may be difficult to be exhibited. On the other hand, if it exceeds 100 parts by mass, the mechanical strength of the film may decrease.

((B) photosensitive acid generator)
The photosensitive acid generator (B) contained in the photosensitive resin composition of the present invention is a component that generates an acid upon irradiation with radiation (hereinafter also referred to as “exposure”). The compound represented is included.

The compound represented by the general formula (1) has a wide absorption in the g-line, h-line, and i-line regions, and obtains an insulating cured product having high acid generation efficiency and high residual film ratio. Can do. In the general formula (1), the alkyl group having 1 to 4 carbon atoms represented by R ¹ includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an iso-butyl group. , Sec-butyl group, tert-butyl group and the like. Examples of the alkoxyl group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group and the like. In addition, R ¹ in the general formula (1) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

  In the general formula (1), the halogen atom represented by X is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom. Further, Y in the general formula (1) is more preferably an oxygen atom.

Specific examples of the compound represented by the general formula (1) include 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (Z═O, ^{R 3 = H, Y = Cl} ), 2- [2- (5- methyl-furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine ^{(Z = O, R 3 =} CH ₃ and Y = Cl). In addition, these compounds can be used individually by 1 type or in combination of 2 or more types.

(B) The content of the photosensitive acid generator is (A) 100 parts by mass of a polyimide resin having a hydroxyl group (however, when (A) other polymer other than the polyimide resin having a hydroxyl group is further contained, A) In general, it is 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass in total of the polymer and other polymers. If it is less than 0.1 part by mass, it may be difficult to cause a chemical change due to the catalytic action of the acid generated by exposure. On the other hand, when it is more than 20 parts by mass, uneven coating may occur when the photosensitive resin composition is applied, or insulation after curing may decrease.

((C) Crosslinking agent)
(C) The crosslinking agent is a compound that forms a bond with a compounded composition such as a resin or other crosslinking agent molecules by the action of heat or acid. Specific examples of the (C) crosslinking agent include polyfunctional (meth) acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenol compounds, and compounds having an alkoxyalkylated amino group. Of these, compounds having an alkoxyalkylated amino group are preferred. In addition, these (C) crosslinking agents can be used individually by 1 type or in combination of 2 or more types.

  Examples of polyfunctional (meth) acrylate compounds include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth). ) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate And diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and the like. it can.

  Examples of the epoxy compound include novolak type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

  Examples of the hydroxymethyl group-substituted phenol compound include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6-bis ( Hydroxymethyl) -p-cresol] and the like.

  Examples of the compound having an alkoxyalkylated amino group include (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea, and a plurality of active methylol groups in one molecule. And a compound in which at least one hydrogen atom of the hydroxyl group of the methylol group is substituted with an alkyl group such as a methyl group or a butyl group. In addition, the compound having an alkoxyalkylated amino group may be a mixture of a plurality of substituted compounds, and some of them contain an oligomer component that is partially self-condensed. Can do.

  More specific examples of the compound having an alkoxyalkylated amino group include compounds represented by the following formulas (8) to (14).

  In addition, the compound (hexakis (methoxymethyl) melamine) represented by the said Formula (8) is marketed as a brand name "Cymel 300" (made by Cytec Industries). In addition, the compound represented by the formula (10) (tetrakis (butoxymethyl) glycoluril) is commercially available under the trade name “Cymel 1170” (manufactured by Cytec Industries).

  Compounds having an alkoxyalkylated amino group include hexakis (methoxymethyl) melamine (formula (8)), tetrakis (methoxymethyl) glycoluril (formula (11)), tetrakis (butoxymethyl) glycoluril ( The formula (10)) is particularly preferable, and hexakis (methoxymethyl) melamine (the formula (8)) is most preferable.

(C) The content rate of a crosslinking agent is suitably set so that it may become the quantity which the film | membrane formed with the photosensitive resin composition fully hardens | cures. Specifically, the content ratio of (C) the crosslinking agent is (A) 100 parts by mass of a polyimide resin having a hydroxyl group (however, when (A) other polymer other than the polyimide resin is further contained, (A ) The polymer is usually 5 to 50 parts by mass, and preferably 10 to 40 parts by mass with respect to 100 parts by mass in total of the polymer and other polymers. If it is less than 5 parts by mass, the resulting insulating layer may have insufficient solvent resistance and plating solution resistance. On the other hand, if it exceeds 50 parts by mass, the developability of the thin film formed by the photosensitive resin composition may be insufficient.

(solvent)
In the photosensitive resin composition of the present invention, in order to improve the handleability and to adjust the viscosity and storage stability, the organic resin is used as necessary within a range not impairing the effects of the present invention. A solvent can be contained. Although the kind of solvent which can be contained is not specifically limited, For example, aprotic solvents, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, (gamma) butyrolactone, dimethylsulfoxide; A phenolic protic solvent such as metacresol is preferably used.

  Further, the photosensitive resin composition of the present invention includes propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, aliphatic alcohols instead of or together with the above solvents. Organic solvents such as lactic acid esters, lactic acid esters, aliphatic carboxylic acid esters, alkoxy aliphatic carboxylic acid esters, and ketones.

  Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like. Examples of propylene glycol dialkyl ethers include propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether.

  Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like. Examples of aliphatic alcohols include 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 4-methyl-2-pentanol, 1-hexanol and the like.

  Examples of lactic acid esters include methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate. Examples of aliphatic carboxylic acid esters include n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, and isobutyl propionate. Can do.

  Examples of the alkoxy aliphatic carboxylic acid esters include methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate and the like. Examples of ketones include 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, and cyclohexanone.

  Of these solvents, ethyl lactate, 2-heptanone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and butyl acetate are preferred, and ethyl lactate and propylene glycol monomethyl ether are particularly preferred. These solvents can be used singly or in combination of two or more. In addition, a solvent is normally used so that the total content rate of components other than a solvent may be 1-60 mass%.

(Other additives)
The photosensitive resin composition of the present invention can contain a basic compound, an adhesion assistant, a surfactant, other additives, and the like as necessary within a range not impairing the effects of the present invention.

(Basic compound)
Examples of the basic compound include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, Examples thereof include trialkylamines such as tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine and n-dodecyldimethylamine, and nitrogen-containing heterocyclic compounds such as pyridine, pyridazine and imidazole. Content of a basic compound is 5 mass parts or less normally with respect to 100 mass parts of (A) polymers, Preferably it is 3 mass parts or less. If the content of the basic compound is more than 5 parts by mass with respect to 100 parts by mass of the polymer (A), the photosensitive acid generator may not function sufficiently.

(Adhesion aid)
The photosensitive resin composition of the present invention may contain an adhesion assistant in order to improve the adhesion to the substrate. A functional silane coupling agent is effective as the adhesion assistant. Here, the functional silane coupling agent refers to a silane coupling agent having a reactive substituent such as a carbonyl group, a methacryloyl group, an isocyanate group, or an epoxy group. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxylane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. The content of the adhesion assistant is preferably 10 parts by mass or less with respect to 100 parts by mass of the polymer (A).

(Surfactant)
The photosensitive resin composition of the present invention may contain a surfactant for the purpose of improving various properties such as coating properties, defoaming properties, and leveling properties. Examples of the surfactant include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183 (manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC. -135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 (Above, manufactured by Asahi Glass Co., Ltd.), SH-28PA, -190, -193, SZ-6032, SF-8428 (above, manufactured by Toray Dow Corning Silicone), etc. Agents can be used. The content of the surfactant is preferably 5 parts by mass or less with respect to 100 parts by mass of the polymer (A).

  Moreover, the compound represented by the following general formula (15) can be added as an additive for the purpose of improving the storage stability of the photosensitive resin composition of the present invention.

R ⁵ in the general formula (15) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Moreover, R < ⁶ >, R < ⁷ > and R < ⁸ > in the said General formula (15) are mutually independent, and each is a C1-C5 alkyl group and is a C1-C3 alkyl group. It is preferable. Examples of the compound represented by the general formula (15) include orthoformate esters such as trimethyl orthoformate, triethyl orthoformate, and tripropyl orthoformate.

When the photosensitive resin composition of the present invention contains the compound represented by the general formula (15), the viscosity of the photosensitive resin composition is difficult to change, and even after being stored for a long period of time. It becomes easy to use stably, and storage stability can be improved. Moreover, the content rate of the compound represented by the said General formula (15) is 0.1-100 mass parts normally with respect to 100 mass parts of (A) polyimide resins which have a hydroxyl group , Preferably it is 0.1-30. Part by mass, more preferably 0.5 to 10 parts by mass. If it is less than 0.1 part by mass, the viscosity of the photosensitive resin composition tends to change. On the other hand, when it exceeds 100 parts by mass, applicability tends to deteriorate.

In particular, the photosensitive resin composition according to the embodiment of the present invention can be suitably used as a surface protective film or an interlayer insulating film material of a semiconductor element. The photosensitive resin composition according to the embodiment of the present invention is applied to a support (a copper foil with resin, a copper wafer with a copper clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, etc.), and dried to volatilize a solvent or the like. To form a coating film. Then, it exposes through a desired mask pattern, performs a heat treatment (hereinafter, this heat treatment is referred to as “PEB”), and (B) the acid generated by the photosensitive acid generator is (A) a polyimide having a hydroxyl group. The reaction of (C) the crosslinking agent is promoted with at least one of the aromatic ring possessed by and the phenolic hydroxyl group possessed by the polyimide. Promotes the reaction between the phenolic ring and the crosslinking agent. Subsequently, it develops with an alkaline developing solution, A desired pattern can be obtained by melt | dissolving and removing an unexposed part. Furthermore, a cured film can be obtained by performing a heat treatment in order to develop insulating film characteristics.

  As a method for applying the photosensitive resin composition to the support, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, or a spin coating method can be used. The coating thickness can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the composition solution. After coating, in order to volatilize the solvent, a pre-bake treatment is usually performed. The conditions vary depending on the blending composition of the photosensitive resin composition, the used film thickness, and the like, but are usually 70 to 150 ° C., preferably 80 to 140 ° C., and about 1 to 60 minutes.

Examples of radiation used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, ultraviolet rays such as g-line, h-line, and i-line, electron beams, and laser beams. Of these, ultraviolet rays and electron beams such as g-line, h-line and i-line are preferably used, and ultraviolet rays and electron beams of g-line and h-line are more preferably used. The exposure amount is appropriately selected depending on the light source to be used, the resin film thickness, and the like. For example, when irradiating ultraviolet rays from a high-pressure mercury lamp, the exposure film thickness is usually about 100 to 5000 mJ / cm ² when the resin film thickness is 10 to 50 μm.

  After the exposure, PEB is performed in order to promote the curing reaction between the phenol ring and the (C) crosslinking agent by the generated acid. The PEB conditions vary depending on the composition of the photosensitive resin composition, the film thickness used, etc., but are usually 70 to 150 ° C., preferably 80 to 140 ° C., and about 1 to 60 minutes. Thereafter, development is performed with an alkaline developer, and a desired pattern is formed by dissolving and removing unexposed portions. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The development conditions are usually about 20 to 40 ° C. and about 1 to 10 minutes.

  As the alkaline developer, for example, an alkaline compound 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 about 1 to 10% by mass. An aqueous solution can be 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 with an alkaline developer, it is washed with water and dried.

  Furthermore, in order to sufficiently develop the characteristics as an insulating film after development, the film can be sufficiently cured by heat treatment. Such curing conditions are not particularly limited, but the photosensitive resin composition can be cured by heating at a temperature of 100 to 400 ° C. for about 30 minutes to 10 hours depending on the use of the cured product. Can do. Moreover, in order to fully advance hardening or to prevent the deformation | transformation of the obtained pattern shape, it can also heat in multiple steps. For example, when it is performed in two stages, the first stage is heated at a temperature of 50 to 200 ° C. for about 5 minutes to 2 hours, and the second stage is performed at a temperature of 100 to 400 ° C. for about 10 minutes to 10 hours. It can also be cured by heating.

  Under such curing conditions, a hot plate, an oven, an infrared furnace, a microwave oven, or the like can be used as a heating facility.

  Next, a semiconductor element using the photosensitive resin composition of the embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1, a patterned insulating film 3 is formed on a substrate 1 on which a patterned metal pad 2 is formed using the photosensitive resin composition of the present embodiment. Next, if the metal wiring 4 is formed so as to be connected to the metal pad 2, a semiconductor element can be obtained.

  Further, as shown in FIG. 2, a patterned insulating film 5 may be formed on the metal wiring 4 using the photosensitive resin composition of the present embodiment. Thus, if the photosensitive resin composition which is this embodiment is used, the semiconductor element which has the insulating resin layer formed with this photosensitive resin composition can be obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

  [Molecular weight (Mw)]: Tosoh GPC column (one TSKgel α-M, one TSKgel α-2500), flow rate: 1.0 ml / min, elution solvent: N, N-dimethylformamide, column Temperature: Measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of 35 ° C.

  [Mixability]: When each component is mixed at the composition ratio shown in Table 3, a transparent and uniform solution is evaluated as “good”, and a translucent or opaque solution is evaluated as “bad”. did.

  [Coating property]: A photosensitive resin composition was spin-coated on a 6-inch silicon wafer and heated on a hot plate at 110 ° C. for 3 minutes to prepare a uniform coating film having a thickness of 20 μm. Those in which defects such as cracks occurred in the coating film were evaluated as “bad”, and those in which defects such as cracks did not occur were evaluated as “good”.

[Residual film ratio]: A photosensitive resin composition was spin-coated on a 6-inch silicon wafer and heated on a hot plate at 110 ° C. for 3 minutes to prepare a uniform coating film having a thickness of 20 μm. Here, the initial film thickness A was measured. Thereafter, using an aligner (manufactured by Karl Suss, “MA-150”), UV light from a high-pressure mercury lamp was exposed through a pattern mask so that the exposure amount at 420 nm was 500 mJ / cm ² . Subsequently, it heated at 110 degreeC for 3 minute (PEB) with the hotplate, and the predetermined pattern was formed by carrying out immersion development for 120 minutes at 23 degreeC using the 2.38% tetramethylammonium hydroxide aqueous solution. Thereafter, the film thickness of the exposed portion (film thickness B after development) in the formed pattern was measured, and the remaining film ratio was calculated by the following formula.

  (Residual film ratio /%) = (film thickness B after development) / (initial film thickness A) × 100

  [Resolution]: The minimum dimension of the pattern formed according to the method described in [Residual film ratio] described above was defined as the resolution.

(Synthesis Example 1)
2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (monomer “MA-1”) in a separable flask having a capacity of 1000 mL; 9 g, 1,12-dodecylamine (monomer “MB-1”) 36.4 g, and N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”) 384 g were added. After each monomer was dissolved by stirring at room temperature, 156.6 g of 1,2,3,4-butanetetracarboxylic dianhydride (monomer “MC-2”) was charged. After stirring at 120 ° C. for 5 hours under nitrogen, the temperature was raised to 180 ° C. and dehydration reaction was performed for 5 hours. After completion of the reaction, the reaction mixture was poured into water, and the product was reprecipitated, filtered, and vacuum dried to obtain 362 g of the polymer (A-1). The molecular weight Mw of the obtained polymer (A-1) was 19,800. Moreover, IR analysis was conducted and it confirmed that there was absorption of 1778 cm < ^-1 > which shows an imide.

(Synthesis Example 2)
In a 500 mL separable flask, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (monomer “MA-1”) 36. 7 g, 6.0 g of 1,12-dodecylamine (monomer “MB-1”), and 225 g of NMP were added. After stirring at room temperature and the respective monomers dissolved, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (monomer “MC-1”) 32.2 g was charged. After stirring at 120 ° C. for 5 hours under nitrogen, the temperature was raised to 180 ° C. and dehydration reaction was performed for 5 hours. After completion of the reaction, the reaction mixture was poured into water, and the product was reprecipitated, filtered and vacuum dried to obtain 68 g of polymer (A-2). The obtained polymer (A-2) had a molecular weight Mw of 24,000. Moreover, IR analysis was conducted and it confirmed that there was absorption of 1778 cm < ^-1 > which shows an imide.

Example 1
100 parts by mass of the polymer (A-1) obtained in Synthesis Example 1, 200 parts by mass of a solvent (ethyl lactate (EL)), 0.8 part of a photosensitive acid generator (B-1), and a crosslinking agent (C -1) A photosensitive resin composition (Example 1) was obtained by mixing 15 parts. Evaluation of the mixing property of the obtained photosensitive resin composition was “good”, evaluation of coating property was “good”, the remaining film ratio was “98%”, and the resolution was “20 μm”.

(Examples 2 to 4, Comparative Examples 1 and 2)
A photosensitive resin was prepared in the same manner as in Example 1 except that the formulation shown in Table 3 was used, and the additives (D-1 or D-2) were added to Examples 2 to 4 and Comparative Example 2. Compositions (Examples 2 to 4, Comparative Examples 1 and 2) were obtained. Table 4 shows the evaluation results of the mixing property and coating property of the obtained photosensitive resin composition, and the measurement results of the remaining film ratio and resolution. The meanings of the abbreviations in Table 3 are as shown below.

(Phenolic resin)
Cresol novolak resin comprising P-1: m-cresol / p-cresol = 60/40 (molar ratio) (polystyrene equivalent weight average molecular weight = 8,700)
P-2: Phenol / xylylene glycol dimethyl ether condensation resin (Mitsui Chemicals, trade name: Millex (registered trademark) XLC-3L)

(solvent)
EL: Ethyl lactate

(Additive)
D-1: Trimethyl orthoformate D-2: Triethyl orthoformate

(Photosensitive acid generator)
B-1: 2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd., trade name: TME-triazine) B -2: 2-2 [-(furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd., trade name: TFE-triazine)
B-3: Styryl-bis (trichloromethyl) -s-triazine B-4: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

(Crosslinking agent)
C-1: Hexamethoxymethylmelamine (Cytech Industries, trade name: Cymel 300)
C-2: Tetramethoxymethylglycoluril (manufactured by Cytec Industries, trade name: Cymel 1174)

  The photosensitive resin composition of the present invention is suitable for use as a surface protective film, an interlayer insulating film or an insulating film for high-density mounting substrates, and is extremely useful in industry.

It is a schematic cross section of the semiconductor element which has the insulating resin layer formed using the photosensitive resin composition of this invention.

It is a schematic cross section of the semiconductor element which has the insulating resin layer formed using the photosensitive resin composition of this invention.

Explanation of symbols

1: substrate, 2: metal pad, 3: insulating film, 4: metal wiring, 5: insulating film

Claims (6)

(A) a polyimide resin having a hydroxyl group ,
(B) a photosensitive acid generator containing a compound represented by the following general formula (1), and (C) a crosslinking agent,
Containing a photosensitive resin composition.

(In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms, X represents a halogen atom, and Y represents an oxygen atom or a sulfur atom. Show.) The photosensitive resin composition of Claim 1 in which the polyimide resin which has the said (A) hydroxyl group contains the repeating unit shown by following General formula (2).

(In the general formula (2), Z represents a tetravalent aromatic or aliphatic hydrocarbon group, and A represents a divalent group having a hydroxyl group.)   The photosensitive resin composition according to claim 2, wherein Z in the general formula (2) is a tetravalent aliphatic hydrocarbon group. The photosensitive resin composition according to claim 2 or 3, wherein A in the general formula (2) is a group represented by the following general formula (3).

(In the general formula (3), R ² is selected from the group consisting of a single bond, oxygen atom, sulfur atom, sulfone group, carbonyl group, methylene group, dimethylmethylene group, and bis (trifluoromethyl) methylene group. At least one of them, R ³ independently of each other represents a hydrogen atom, an acyl group, or an alkyl group, n ¹ and n ² represent an integer of 0 to ² , and at least one of n ¹ and n ² is 1 or more. And at least one of R ³ is a hydrogen atom.) The photosensitive resin composition as described in any one of Claims 1-4 in which the polyimide resin which has the said (A) hydroxyl group contains the repeating unit shown by following General formula (4).

(In the general formula (4), Z represents a tetravalent aromatic or aliphatic hydrocarbon group, and may be the same as or different from Z in the general formula (2). B has 2 to 20 carbon atoms. A substituted or unsubstituted alkylene group or a divalent group represented by the general formula (5) is shown.)

(In the general formula (5), R ⁴ represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms)   Furthermore, (D) The photosensitive resin composition as described in any one of Claims 1-5 containing the phenol resin which has a phenolic hydroxyl group.

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