JP2008106110A - Polymer and photosensitive resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition obtaining a cured material capable of performing an alkali development, having a high resolution and a small residual stress after its curing, and excellent in various characteristics. <P>SOLUTION: This photosensitive resin is a polymer having a recurring unit expressed by general formula (1) and a recurring unit expressed by general formula (2) [in the general formulae (1), (2), R<SP>1</SP>is an alkylene or the like; A is general formula (3); B is a divalent group having hydroxy; and in the general formula (3), R<SP>2</SP>s are each independently an alkyl or the like; (m) is 1 to 10 integer; and (n) is 1 to 30 integer]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  INDUSTRIAL APPLICABILITY The present invention can be suitably used for 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, and the composition. It relates to a polymer. The present invention can also be used for a protective film, an interlayer insulating film, and the like used for a color filter for a liquid crystal display element (LCD) and a color filter for a charge coupled device (CCD). More specifically, the present invention enables coating with a high film thickness, enables alkali development, high resolution, low residual stress after curing, solvent resistance, thermal shock resistance, adhesion, etc. The present invention relates to a photosensitive resin composition from which a cured product having excellent properties can be obtained, and a polymer that can be suitably used for the composition.

  Conventionally, polyimide-based resins having excellent heat resistance, mechanical properties, and the like have been widely used for surface protective films, interlayer insulating films, and the like used in semiconductor devices of electronic devices. In addition, various photosensitive polyimide resins have been proposed in which photosensitivity is imparted to improve film formation accuracy through high integration of semiconductor elements. For example, Patent Document 1 describes a photosensitive composition using an aromatic polyimide precursor having an acrylic side chain, but these systems cannot only handle high film thickness due to the problem of light transmittance. In addition, the residual stress after curing was large, and there were also problems with the environment and safety due to solvent development.

In order to solve these problems, many proposals have been conventionally made. For example, Patent Document 2 proposes a positive-type photosensitive polyimide composition that can be alkali-developed, but has problems in residual stress and solvent resistance after curing. Patent Document 3 proposes a negative photosensitive polyimide composition that can be alkali-developed, but has a problem in coating properties and has a low resolution and cannot be put into practical use. 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. In particular, the warpage of the semiconductor element due to the large residual stress after curing cannot be ignored, and it has been pointed out that it is difficult to use in industrial implementation.
JP 63-125510 A 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 it has high solubility in common solvents, and can be applied to high film thicknesses and alkali development. And a polyimide polymer suitable for use in surface protective films, interlayer insulating films, and insulating films for high-density mounting substrates, which can obtain a cured product with high transparency and high resolution, and containing the same It is providing the photosensitive 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 this invention, the polymer shown below and the photosensitive resin composition containing it are provided.

[1] A polymer having as a repeating unit a unit having a structure represented by the following general formula (1) and a unit having a structure represented by the following general formula (2).

[In the general formula (1), R ¹ represents a single bond, a substituted or unsubstituted methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and A represents 2 represented by the following general formula (3). Indicates a valent group. ],

［一般式（２）において、Ｒ^１は一般式（１）と同義で、Ｂは水酸基を有する２価の基を示す。］、

[In General Formula (2), R ¹ has the same meaning as in General Formula (1), and B represents a divalent group having a hydroxyl group. ],

[In General Formula (3), each R ² independently represents an alkyl group having 1 to 3 carbon atoms or an aryl group which may have a substituent, m represents an integer of 1 to 10, and n represents 1 to 1. An integer of 30 is shown. ]

[2] The polymer according to [1], wherein n in the general formula (3) is 1.

[3] A photosensitive resin composition containing (A) the polymer described in [1] or [2] above, (B) a photosensitive acid generator, and (C) a crosslinking agent.

[4] The photosensitive resin composition according to [3], wherein the (C) crosslinking agent has an alkoxyalkylated amino group.

[5] A cured film formed using the photosensitive resin composition according to [3] or [4].

  According to the present invention, high-thickness coating is possible, alkali development is possible, resolution is high, residual stress after curing is small, and various properties such as solvent resistance, thermal shock resistance, adhesion, etc. It is possible to provide a photosensitive resin composition suitable for use as a surface protective film, an interlayer insulating film, or an insulating film for a high-density mounting substrate, which can obtain a cured product excellent in the above.

  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.

  Hereinafter, each component which comprises the photosensitive resin composition which concerns on this invention is demonstrated concretely.

Polymer (A):
R ¹ in the general formulas (1) and (2) represents a single bond, a substituted or unsubstituted methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, specifically, a methylene group, ethylene Group, propylene group such as 1,3-propylene group or 1,2-propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group , Dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptadecamethylene group, octadecamethylene group, nonacamethylene group, icosalen group, 1-methyl-1,3 -Propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1 -Methyl-1,4-butylene group, 2-methyl-1,4-butylene group, methylidene group, ethylidene group, propylidene group, or 2-propylidene group.

A in the general formula (1) represents a divalent group represented by the general formula (3), and R ² in the general formula (3) each independently has an alkyl group having 1 to 3 carbon atoms and a substituent. And m represents an integer of 1 to 10, and n represents an integer of 1 to 30. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group, preferably a methyl group and an ethyl group, and a methyl group is particularly preferable. Examples of the aryl group which may have a substituent include a phenyl group and a naphthyl group, and a phenyl group is preferable. As the aryl group having a substituent, hydrogen of the above aryl group is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl. Examples include a group replaced with a group, a hydroxyl group, a carboxyl group and the like, preferably a methyl group and a hydroxyl group. m is preferably an integer of 1 to 7, and an integer of 1 to 5 is particularly preferable. n is preferably an integer of 1 to 20, particularly preferably an integer of 1 to 15.

  In the general formula (2), B represents a divalent group having a hydroxyl group.

A divalent group having one hydroxyl group, such as

A divalent group having two hydroxyl groups, such as

A divalent group having three hydroxyl groups such as

And divalent groups having four hydroxyl groups.

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

Is particularly preferred.

  The polymer (A) is usually a monomer represented by the following general formula (4) (hereinafter referred to as monomer 4), a monomer represented by the general formula (5) (hereinafter referred to as monomer 5), and a general formula. It is obtained by reacting the monomer represented by (6) (hereinafter referred to as monomer 6) in a polymerization solvent to synthesize a polyamic acid, and further carrying out an imidization reaction. The following two types of methods are generally known for the polyamic acid synthesis procedure, and the synthesis may be performed by any method. That is, there are a method in which the monomer 5 and the monomer 6 are dissolved in the polymerization solvent and the monomer 4 is reacted, and a method in which the monomer 4 is dissolved in the polymerization solvent, the monomer 5 is reacted, and the monomer 6 is further reacted.

  The polymer (A) may contain a unit having the structure represented by the formula (1) and the formula (2) as a repeating unit, and may be any of a block copolymer and a random copolymer. good.

  Actually, as the monomer 5, commercially available products, for example, product names manufactured by Toshiba Silicone Co., Ltd .: TSL9386, TSL9346, TSL9306, product names manufactured by Toray Dow Corning: BY16-853C, BY16-871EG, products manufactured by Shin-Etsu Chemical Co., Ltd. Name: X-22-161AS, product name manufactured by Nippon Unicar Co., Ltd .: F2-053-01, product name manufactured by Chisso Corp .: Silaplane FM3325, FM3321, FM3311, etc. can be used.

  As a polymerization solvent, aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide and the like, and protic solvents such as metacresol are usually used. Alcohol solvent such as methanol, ethanol, propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, diglyme, An ether solvent such as triglyme and an aromatic hydrocarbon solvent such as toluene and xylene may be added. The reaction is usually carried out at 20 to 130 ° C. for 1 to 48 hours.

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

  The polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC) is usually about 2,000 to 500,000, preferably about 3,000 to 100,000. is there. If Mw is less than 2,000, sufficient mechanical properties as an insulating film tend not to be obtained, and if Mw exceeds 500,000, solubility in a solvent or a developer tends to be poor.

  The molar ratio of the monomer 4 in the total monomers is usually 40 to 60 mol%, preferably 45 to 55 mol%. When the molar ratio of the monomer 4 to the total monomer is less than 40 mol% or more than 60 mol%, the molecular weight of the polymer (A) tends to decrease.

  The molar ratio of the monomer 5 to the total of the monomer 5 and the monomer 6 is usually 1 to 80 mol%, preferably 5 to 70 mol%. When the molar ratio of the monomer 5 is within the above range, it is preferable in terms of improving transparency, reducing warpage, and improving alkali developability.

Photosensitive acid generator (B):
The photosensitive acid generator (B) used in the present invention is a compound that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”). This compound includes a chemical amplification system and a naphthoquinone diazide (NQD) system. Specific examples include iodonium salt compounds, sulfonium salt compounds, sulfone compounds, sulfonic acid ester compounds, halogen-containing compounds, diazoketone compounds, sulfonimide compounds, and diazomethane compounds.

  More specifically, chemical amplification type acid generators include iodonium salt compounds, sulfonium salt compounds, sulfone compounds, sulfonic acid ester compounds, halogen-containing compounds, sulfonimide compounds, diazomethane compounds, and the like.

  Moreover, as a naphthoquinone diazide (NQD) type acid generator, a diazo ketone compound or the like is applicable.

  Examples of the iodonium salt compound include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate. Bis (4-t-butylphenyl) iodonium nonafluorobutanesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, and the like.

  Examples of the sulfonium salt compounds include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium naphthalenesulfonate, 4-hydroxyphenyl benzylmethylsulfonium p-toluenesulfonate, 4- ( Phenylthio) phenyl diphenylsulfonium hexafluorophosphate, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4,7-di-n-hydroxy-1-naphthyltetrahydrothiophenium trifluoro Lomethanesulfonate, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium hexafur Rofosufeto, like 4-n-butoxy-1-naphthyl tetrahydrothiophenium trifluoromethanesulfonate.

  Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. More specifically, phenacyl phenyl sulfone, mesityl phenacyl sulfone, bis (phenylsulfonyl) methane, 4-trisphenacyl sulfone and the like can be mentioned.

  Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, and imino sulfonate. More specifically, benzoin tosylate, pyrogallol tris-trifluoromethanesulfonate, pyrogallolmethanesulfonic acid triester, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, α-methylolbenzointosylate, α-methylolbenzoinoctane Examples include sulfonate, α-methylol benzoin trifluoromethane sulfonate, α-methylol benzoindodecyl sulfonate, and the like.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -S-triazine, 4-methoxyphenyl-bis (trichloromethyl). ) -S-triazine, styryl-bis (trichloromethyl) -S-triazine, 4-methoxystyryl-bis (trichloromethyl) -S-triazine, naphthyl-bis (trichloromethyl) -S-triazine and other S-triazine derivatives Can be mentioned.

  Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like. Specific examples of preferred diazoketone compounds include 1,2-naphthoquinonediazide-4-sulfonic acid ester compounds of phenols.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). And (oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, and the like.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.

  Of these photosensitive acid generators, sulfonium salt compounds, sulfone compounds, halogen-containing compounds, diazoketone compounds, sulfonimide compounds and diazomethane compounds are preferred, and sulfonium salt compounds and halogen-containing compounds are more preferred. Particularly preferred are 4- (phenylthio) phenyl diphenylsulfonium hexafluorophosphate, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4,7-di-n-hydroxy- 1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4 -Methoxyphenyl-bis (trichloromethyl) -S-triazine, styryl-bis (trichloromethyl) -S-triazine, 4-methoxystyryl-bis (trichloromethyl) -S-triazine.

  These photosensitive acid generators (B) can be used alone or in admixture of two or more. Moreover, a photosensitive acid generator (B) is 0.1-20 mass parts normally with respect to 100 mass parts of polymers (A), Preferably it is used in the quantity of 0.5-10 mass parts. desirable. If the amount of the photosensitive acid generator (B) is less than the above lower limit, it may be difficult to cause a sufficient chemical change due to the catalytic action of the acid generated by exposure. When the resin composition is applied, uneven coating may occur, or the insulation after curing may be reduced.

Cross-linking agent (C):
The cross-linking agent (C) is a compound that forms a bond with a compounded composition such as a resin or other cross-linking agent molecules by the action of heat or acid, and one of these may be used alone or in combination of two or more. Can do. Specific examples include polyfunctional (meth) acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenol compounds, and compounds having alkoxyalkylated amino groups.

  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 DOO, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate.

  Examples of the epoxy compound include novolac 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. Of these compounds, preferred are compounds having an alkoxyalkylated amino group as described above.

  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 formed by self-condensation, but these can also be used. . More specifically, for example, hexamethoxymethyl melamine (“Cymel 300” manufactured by Mitsui Cyanamid Co., Ltd.), tetrabutoxymethyl glycoluril (“Cymel 1170” manufactured by Mitsui Cyanamid Co., Ltd.), tetramethoxymethyl glycoluril (“Mitsui Cyanamid Co., Ltd.“ Examples include products of the Cymel series such as “Cymel 1174”, products of the My Coat series, products of the UFR series, etc. Among these compounds, hexamethoxymethylmelamine is particularly preferable.

  In the composition of the present invention, the use ratio of the cross-linking agent (C) needs to be within a range in which the film of the composition is sufficiently cured, and specifically 5 relative to the polymer (A). -50 mass%, preferably 10-40 mass%. If this ratio is too small, the resulting insulating layer may be insufficient in solvent resistance and plating solution resistance. On the other hand, if this ratio is excessive, a thin film of the resulting composition will be sufficiently developed. There is a risk that it will not have the property.

solvent:
A solvent is added in order to improve the handleability of a resin composition, or to adjust a viscosity or storage stability. The kind of the organic solvent that is usually used as such a solvent is not particularly limited, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, An aprotic solvent such as dimethyl sulfoxide or a phenolic protic solvent such as metacresol is used.

When the boiling point at normal pressure is 100 ° C. or higher and at least one solvent selected from the following group is contained in an amount of 10% by mass or more with respect to the total solvent, such a solvent suitably acts as a photosensitive composition. To do. Here, the boiling point at normal pressure is 100 ° C. or more, and the ratio of the solvent selected from the following group to the total solvent is more preferably 30% by mass or more, and particularly preferably 50% by mass or more.
Group: Propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, aliphatic alcohols, lactic acid esters, aliphatic carboxylic acid esters, alkoxy aliphatic carboxylic acid esters, ketones.

  More specifically, for example, as propylene glycol monoalkyl ethers, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like, among these, propylene glycol dialkyl ether Examples include propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether and the like.

  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 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, and acetic acid. Examples include n-amyl, isoamyl acetate, isopropyl propionate, n-butyl propionate, and isobutyl propionate.

  Examples of the alkoxy aliphatic carboxylic acid esters include methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate and the like. Mention may be made of ketones such as heptanone, 4-heptanone, cyclopentanone, cyclohexanone. These organic solvents can be used alone or in combination of two or more.

  When at least one solvent selected from the above group is less than 10% by mass with respect to the total solvent, there is a problem in applicability or the resolution tends to decrease.

  Of the above group of solvents, ethyl lactate, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and butyl acetate are more preferred, and ethyl lactate and propylene glycol monomethyl ether are particularly preferred.

  The amount of all solvents used is usually such that the total amount of components other than the solvent is 1 to 60% by mass.

Other additives:
The positive photosensitive insulating resin composition of the present invention may contain a basic compound, an adhesion assistant, a surfactant, and the like as other additives. These other additives can be contained to such an extent that the characteristics of the resulting photosensitive insulating resin composition are not impaired.

Basic compounds:
Triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri Examples include trialkylamines such as -n-decylamine, tri-n-dodecylamine, and n-dodecyldimethylamine, and nitrogen-containing heterocyclic compounds such as pyridine, pyridazine, and imidazole. The basic compound is desirably used in an amount of usually 5 parts by mass or less, preferably 3 parts by mass or less, relative to 100 parts by mass of the polymer (A). If the amount of the basic compound exceeds the above upper limit, the photosensitive acid generator may not function sufficiently.

Adhesion aid:
In the photosensitive resin composition of the present invention, an adhesion assistant can be used 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 means a silane coupling agent having a reactive substituent such as a carbonyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri And methoxysilane. As for the compounding quantity of adhesion assistant, 10 mass parts or less are preferred to 100 mass parts of polymers (A).

Surfactant:
In the photosensitive resin composition of the present invention, a surfactant can be blended for the purpose of improving coating properties, antifoaming properties, leveling properties and the like. Examples of such surfactants include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, and F183 (manufactured by Dainippon Ink and 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, Fluorine commercially available under trade names such as S-145 (above, manufactured by Asahi Glass Co., Ltd.), SH-28PA, i-190, i-193, SZ-6032, SF-8428 (above, made by Toray Dow Corning Silicone) System surfactants can be used. These surfactants are preferably used in an amount of 5 parts by mass or less with respect to 100 parts by mass of the polymer (A).

  In particular, the photosensitive resin composition of the present invention can be suitably used as a surface protective film or an interlayer insulating film material of a semiconductor element.

  Apply the photosensitive resin composition of the present invention to a support (a copper foil with resin, a copper-clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, etc.), and dry and evaporate the solvent. A film is formed. Thereafter, exposure is performed through a desired mask pattern, and heat treatment (hereinafter, this heat treatment is referred to as “PEB”) is performed to promote the reaction between the phenol 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 to develop the insulating film characteristics.

  As a method of applying the 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 amount of the resin composition and the film thickness used, 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, g-line steppers, i-line steppers, and other ultraviolet rays, electron beams, and laser beams. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the thickness is about 100 to 5,000 mJ / cm ² when the resin film thickness is 10 to 50 μm.

  After the exposure, PEB treatment is performed to promote the curing reaction between the phenol ring and the crosslinking agent (C) caused by the generated acid. The conditions vary depending on the blending amount of the resin composition and the film thickness used, 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, a paddle developing method, and the like. The developing conditions are usually 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, and choline is dissolved in water so as to have a concentration of about 1 to 10% by mass. 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 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.

  Moreover, in order to fully advance hardening and to prevent the deformation | transformation of the obtained pattern shape, it can also heat in multiple steps, for example, when performing in two steps, at the temperature of 50-200 degreeC in the first step, It can also be heated for about 5 minutes to 2 hours, and further cured at a temperature of 100 to 400 ° C. for about 10 minutes to 10 hours.

  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 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 resin composition of the present invention. Next, when the metal wiring 4 is formed so as to be connected to the metal pad 2, a semiconductor element is obtained.

  Further, as shown in FIG. 2, a patterned insulating film 5 may be formed on the metal wiring 4 by using the resin composition of the present invention.

  Thus, in the present invention, a semiconductor element having an insulating resin layer formed using the photosensitive resin composition as described above can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples. In addition, unless otherwise indicated, the part in a following example and a comparative example is used by the meaning of a mass part. Moreover, about each characteristic of hardened | cured material, it implemented in the following way.

Molecular weight (Mw):
Using Tosoh GPC columns (TSKgel α-M: 1, TSKgel α-2500: 1), the flow rate was 1.0 ml / min, the elution solvent N, N-dimethylformamide, and the column temperature of 35 ° C. were used. It was measured by gel permeation chromatography (GPC) using dispersed polystyrene as a standard.

Mixability:
When a sample for evaluation was prepared using the resins obtained in the synthesis examples and comparative synthesis examples, it was judged as “good” when it became a homogeneous solution, and “bad” when it did not become a homogeneous solution.

Applicability:
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. The obtained coating film was observed with the naked eye, and those in which defects such as cracks were generated were defined as “bad”, and those in which defects such as cracks were not generated were defined as “good”.

Resolution:
Using an aligner (MAS-150 manufactured by Suss Microtec), UV light from a high-pressure mercury lamp is obtained through a pattern mask so that the exposure amount at a wavelength of 350 nm is 1,000 to 5,000 mJ / cm ^2. The resulting coated wafer was exposed. Subsequently, it heated at 110 degreeC for 3 minute (PEB) with the hotplate, and was developed by immersion for 60 seconds at 23 degreeC using the 2.38 mass% tetramethylammonium hydroxide aqueous solution. The minimum dimension of the obtained pattern was taken as the resolution.

Residual stress:
A photosensitive resin composition was spin-coated on an 8-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. Furthermore, using an aligner (MAS-150 manufactured by Suss Microtec), the entire surface was exposed to ultraviolet light from a high-pressure mercury lamp so that the exposure amount at a wavelength of 350 nm was 2,000 mJ / cm ^2, and heated on a hot plate at 110 ° C. for 3 minutes. (PEB) and heated in an oven at 300 ° C. for 2 hours to obtain a cured film. The change in wafer curvature before and after the formation of this cured film was measured with FLX-2320-S manufactured by Toago Technology Co., Ltd., and the residual stress was calculated.

i-line transmittance:
A photosensitive resin composition was spin-coated on a 6-inch glass substrate and heated on a hot plate at 110 ° C. for 3 minutes to prepare a uniform coating film having a thickness of 20 μm. The UV transmittance was measured with a UV measuring instrument (V-550 UV / VIS Spectrophotometer manufactured by JAS.CO), and the transmittance at a wavelength of 365 nm was determined.

Solvent resistance:
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. Furthermore, using an aligner (MAS-150 manufactured by Suss Microtec), the entire surface was exposed to ultraviolet light from a high-pressure mercury lamp so that the exposure amount at a wavelength of 350 nm was 2,000 mJ / cm ^2, and heated on a hot plate at 110 ° C. for 3 minutes. (PEB) and heated in an oven at 300 ° C. for 2 hours to obtain a cured film. This cured film-coated wafer was immersed in N-methylpyrrolidone (hereinafter abbreviated as NMP) heated to 60 ° C. for 30 minutes to examine whether the film thickness had changed. When the film thickness change was 3% or more, it was judged as “bad”, and when it was less than 3%, it was judged as “good”.

Thermal shock resistance:
The resin composition was applied to a substrate as shown in FIGS. 3 and 4 and heated on a hot plate at 110 ° C. for 3 minutes to produce a 10 μm thick resin coating on the conductor. 3 and 4, 6 is a base material, 7 is a substrate, and 8 is a copper foil. Thereafter, using an aligner, the whole surface was exposed to ultraviolet rays from a high pressure mercury lamp so that the exposure amount at a wavelength of 350 nm was 2,000 mJ / cm ² . Subsequently, it heated at 110 degreeC for 3 minute (PEB) with the hotplate, and heated at 300 degreeC for 2 hours in oven, and obtained the cured film. This substrate was subjected to a resistance test for 500 cycles using a thermal shock tester (manufactured by Tabai Espec) at -55 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle. The obtained cured film was visually observed, and “defect” indicates that a defect such as a crack was generated, and “good” indicates that a defect such as a crack did not occur.

  Next, the synthesis example of the polymer used for an Example is described.

(Synthesis Example 1)
In a separable flask having a volume of 2 L, 60.9 g of 1,2,3,4-butanetetracarboxylic dianhydride (referred to as “monomer 4-1” shown below) and N-methyl-2-pyrrolidone ( (Hereinafter abbreviated as NMP) 800 g was added. Under stirring, 49.1 g of diaminopolysiloxane (trade name of Toray Dow Corning: BY16-853C, amine equivalent 400, “monomer 5-1” shown below) is charged, and then 2,2-bis (3 90.0 g of -amino-4-hydroxyphenyl) hexafluoropropane (referred to as "monomer 6-1" shown below) was charged. After stirring at 60 ° C. for 8 hours, the temperature was raised to 200 ° 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 179 g of a polymer. The molecular weight was 9300. Further, IR analysis was performed, and it was confirmed that there was absorption at 1778 cm ⁻¹ indicating imide.

(Synthesis Examples 2 to 12)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the monomers 4 and 5 and / or the monomers 6 were replaced with the raw materials having the molar ratios shown in Table 1 and the weights shown in Table 2. Went. The structure of the monomer used is as shown below, and this synthesis method is indicated as “A” in the table.

(Comparative Synthesis Example 1)
In a separable flask having a volume of 2 L, 71.3 g of 4,4′-diamino-3,3′-dihydroxybiphenyl (monomer 6-2) and 800 g of NMP were charged. Under stirring, 128.7 g of monomer 4-2 was added and stirred at 60 ° C. for 8 hours, and then the temperature was raised to 200 ° C. to conduct dehydration reaction 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 181 g of a polymer. The molecular weight was 16000. The polymer was subjected to IR analysis and confirmed to have an absorption of 1778 cm ⁻¹ indicating imide. In the table, this synthesis method is indicated as “B”.

(Comparative Synthesis Example 2)
In a separable flask having a volume of 2 L, 61.1 g of 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA, “monomer 4-3” shown below) and 800 g of NMP were added. Under stirring, 67.2 g of diaminopolysiloxane (trade name of Toray Dow Corning: BY16-853C, amine equivalent 400, "monomer 5-1" shown below)) was charged, and then monomers 6-1 and 71 .8 g was charged. After stirring at 60 ° C. for 8 hours, the temperature was raised to 200 ° 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 184 g of a polymer. The molecular weight was 20000. Further, IR analysis was performed, and it was confirmed that there was absorption at 1778 cm ⁻¹ indicating imide.

(Comparative Synthesis Example 3)
In a separable flask having a volume of 2 L, 123.4 g of bis (3,4-dicarboxyphenyl) sulfone (DSDA, “monomer 4-4” shown below) and 800 g of NMP were added. With stirring, 17.1 g of diaminopolysiloxane (trade name of Toray Dow Corning: BY16-871EG, amine equivalent 400, “monomer 5-2” shown below) is charged, and then monomers 6-2, 59. 6 g was charged. After stirring at 60 ° C. for 8 hours, the temperature was raised to 200 ° 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 176 g of a polymer. The molecular weight was 22100. Further, IR analysis was performed, and it was confirmed that there was absorption at 1778 cm ⁻¹ indicating imide.

(Examples 1-12, Comparative Examples 1-4)
The composition was prepared so as to have the composition shown in Table 3. These compositions were tested for mixability, coatability, resolution, residual stress, solvent resistance, and thermal shock resistance. The results are shown in Table 4.

  In addition, the meaning of the symbol in the said table | surface is as follows.

(solvent)
EL: ethyl lactate NMP: N-methyl-2-pyrrolidone DMAc: N, N-dimethylacetamide PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether MAK: 2-heptanone GBL: γ-butyrolactone

(Photoacid generator)
C-1: styryl-bis (trichloromethyl) -s-triazine C-2: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

(Crosslinking agent)
D-1: Hexamethoxymethylmelamine (Mitsui Cytec Co., Ltd., trade name: Cymel 300)
D-2: Tetramethoxymethyl glycoluril (trade name; Cymel 1174, manufactured by Mitsui Cytec Co., Ltd.)

  The present invention is a photosensitive resin composition containing a ring-closed polyimide, and by using this, a high film thickness coating is possible, alkali development is possible, resolution is high, and after curing. It is suitable for surface protection film, interlayer insulation film and insulation film for high-density mounting substrate that can obtain cured products with low residual stress and excellent properties such as solvent resistance, thermal shock resistance and adhesion. Very useful.

FIG. 1 is a schematic cross-sectional view of a semiconductor element having an insulating resin layer formed using the photosensitive resin composition of the present invention. FIG. 2 is a schematic cross-sectional view of a semiconductor element having an insulating resin layer formed using the photosensitive resin composition of the present invention. FIG. 3 is a schematic cross-sectional view of a substrate to which the photosensitive resin composition of the present invention is applied. FIG. 4 is a schematic view of the surface of a substrate to which the photosensitive resin composition of the present invention is applied.

Explanation of symbols

1: substrate, 2: metal pad, 3: insulating film, 4: metal wiring, 5: insulating film, 6: base material, 7: substrate, 8: copper foil

Claims (5)

The polymer which has as a repeating unit the unit which has a structure shown by the following general formula (1), and the unit which has a structure shown by the following general formula (2).

[In the general formula (1), R ¹ represents a single bond, a substituted or unsubstituted methylene group or a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and A represents 2 represented by the following general formula (3). Indicates a valent group. ],

[In General Formula (2), R ¹ has the same meaning as in General Formula (1), and B represents a divalent group having a hydroxyl group. ],

[In General Formula (3), each R ² independently represents an alkyl group having 1 to 3 carbon atoms or an aryl group which may have a substituent, m represents an integer of 1 to 10, and n represents 1 to 1. An integer of 30 is shown. ]     The polymer according to claim 1, wherein n in the general formula (3) is 1. (A) The polymer according to claim 1 or 2,
(B) a photosensitive acid generator, and (C) a crosslinking agent,
Containing a photosensitive resin composition.   The photosensitive resin composition according to claim 3, wherein the (C) crosslinking agent has an alkoxyalkylated amino group.   The cured film formed using the photosensitive resin composition of Claim 3 or 4.

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