KR20190017807A - Photosensitive resin composition - Google Patents

Abstract

The present invention also provides a photosensitive resin composition having a curable film excellent in adhesiveness to a metal material, particularly copper, even in a heat treatment at a low temperature, and having high applicability. (A) an alkali-soluble resin having an organic group derived from an aliphatic diamine, (B) a photosensitive agent, (C) a photosensitive resin composition containing 1013 hPa and a compound which is liquid at 25 DEG C and has a boiling point of 210 DEG C or higher, (C) 0.113 to 15 parts by mass based on 100 parts by mass of an alkali-soluble resin having an organic group derived from an aliphatic diamine (A) under the conditions of 1013 hPa and 25 ° C and having a boiling point of 210 ° C or higher By weight.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition. More particularly, the present invention relates to a photosensitive resin composition suitably used for a surface protective film of a semiconductor device, an interlayer insulating film, an insulating layer of an organic electroluminescent device, and the like.

BACKGROUND ART Conventionally, polyimide resins, polybenzoxazole resins and the like having excellent heat resistance and mechanical properties have been widely used as surface protective films and interlayer insulating films of semiconductor devices of electronic devices. When polyimide or polybenzoxazole is used as a surface protective film or an interlayer insulating film, one of the forming methods of through holes and the like is etching using a positive type photoresist. However, in this method, there is a problem that the process involves application or peeling of the photoresist, which is troublesome. Therefore, a heat-resistant material imparting photosensitivity has been studied for the purpose of rationalizing the working process.

Polyimide or polybenzoxazole can thermally dehydrate and cyclize the coating film of the precursor thereof to obtain a thin film having excellent heat resistance and mechanical properties. However, in this case, it is usually necessary to carry out a heat treatment at a high temperature of about 350 캜. However, for example, a magnetoresistive random access memory (MRAM), which is promising as a next generation memory, is vulnerable to a high temperature process. Therefore, the surface protective film is cured by a heat treatment at a low temperature of about 250 占 폚 or lower, a polyimide resin which is comparable to a cured film which has conventionally been cured by a heat treatment at a high temperature of around 350 占 폚, Resin is required.

As a method of obtaining a polyimide-based resin or a polybenzoxazole-based resin which is cured by a heat treatment at a low temperature, the following method is known. That is, a method of adding a cyclization accelerator, introducing an organic group that promotes cyclization at a low temperature into the unit structure, and a method of using a polyimide or polybenzoxazole that has been previously ring closed after imparting alkali solubility.

Further, when the heat-resistant resin composition is used for applications such as semiconductors, the cured film obtained by heat treatment remains as a permanent film in the device, so physical properties as a cured film are very important. In order to ensure reliability in the semiconductor package, adhesion with a material formed on the surface of the semiconductor chip is important. In particular, when used as an insulating film or the like between wiring layers of a wafer level package, adhesion with metal materials used for electrodes, wiring, and the like becomes important.

However, the resin composition containing a resin that can be cured by the above-described heat treatment at a low temperature has a problem in that adhesion to a metal used as the wiring material is low.

The heat-resistant resin generally has a high adhesion strength to a metal material from its rigid backbone structure. Particularly, in the case of a cured film of a resin composition to which photosensitivity is imparted, additives such as a photosensitizer, a sensitizer, an acid generator, and a dissolution regulating agent constituting the resin composition remain in the cured film even after heat curing. Therefore, the adhesion strength is lower than that which does not contain an additive. As a solution therefor, a positive-type photosensitive resin composition comprising an alkaline aqueous solution-soluble polymer, a photoacid generator and a silane compound containing at least four specific functional groups directly bonded to Al atoms, Ti atoms and Si atoms (see Patent Document 1) , A heat resistant resin precursor such as a polyimide precursor, and a specific amino compound or thiol derivative (see Patent Documents 2 to 5).

Japanese Patent Application Laid-Open No. 2008-276190 (pages 1-3) Japanese Patent Application Laid-Open No. 2007-39486 (pages 1-3) Japanese Patent Application Laid-Open No. 2003-5369 (pages 1-3) International Publication No. 2014/115233 (pages 1-3) Japanese Patent Application Laid-Open No. 2015-232688 (pages 1-4)

However, the photosensitive resin compositions and the heat-resistant resin precursor compositions described in Patent Documents 1 to 4 have poor compatibility with resins and additives and have poor applicability. For this reason, voids are formed when coating and prebaking are performed on the irregular metal wiring, and the adhesion between the resulting cured film and the metal wiring is sometimes deteriorated. In addition, the resin composition described in Patent Document 5 can not produce unreacted compounds at the time of polymerization, and sufficient adhesiveness can not be ensured when it is used as a cured film. It is therefore an object of the present invention to provide a photosensitive resin composition which can obtain a cured film excellent in adhesion to a metal material, particularly copper, even in a heat treatment at a low temperature, and has a high coating property.

In order to solve the above problems, the photosensitive resin composition of the present invention has the following constitution. (A) an alkali-soluble resin having an organic group derived from an aliphatic diamine, (B) a photosensitizer, (C) a photosensitive resin composition containing 1013 hPa and a compound which is liquid at 25 ° C and has a boiling point of 210 ° C or higher,

(C) 0.1 to 15 parts by mass of a compound which is liquid at 1013 hPa at 25 캜 and has a boiling point of not less than 210 캜, relative to 100 parts by mass of an alkali-soluble resin having an organic group derived from an aliphatic diamine (A) Wherein the photosensitive resin composition is a photosensitive resin composition.

The photosensitive resin composition of the present invention has excellent coatability and can obtain a cured film having excellent adhesion with a metallic material, particularly copper, even in a heat treatment at a low temperature.

The present invention relates to a photosensitive resin composition comprising (A) an alkali-soluble resin having an organic group derived from an aliphatic diamine, (B) a photosensitizer, (C) a liquid at 1013 hPa, a temperature of 25 ° C, (C) 0.1 to 15 parts by mass of a compound which is liquid at 1013 hPa at 25 캜 and has a boiling point of not less than 210 캜, relative to 100 parts by mass of an alkali-soluble resin having an organic group derived from an aliphatic diamine (A) By weight. Hereinafter, the components (A), (B) and (C) may be omitted.

The reason why the cured film formed by curing the photosensitive resin composition of the present invention by heat treatment is excellent in adhesion to metals, particularly copper, is as follows. That is, the amount of the compound (C) contained in the curable film is 0.1 to 15 parts by mass based on 100 parts by mass of the component (A) (C) remaining on the film can be confined to the boundary with the copper substrate which is difficult to evaporate. As a result, the vicinity of the interface between the copper substrate of the cured film is locally swollen and softened. As a result, the cured film can intrude into the fine unevenness of the copper substrate, and the adhesion with the copper substrate is improved by the anchor effect. Further, since the structure has an amide group and the nitrogen atom is coordinated to copper, adhesion between the cured film and copper can be improved both physically and chemically. Further, the above-mentioned photosensitive resin composition can further improve the adhesion with copper by containing (D) the compound represented by the general formula (5) and the compound represented by the general formula (6).

(In the general formula (5), R ⁷ to R ^{9 each} represent an oxygen atom, a sulfur atom or a nitrogen atom, and at least one of R ⁷ to R ⁹ represents a sulfur atom. R ⁷ represents an oxygen atom or a sulfur atom when l is 0 and represents a nitrogen atom when l is 1. m and n represent 1 or 2. R ¹⁰ to R ¹² each independently represent hydrogen An atom or an organic group having 1 to 20 carbon atoms.

(In the general formula (6), R ¹³ represents a hydrogen atom or an alkyl group having 1 or more carbon atoms, R ¹⁴ represents an alkylene group having 2 or more carbon atoms, R ¹⁵ represents an alkylene group having 2 or more carbon atoms, And k represents an integer of 1 to 4.)

For this reason, the photosensitive resin composition of the present invention can obtain a cured film having high adhesion to metallic materials, particularly copper, even in the heat treatment at a low temperature of 250 캜 or less.

Further, the photosensitive resin composition of the present invention is excellent in coating property. The coating property was judged to be excellent when the photosensitive resin composition was coated on the metal wiring having concavo-convex and then pre-baked, and no vertical stripes appeared on the surface or the surface of the coating film. The reason that the photosensitive resin composition of the present invention is excellent in the applicability is that it is possible to suppress the volatilization of the solvent at the time of coating and suppress the voids and vertical stripe of the prebaked film because the compound (C) has a high boiling point .

The alkali-soluble resin having an organic group derived from the aliphatic diamine (A) used in the present invention preferably contains one or more kinds of resins selected from polyimide, polybenzoxazole, polyamideimide and their precursor resins Do.

Examples of the polyimide precursor which is preferably used in the present invention include polyamic acid, polyamide acid ester, polyamide acid amide, polyisoimide and the like. For example, the polyamic acid can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, a tetracarboxylic acid diester dichloride, etc. with a diamine, a corresponding diisocyanate compound, or trimethylsilylated diamine. The polyimide can be obtained, for example, by dehydrating and ring closure of the polyamic acid obtained by the above-mentioned method by heating or chemical treatment such as acid or base.

As polybenzoxazole precursors preferably used in the present invention, polyhydroxy amides can be mentioned. For example, polyhydroxyamides can be obtained by reacting bisaminophenol with dicarboxylic acid, the corresponding dicarboxylic acid chloride, dicarboxylic acid active ester, and the like. The polybenzoxazole can be obtained, for example, by dehydration ring closure of polyhydroxy amide obtained by the above-mentioned method by heating or chemical treatment such as anhydrous phosphoric acid, a base or a carbodiimide compound.

The polyamideimide precursor preferably used in the present invention can be obtained by reacting a diamine or a diisocyanate with, for example, a tricarboxylic acid, a corresponding tricarboxylic acid anhydride, a tricarboxylic acid anhydride halide and the like. The polyamide imide can be obtained, for example, by dehydrating and ring closure of the precursor obtained by the above-mentioned method by heating or chemical treatment such as acid or base.

The alkali-soluble resin having an organic group derived from the aliphatic diamine (A) used in the present invention preferably has at least one kind selected from the structural units represented by the following general formulas (7) to (10). And may be composed of two or more resins having these structural units, or may be a resin obtained by copolymerizing two or more structural units.

(Formula (7) to (10), R ¹⁶ and R ¹⁹ is a tetravalent organic group, R ^17, R ¹⁸ and R ²¹ is a divalent organic group, R ²⁰ is a trivalent organic group, R ²² is 2 to And R ²³ represents an organic group having a valency of 2 to 12. It is preferable that all of R ¹⁶ to R ²³ have an aromatic ring and / or an aliphatic ring, and R ²⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms P represents an integer of 0 to 2, and q represents an integer of 0 to 10.)

In the general formulas (7) to (10), R ¹⁶ is a tetracarboxylic acid derivative residue, R ¹⁸ is a dicarboxylic acid derivative residue, R ²⁰ is a tricarboxylic acid derivative residue, R ²² is a di- Tetra-carboxylic acid derivative residue. Examples of the acid component constituting R ¹⁶ , R ¹⁸ , R ²⁰ and R ²² (COOR ²⁴ ) p include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) Examples of the tricarboxylic acid include trimellitic acid, trimethic acid, diphenyl ether tricarboxylic acid, diphenyl ether tricarboxylic acid, diphenyl ether tricarboxylic acid, diphenyl ether tricarboxylic acid, Examples of the biphenyltricarboxylic acid and the tetracarboxylic acid include pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid Benzoic acid, 2,2 ', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 2,2 ', 3,3'-benzophenonetetra (3, 4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1- Dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis 5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracar Aromatic tetracarboxylic acids such as tetracarboxylic acid and tetracarboxylic acid, and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Of these, in the general formula (10), one or two carboxyl groups of the tricarboxylic acid and the tetracarboxylic acid respectively correspond to the COOR ²⁴ group. These acid components can be used as they are, or as acid anhydrides, active esters and the like. These two or more acidic components may be used in combination.

In the general formulas (7) to (10), R ¹⁷ , R ¹⁹ , R ²¹ and R ²³ represent a diamine derivative residue. Examples of the diamine component constituting R ¹⁷ , R ¹⁹ , R ²¹ and R ²³ (OH) q include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis Amino-4-hydroxy) biphenyl and bis (3-amino-4-hydroxyphenyl) fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4'-diaminodiphenyl ether Diamine, and dimercaptophenylenediamine; diamines such as 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenylmethane;'-Diaminodiphenylmethane,3,4'-diaminodiphenylsulfone,4,4'-diaminodiphenylsulfone,3,4'-diaminodiphenylsulfide,4,4'-diaminodi Phenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, benzene, m-phenylenediamine, (4-aminophenoxy) sulfone, bis (4-aminophenoxy) biphenyl, bis Bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Diethyl-4,4'-diaminobiphenyl,3,3'-dimethyl-4,4'-diaminobiphenyl,3,3'-diethyl-4,4'-diaminobiphenyl, 2 , 2 ', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'- Aromatic diamines such as bis (trifluoromethyl) -4,4'-diaminobiphenyl, and aromatic diamines such as those obtained by substituting a part of the hydrogen atoms of these aromatic rings with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom or the like Compounds, alicyclic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine, and the like. These diamines can be used as such or as a corresponding diisocyanate compound or trimethylsilylated diamine. These two or more diamine components may be used in combination. In applications where heat resistance is required, it is preferable to use an aromatic diamine in an amount of 50 mol% or more of the entire diamine.

R ¹⁶ to R ²³ in formulas (7) to (10) may include a phenolic hydroxyl group, a sulfonic acid group, a thiol group and the like in the skeleton thereof. By using a resin having a phenolic hydroxyl group, a sulfonic acid group or a thiol group, a photosensitive resin composition having alkali solubility is obtained.

Further, it is preferable to have a fluorine atom in the structural unit of the component (A). The fluorine atom imparts water repellency to the surface of the film during alkali development, so that impregnation from the surface can be suppressed. The fluorine atom content in 100 mass% of the component (A) is preferably 10 mass% or more in order to sufficiently obtain the effect of preventing the interface from becoming impregnated, and 20 mass% or less from the viewpoint of solubility in an aqueous alkali solution.

The alkali-soluble resin having an organic group derived from the aliphatic diamine (A) used in the present invention preferably has an organic group derived from the aliphatic diamine at R ¹⁷ , R ²¹ and R ²³ . The organic group derived from the aliphatic diamine can be obtained by copolymerizing (a) an aliphatic diamine.

The content ratio of the organic group derived from the aliphatic diamine is preferably at least 1 mol%, more preferably at least 3 mol% of the entire diamine from the viewpoint of improving adhesion between the cured film and the metal. On the other hand, it is preferably not more than 50 mol%, more preferably not more than 40 mol% from the viewpoint of improving the heat resistance.

Examples of the aliphatic diamine (a) include the following. That is, it is preferable to use one or more selected from the group consisting of ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, Diaminohexane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11- 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-cyclohexanediamine, 1,3-cyclohexanediamine, -Bis (aminomethyl) cyclohexane, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D- 200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP- RT-1000, HE-1000, HT-1100 and HT-1700 (trade names, ), And the like. These compounds include, but are not limited to, -S-, -SO-, -SO 2 -, -NH-, -NCH 3 -, -N (CH 2 CH 3) -, -N (CH 2 CH 2 CH 3) COO-, -CONH-, -OCONH-, -NHCONH-, and the like.

Further, in order to improve the storage stability of the photosensitive resin composition of the present invention, the component (A) is sealed with a terminal sealing agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, .

The introduction ratio of the monoamine used as the terminal sealing agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, based on the total amine component. On the other hand, it is preferably at most 60 mol%, particularly preferably at most 50 mol%.

The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as a terminal sealing agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more with respect to the diamine component , Preferably not more than 100 mol%, particularly preferably not more than 90 mol%. A plurality of different terminal groups may be introduced by reacting a plurality of terminal sealing agents.

Examples of the monoamine include aniline, 2-ethynyl aniline, 3-ethynyl aniline, 4-ethynyl aniline, 5-amino-8-hydroxyquinoline, 1-hydroxy- Aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy- Amino-naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy- Aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3- aminobenzenesulfonic acid, 4-aminophenol, 4-aminophenol, 2-amino-4-aminophenol, 4-aminophenol, Oh phenol, such as 3-amino-thiophenol, 4-amino-thiophenol are preferred. Two or more of these may be used.

Examples of the acid anhydride, monocarboxylic acid, monoacid chloride compound and mono-active ester compound include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride and 3-hydroxyphthalic acid anhydride, -Carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1- , Monocarboxylic acids such as 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4- A monoacid chloride compound in which the carboxyl group of the carboxyl group is acid chloridized, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxy naphthalene, 1,6- dicarboxy naphthalene, 2,6-di A monoacid chloride compound in which only one carboxyl group of a dicarboxylic acid such as carboxynaphthalene is converted into an acid chloride, a monoacid chloride compound, a N-hydroxybenzotriazole or an N-hydroxy-5-norbornene- - an active ester compound obtained by the reaction of dicarboxyimide and the like are preferable. Two or more of these may be used.

The end sealant introduced into the component (A) can be easily detected by the following method. For example, by dissolving a resin into which an end sealant is introduced in an acidic solution and decomposing it into an amine component and an acid anhydride component as constituent units and measuring the result by gas chromatography (GC) or nuclear magnetic resonance (NMR) The end sealant used in the invention can be easily detected. Apart from this, the resin component into which the end sealant has been introduced can be easily detected directly by pyrolysis gas chromatography (PGC), infrared spectroscopy and ¹³ C-NMR spectrum measurement.

It is preferable that the repeating number of one or more structural units selected from the structural units represented by the general formulas (7) to (10) in the component (A) used in the present invention is in the range of 3 to 1000 . When the repeating number of the structural unit is 3 or more, it is preferable because a thick film can be easily formed, and when it is 1000 or less, the photosensitive property of the photosensitive resin composition can be maintained.

The component (A) in the present invention may be composed solely of one or more structural units selected from the structural units represented by the general formulas (7) to (10), or may be a copolymer or mixture It may be.

It is preferable that at least one structural unit selected from the structural units represented by the general formulas (7) to (10) is contained in an amount of 10 mass% or more of the entire component (A) from the viewpoint of improving the heat resistance of the obtained cured film, By mass or more, and most preferably 100% by mass.

When copolymerizing or mixing with other structural units, it is preferable to select the type and amount of structural units used for copolymerization or mixing within a range that does not impair the mechanical properties of the thin film obtained by the final heat treatment. Examples of the main chain skeleton of the other structural unit include benzimidazole, benzothiazole, and the like.

The photosensitive resin composition of the present invention contains (B) a photosensitizer. (B) The photosensitizer may be a negative type which is cured by light, or a positive type which is solubilized by light. The former is preferably used as the photopolymerization initiator (b-1) and the polymerizable unsaturated compound, and the latter is preferably used as the quinone diazide compound (b-2).

Examples of the photopolymerization initiator in (b-1) include benzophenone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 3,3,4,4-tetra (Diethylaminobenzylidene) -N-ethyl-4-piperidone such as 3,5-bis (diethylaminobenzylidene) -N- Benzylidenes such as piperidone, 7-diethylamino-3-tennylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7 Coumarins such as diethylamino-3- (1-methylbenzoimidazolyl) coumarin and 3- (2-benzothiazolyl) -7-diethylaminocoumarin, 2-t-butyl anthraquinone, 2- Anthraquinone such as anthraquinone and 1,2-benzanthraquinone, benzoin such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, ethylene glycol di (3-mercaptopropionate), 2 - mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenz Imidazole and the like, glycines such as N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p- chlorophenyl) glycine and N- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o (methoxycarbonyl) oxime, (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (Trade name, manufactured by Ciba Specialty Chemicals), NCI-831 (trade name, manufactured by Ciba Specialty Chemicals), 1,2-hexanediol 2-dimethylamino-1- (4-morpholinophenyl) -butane-l-2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, and the like, [alpha] -aminoalkylphenones such as 2,2'-bis (o- chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole .

Of these, oximes are preferable, and particularly preferable are 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl- (o-benzoyloxime), OXE02 (o-benzoyloxy) oxime, bis (a-isonitroprophenone oxime) isophthalate, , NCI-831. These may be used alone or in combination of two or more.

Of these, benzophenones, glycines, mercaptans, oximes,? -Aminoalkylphenols, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl Combinations selected from nonimidazoles are suitable in terms of photoreaction.

The content of the photopolymerization initiator in the component (b-1) is preferably from 0.1 to 60 parts by mass, more preferably from 0.2 to 40 parts by mass, based on 100 parts by mass of the total amount of the component (A). When the amount is at least 0.1 part by mass, sufficient radicals are generated due to light irradiation and the sensitivity is improved. When the amount is less than 60 parts by mass, the occurrence of excessive radicals does not cause curing of the unsprayed portions and alkalinity developability is improved .

Examples of the polymerizable unsaturated compound in the component (b-1) include unsaturated double bond functional groups such as a vinyl group, an allyl group, an acryloyl group and a methacryloyl group, and unsaturated triple bond functional groups such as a propargyl group Among them, a conjugated vinyl group, an acryloyl group and a methacryloyl group are preferable in terms of polymerizability.

The number of the functional groups to be contained is preferably 1 to 4 in terms of stability, and each may not be the same group.

The average molecular weight of the polymerizable unsaturated compound in the component (b-1) is not particularly limited, but it is preferable that the number average molecular weight is 800 or less in view of good compatibility with the polymer and the reactive diluent. Further, for the purpose of suppressing the solubility in a developing solution after exposure, the number average molecular weight is preferably 30 or more.

Specific examples of the polymerizable unsaturated compound in the component (b-1) include diethyleneglycol diacrylate, triethyleneglycol diacrylate, tetraethyleneglycol diacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate Trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene,? -Methylstyrene, 1,2-propanediol, 1,6-hexanediol dimethacrylate, Diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl Acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6- Hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, Ethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide , N-methylol acrylamide, 2,2,6 , 6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N Methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, N-vinyl Caprolactam, and the like. These may be used alone or in combination of two or more.

Of these, particularly preferred are 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexa methacrylate, dipentaerythritol triacrylate, Methylene bisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl Acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A Diacrylate, ethylene oxide Bisphenol A dimethacrylate, and the like can be mentioned N- vinylpyrrolidone, N- vinylcaprolactam.

The content of the polymerizable unsaturated compound in the component (b-1) is preferably 1 to 40 parts by mass relative to 100 parts by mass of the component (A). More preferably not less than 3 parts by mass for the purpose of suppressing the solubility in a developer after exposure, and more preferably not more than 20 parts by mass for the purpose of obtaining a highly vertical pattern.

Examples of the quinone diazide compound of the formula (b-2) include a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxy compound, a compound in which a sulfonic acid of quinone diazide is sulfonamide bonded to a polyamino compound, Diazide sulfonic acid is ester-bonded and / or sulfonamide-bonded. Although not all of the functional groups of the polyhydroxy compound, polyamino compound and polyhydroxypolyamino compound may be substituted with quinone diazide, it is preferable that on average at least 40 mol% of the functional groups are substituted with quinone diazide . By using such a quinone diazide compound, a positive photosensitive resin composition which is exposed to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) have.

Bisp-PZ, BisP-IPZ, BisP-PZ, BisP-PZ, BisP-PZ, BisP-ZZ, BisP- DML-OCHP, DML-PCHP, DML-PCC, BisRS-26P, BisCl-MBP, DMSO-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris- PML, TML-BP, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML- PC, BIR-PC, BIR-PTBP, and HML-TPHAP (all trade names, manufactured by Honshu Chemical Industries, Ltd.) BIP-A (trade name, manufactured by Asahi Yuki Kai Kogyo Co., Ltd.), 2,6-diisopropylphosphoric anhydride (BIP-BOP) Dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, glycine methyl ester, bisphenol A , Bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), novolak resin, and the like But are not limited to these.

Examples of the polyamino compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.

Examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine. Do not.

Among them, it is more preferable that the (b-2) quinone diazide compound includes a phenol compound and an ester of a 5-naphthoquinone diazidesulfonyl group or a 4-naphthoquinone diazidesulfonyl group. Thereby, high sensitivity and higher resolution can be obtained by i-line exposure.

The content of the quinonediazide compound (b-2) is preferably 20 parts by mass or more, and more preferably 40 parts by mass or more, for the purpose of improving the contrast of the pattern with respect to 100 parts by mass of the component (A). Further, 200 parts by mass or less is preferable, and 150 parts by mass or less is more preferable for the purpose of improving the sensitivity and decreasing the necessary exposure amount. A sensitizer may also be added as needed.

The photosensitive resin composition of the present invention contains (C) a compound which is liquid at 1013 hPa at 25 캜 and has a boiling point of 210 캜 or higher. By containing the compound (C) in an amount of 0.1 to 15 parts by mass based on 100 parts by mass of the component (A) and further having a high boiling point, the residual amount of the compound (C) can be minimized. The residual (C) compound has a higher concentration at the interface with the copper substrate, which is difficult to evaporate. Thereby, the cured film in the vicinity of the copper substrate interface is locally swollen, and the cured film is softened. As a result, the cured film can enter the fine irregularities of the copper substrate, and the adhesion with the copper substrate is improved by the anchor effect. When the photosensitive resin composition of the present invention is cured, the total content of the compound (C) in the cured film is preferably 0.005% by mass or more, more preferably 0.05% by mass or more based on the total mass of the cured film By mass, preferably 5% by mass or less, and more preferably 3% by mass or less. When the total content of the compound (C) is 0.005% by mass or more, adhesiveness to the copper substrate is improved. When the total content of the compound (C) is 3% by mass or less, the compound itself can become an outgassing.

The reason why the coating property is excellent is that the compound (C) has a high boiling point and can suppress the rapid volatilization at the time of coating, whereby the coating can be carried out on the metal wiring having unevenness without generating voids .

From the viewpoint of easily allowing the compound (C) to remain in the film after the heat treatment, it is preferable that the boiling point is 210 占 폚 or higher. From the viewpoint of the process time of the prebake and the developability of the prebaked film, the boiling point is preferably 400 DEG C or less. If the boiling point can not be measured at atmospheric pressure, the method described in Tokyo Kasei Kogyo Kogyo Kogyo Co., Ltd. Catalog 2008-2009 (No.39) p.2173 (Exhibit: Sceience and Petroleum, Vol. From the boiling point table, it can be converted to the boiling point at normal pressure.

The mass% of the compound (C) in the cured film can be measured by measuring the mass of the compound by using a purge-and-trap method, a TPD-MS method or the like and comparing the value with the specific gravity of the alkali- , The mass% of the compound in the cured film can be calculated.

Specific examples of the compound (C) include 1,3-dimethyl-2-imidazolidinone (boiling point 220 ° C), N, N-dimethylpropylene urea (boiling point 246 ° C) Amide (boiling point 216 占 폚), 3-butoxy-N, N-dimethylpropionamide (boiling point 252 占 폚), delta valerolactone (boiling point 230 占 폚), 2-phenoxyethanol (Boiling point: 260 占 폚), butyl benzoate (boiling point: 230 占 폚), pyrrolidone (boiling point: 245 占 폚), 2-methyl-1,3-propanediol (Boiling point 250 ° C), cyclohexylbenzene (236 ° C), bicyclohexyl (239 ° C), o-nitroanisole (273 ° C), diethylene glycol monobutyl ether (230 ° C), triethylene glycol monomethyl ether N-cyclohexyl-2-pyrrolidone (boiling point: 154 占 폚 / 7 mmHg, at atmospheric pressure boiling point: 305 占 폚), 3-methoxy- Pyrrolidone (boiling point: 175 占 폚 / 10 mmHg, atmospheric pressure boiling point: 313 占 폚) There. Among them, from the viewpoint of adhesion with copper, the compound (C) preferably has a structure represented by the following general formulas (1) to (4).

(In the formulas (1) to (4), R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, R ² represents a divalent organic group having 1 to 5 carbon atoms, R ⁵ represents hydrogen, R ³ , R ⁴ and R ⁶ each independently represent an organic group having 1 to 5 carbon atoms, and n represents an integer within a range of 1 to 3.)

The compound (C) may contain two or more kinds of compounds, and may be a polymerization solvent of the component (A).

When the polymerization solvent of the component (A) is used, the photosensitive resin composition of the present invention may contain a specified amount by reprecipitating a poor solvent such as pure water after completion of the polymerization reaction, washing, and drying.

The content of the compound (C) is preferably 0.1 part by mass or more, more preferably 0.5 parts by mass or more, and preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the resin (A) Or less. When the amount is 0.1 parts by mass or more, the adhesion with copper can be enhanced. When the amount is 15 parts by mass or less, a desired patterning film can be formed as a developing film.

The photosensitive resin composition of the present invention preferably contains (D) a compound represented by the general formula (5) (hereinafter may be abbreviated as the (D) component). (D), the adhesiveness between the film after heat curing and the metal material, particularly copper, is remarkably improved. This is due to the fact that the sulfur atom or nitrogen atom of the compound represented by the general formula (5) is derived from the efficient interaction with the metal surface and has a three-dimensional structure which is easy to interact with the metal surface. By these effects, the photosensitive resin composition of the present invention can obtain a cured film excellent in adhesion to a metal material. Particularly, it is a compound which interacts with copper, and the adhesion between the film after heat curing and the metal material is greatly improved.

(In the general formula (5), R ⁷ to R ^{9 each} represent an oxygen atom, a sulfur atom or a nitrogen atom, and at least one of R ⁷ to R ⁹ represents a sulfur atom. R ⁷ represents an oxygen atom or a sulfur atom when l is 0 and represents a nitrogen atom when l is 1. m and n represent 1 or 2. R ¹⁰ to R ¹² each independently represent hydrogen As it represents an organic group of an atom or group having 1 to 20. R ¹⁰ to R ^12, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, A carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and combinations thereof, and may further have a substituent.)

Examples of the compound represented by the general formula (5) include, but are not limited to, the following structures.

The content of the compound (D) represented by the general formula (5) is preferably from 1 to 40 parts by mass per 100 parts by mass of the component (A), more preferably from 3 parts by mass or more for the purpose of suppressing solubility in a developing solution after exposure More preferably 20 parts by mass or less from the viewpoint of storage stability.

The photosensitive resin composition of the present invention preferably contains (E) a compound represented by the following general formula (6) (hereinafter occasionally referred to as component (E)). By containing the component (E), the mechanical properties of the cured film after the reliability evaluation and the deterioration of the adhesiveness with the metal material can be suppressed.

(In the general formula (6), R ¹³ represents a hydrogen atom or an alkyl group having 1 or more carbon atoms, R ¹⁴ represents an alkylene group having 2 or more carbon atoms, R ¹⁵ represents an alkylene group having 2 or more carbon atoms, And k represents an integer of 1 to 4.)

The component (E) acts as an antioxidant to inhibit oxidation of the aliphatic group or the phenolic hydroxyl group of the component (A). In addition, oxidation of the metal material can be suppressed by a rust-inhibiting action on the metal material.

Further, when the cured film is used, the adhesion between the cured film and the metal material can be improved by interacting with both the component (A) and the metal material in the cured film. In order to more effectively interact with both the component (A) and the metal material in the cured film, k is more preferably an integer of 2 to 4. Examples of R ¹⁵ include alkyl groups, cycloalkyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, And may further have a substituent. Among them, it is preferable to contain an alkyl ether, -NH- in view of the solubility in a developing solution and the adhesion of the metal, and in view of the interaction with the component (A) and the metal adhesion by metal complex formation, More preferable.

The amount of the component (E) to be added is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass, per 100 parts by mass of the component (A). When the addition amount is 0.1 parts by mass or more, oxidation deterioration of the aliphatic group and the phenolic hydroxyl group can be suppressed, and oxidation of the metal material can be suppressed by a rust-inhibitive action to the metal material. It is also preferable that the addition amount is 10 parts by mass or less because the sensitivity of the positive photosensitive resin composition before curing can be suppressed by interaction with the photosensitizer.

The component (E) includes, for example, the following components, but is not limited to the following structure.

The photosensitive resin composition of the present invention may contain a solvent as required. Preferable examples of the solvent include a polar aprotic solvent such as N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Ketones such as acetone, methyl ethyl ketone and diisobutyl ketone; ketones such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether; Esters such as ethyl lactate, methyl lactate, diacetone alcohol and 3-methyl-3-methoxybutanol; alcohols such as toluene and xylene; Aromatic hydrocarbons and the like. Two or more of these may be contained.

The content of the solvent is preferably 70 parts by mass or more, more preferably 100 parts by mass or more, from the viewpoint of improving the solubility of the resin with respect to 100 parts by mass of the component (A). In view of obtaining a proper film thickness, Preferably 1800 parts by mass or less, and more preferably 1500 parts by mass or less.

The photosensitive resin composition of the present invention may contain a low molecular weight compound having a phenolic hydroxyl group within a range that does not decrease the shrinkage residual film ratio after curing, if necessary. By containing a low molecular weight compound having a phenolic hydroxyl group, the alkali solubility during pattern processing can be easily controlled.

The content of the low molecular weight compound having a phenolic hydroxyl group is preferably 0.1 part by mass or more, more preferably 1 part by mass or more based on 100 parts by mass of the component (A) Preferably 30 parts by mass or less, and more preferably 15 parts by mass or less from the viewpoint of maintaining the mechanical properties of the resin.

The photosensitive resin composition of the present invention may contain a heat crosslinking agent if necessary. As the thermal cross-linking agent, a compound having at least two alkoxymethyl groups and / or methylol groups, and a compound having at least two epoxy groups and / or oxetanyl groups are preferably used, but are not limited thereto. By containing these compounds, a condensation reaction with the component (A) occurs upon curing after patterning to form a crosslinked structure, and the mechanical properties such as elongation of the cured film are improved. In addition, two or more kinds of thermal crosslinking agents may be used, thereby enabling a wider design.

Preferred examples of the compound having at least two alkoxymethyl groups and / or methylol groups include DML-PC, DML-PEP, DML-OC, DML-BisOC-P, DML-BisOC-P, DML-BisOC-P, DML-POC, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML- TML-BPAP, TML-BPAP, TML-BPAP, TML-BPP, TML-BP-BP, TML-BPE, TML- HMOM-TPHAP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), " NIKALAC (registered trademark of NIKALAC Corporation), TMOM-BPA, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML- NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM and NIKALAC MX-750LM (trade names, available from Sanwa Chemical Co.) Available from each company. Two or more of these may be contained.

Preferable examples of the compound having at least two epoxy groups and / or oxetanyl groups include bisphenol A type epoxy resin, bisphenol A type oxetanyl resin, bisphenol F type epoxy resin, bisphenol F type oxetanyl resin, And epoxy group-containing silicones such as propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polymethyl (glycidyloxypropyl) siloxane, but are not limited thereto.

EPICLON HP-820-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EPICLON EXA-4816, EPICLON EXA-4822 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), "EPICLON EXA- EP-4000S (trade name, manufactured by ADEKA Co., Ltd.), and the like, and they are available from each company . Two or more of these may be contained.

The content of the thermal crosslinking agent used in the present invention is preferably at least 0.5 part by mass, more preferably at least 1 part by mass, and even more preferably at least 3 parts by mass, relative to 100 parts by mass of the component (A). Preferably not more than 300 parts by mass, more preferably not more than 200 parts by mass, further preferably not more than 100 parts by mass, still more preferably not more than 70 parts by mass, particularly preferably not more than 40 parts by mass, particularly preferably not more than 40 parts by mass, Parts by mass or less.

For the purpose of improving the wettability with the substrate as required, the photosensitive resin composition of the present invention may contain a surfactant, esters such as ethyl lactate or propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl isobutyl Ketones such as ketones, and ethers such as tetrahydrofuran and dioxane.

The preferable content of the compound used for the purpose of improving the wettability with these substrates is 0.001 part by mass or more based on 100 parts by mass of the component (A), and from the viewpoint of obtaining a proper film thickness, preferably 1800 parts by mass or less Preferably 1500 parts by mass or less.

The photosensitive resin composition of the present invention may contain inorganic particles. Preferable specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, talc, and the like.

The average primary particle diameter of these inorganic particles is preferably 1 nm or more and 100 nm or less, and more preferably 10 nm or more and 60 nm or less, from the viewpoint of photosensitivity. The individual particle diameters of these inorganic particles can be measured with a scanning electron microscope, for example, a scanning electron microscope manufactured by Nippon Denshi Co., Ltd., JSM-6301NF. In addition, the average primary particle diameter can be calculated by measuring the diameter of 100 particles randomly selected from the photograph and calculating an arithmetic average thereof.

In order to improve the adhesion with the silicon substrate, a silane coupling agent such as trimethoxyaminopropylsilane, trimethoxyepsiloxy, trimethoxyvinylsilane, trimethoxythiopropylsilane, .

The preferable content of the compound used for enhancing the adhesion to these silicon substrates is 0.01 part by mass or more based on 100 parts by mass of the component (A), preferably 5 parts by mass or less from the viewpoint of maintaining the mechanical properties such as elongation .

The viscosity of the photosensitive resin composition of the present invention is preferably 2 to 5000 mPa · s. It is easy to obtain a desired film thickness by adjusting the solid content concentration so that the viscosity is 2 mPa s or more. On the other hand, when the viscosity is 5000 mPa s or less, it is easy to obtain a highly uniform coating film. The resin composition having such a viscosity can be easily obtained by, for example, setting the solid content concentration to 5 to 60 mass%.

Next, a method of forming a resin pattern using the photosensitive resin composition of the present invention will be described.

When the photosensitive resin composition of the present invention is directly applied to a substrate, the substrate may be a wafer of silicon, ceramics, or gallium arsenide, or a metal on which a metal is formed as an electrode or a wiring, but is not limited thereto. As a coating method, spin coating using a spinner, spray coating, roll coating and the like are available. The thickness of the coating film varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 mu m. The substrate may be pretreated with the above-described silane coupling agent in order to improve adhesion between the substrate such as a silicon wafer and the photosensitive resin composition. For example, the silane coupling agent may be dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate or diethyl adipate in an amount of 0.5 to 20 mass% Is subjected to surface treatment by spin coating, dipping, spray application, steam treatment, or the like. In some cases, heat treatment is then performed at 50 to 300 캜 to advance the reaction between the substrate and the silane coupling agent.

Subsequently, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. The drying is preferably performed at a temperature in the range of 50 to 150 DEG C for 1 minute to several hours by using an oven, a hot plate, an infrared ray or the like.

On the other hand, when the photosensitive resin composition of the present invention is used as a photosensitive resin sheet, it is preferable to form a photosensitive resin sheet by applying and drying on a support film. The supporting film to be used is not particularly limited, but various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used. The bonding surface of the support film and the photosensitive resin sheet may be subjected to a surface treatment such as a silicone, a silane coupling agent, an aluminum chelating agent, or a polyurethane to improve adhesion and peelability. The thickness of the support film is not particularly limited, but is preferably in the range of 10 to 100 mu m from the viewpoint of workability. The photosensitive resin composition applied on the support film is subjected to a drying step. The drying temperature is preferably 50 占 폚 or higher from the viewpoint of drying property and is preferably 150 占 폚 or lower from the viewpoint of not impairing photosensitivity. At this time, the film thickness of the photosensitive resin sheet is preferably 5 占 퐉 or more from the viewpoint of step embeddability during lamination, and 150 占 퐉 or less from the viewpoint of film thickness uniformity.

In order to protect the surface of the photosensitive resin sheet of the present invention, a protective film may be provided on the sheet. Thereby, the surface of the photosensitive adhesive film can be protected from contaminants such as dust and dust in the air.

Examples of the protective film include a polyolefin film and a polyester film. It is preferable that the protective film has a small adhesive force with the photosensitive resin sheet.

The obtained photosensitive resin sheet is bonded to the substrate. As the substrate, a wafer such as silicon, ceramics or gallium arsenide, or a metal on which a metal is formed as an electrode or a wiring is used, but the present invention is not limited thereto. When the photosensitive resin sheet has a protective film, it is peeled off, and the photosensitive resin sheet and the substrate are opposed to each other and bonded together by thermocompression bonding to obtain a photosensitive adhesive composition film. The thermocompression bonding can be performed by hot pressing, thermal lamination, thermal vacuum lamination, or the like. The bonding temperature is preferably 40 占 폚 or higher in terms of adhesion to the substrate and filling property. Further, in order to prevent the photosensitive adhesive film from hardening at the time of bonding and deteriorate the resolution of pattern formation in the exposure and development process, the bonding temperature is preferably 150 ° C or lower.

Subsequently, the photosensitive resin composition film formed on the substrate is exposed to actinic radiation through a mask having a desired pattern and exposed. Examples of the actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X rays. In the present invention, it is preferable to use i line (365 nm), h line (405 nm), and g line (436 nm) Do.

In order to form a pattern of the heat-resistant resin, after exposure, the exposed portion is removed using a developing solution. Examples of the developer include aqueous solutions such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. Further, in some cases, an aqueous alkali solution of these may be added to an aqueous solution of an alkali, such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, , Ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, and the like, and the like, and alcohols such as methanol, ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, Alone or in combination of several species may be added. After development, rinsing with water is preferred. Herein, alcohol such as ethanol and isopropyl alcohol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate and the like may be added to water and rinsed.

After development, a temperature of 150 to 500 占 폚 is applied to promote thermal crosslinking reaction, imide ring closure reaction, and oxazole ring closure reaction to improve heat resistance and chemical resistance. In this heating treatment, the temperature is selected and the temperature is raised stepwise, and the temperature is successively raised for 5 minutes to 5 hours by selecting a certain temperature range. As an example, heat treatment is performed at 130 캜 and 200 캜 for 30 minutes each. Or a method in which the temperature is raised linearly from room temperature to 400 DEG C over 2 hours.

The heat-resistant resin film formed from the photosensitive resin composition of the present invention is suitably used for applications such as passivation films for semiconductors, protective films for semiconductor devices, interlayer insulating films for high-density mounting multilayer wiring, and insulating layers for organic electroluminescent devices.

Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. First, evaluation methods in the respective examples and comparative examples will be described. In the evaluation of the photosensitive resin composition (hereinafter referred to as varnish), a varnish filtered through a filter made of polytetrafluoroethylene (manufactured by Sumitomo Heavy Industries, Ltd.) of 1 mu m in advance was used.

(1) Measurement of the content of the (C) compound in the photosensitive resin composition (varnish)

0.03 g of the component (A) polymerized with the compound (C) and 0.01 g of methyl 3-nitrobenzoate as an internal standard substance were dissolved in deuterated dimethylsulfoxide (0.7 g) and NMR (GX- 270). Based on the peak area near 3.9 ppm derived from 3-nitrobenzoate, the amount of the compound (C) containing the component (A) was determined from each peak area.

(2) calculation of the total content of the compound (C) in the cured film

Varnish was applied on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus Mark-7 (manufactured by Tokyo Electron Co., Ltd.), and baking was performed with a hot plate at 120 캜 for 3 minutes to form a film having a thickness of 3.2 탆 Prebake film was produced. Thereafter, development was carried out using 2.38 parts by mass of a tetramethylammonium aqueous solution (hereinafter referred to as 2.38% TMAH, produced by Tamagagaku Kogyo Co., Ltd.) using the Mark-7 developing apparatus, rinsing with distilled water, After drying, the solid film was cured at 200 DEG C for 60 minutes in a nitrogen atmosphere to obtain a cured film.

The film thickness of the obtained cured film was measured, and 1 x 5 cm of the film was cut out, and adsorbed and captured by the purge-and-trap method. Specifically, the cured film thus obtained was heated at 400 DEG C for 60 minutes using helium as a purge gas, and the desorbed components were collected in a suction tube.

The collected components were subjected to thermal desorption in a primary desorption condition at 260 占 폚 for 15 minutes, a secondary desorption desorption condition at -27 占 폚 and 320 占 폚 for 5 minutes, and then a GC-MS apparatus 7890 / 5975C (Agilent GC-MS analysis was carried out under the conditions of column temperature: 40 to 300 占 폚, carrier gas: helium (1.5 ml / min), and scan range: m / (C) compound was subjected to GC-MS analysis under the same conditions as described above to prepare a calibration curve, and the amount of generated gas was calculated.

The obtained value (占 퐂) was divided by an area of 5 cm2, and was set to 占 퐂 / cm2. The value was divided by the specific gravity of the alkali-soluble resin (a) multiplied by the film thickness multiplied by 100, and the total content of the compound (c) in the cured film was calculated.

(3) Method of measuring film thickness

After pre-baking, the pre-baked film was measured with a refractive index of 1.629, and the cured film was measured with a refractive index of 1.773, based on polyimide, using Lambda Ace STM-602 manufactured by Dainippon Screen Seisak Co.,

(4) Adhesion test

The adhesion test with a metal material was carried out in the following manner.

≪ Preparation of cured film &

Copper was sputtered on a silicon wafer, and a substrate (copper sputter substrate) having a metal material layer formed to a thickness of 200 nm on each surface was prepared. The varnish was applied on the substrate by a spin coating method using a spinner (MIKASA CO., LTD.), And then baked at 120 ° C for 3 minutes using a hot plate (D-SPIN made by Dainippon Screen- , And finally a prebaked film having a thickness of 8 占 퐉 was produced. The negative type photosensitive resin composition was then exposed to the entire surface of the substrate at an exposure amount of 1000 mJ / cm < 2 > using an exposure machine i-line stepper NSR-2005i9C (Nikon Corporation). These films were heated again at 140 占 폚 for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less) using a clean oven (CLH-21CD-S made by Koyo Thermo System Co., Ltd.) , A photosensitive resin cured film was obtained.

≪ Evaluation of adhesion property &

The substrate was divided into two, and cuts on a checkerboard eye of 10 rows and 10 columns were inserted at intervals of 2 mm on each of the substrates after curing by using one blade. Using one of the sample substrates, the number of peeling of 100 masses by peeling with a cellophane tape was counted, and the adhesion property between the metal material and the resin cured film was evaluated. The other sample substrate was subjected to a PCT treatment for 400 hours at 121 ° C and a saturation condition of 2 atmospheres using a pressure cooker test (PCT) apparatus (HAST CHAMBER EHS-211MD manufactured by Tavai ESPEC Corp.) Then, the above peel test was carried out. A substrate was peeled off in a peeling test to find that the number of substrates was less than 10, A was more than 10, B was less than 20, and C was more than 20.

(5) Evaluation of application property

The varnish was spin coated on a substrate having a step and then baked for 3 minutes by a hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Limited) at 120 캜 to prepare a prebaked film having an average thickness of 10 탆 did. The prebaked film was irradiated with sodium lamp, and the surface was observed with eyes. &Quot;, and " x " Subsequently, the thickness of the film covering the stepped portion of the substrate and the upper portion of the buried portion of the pre-baked film was measured by observing the cross section of the stepped portion of the substrate using a field emission scanning electron microscope (Hitachi High Technologies, S-4800) . The measurement points were divided into 30 parts, except for 10 mm on each side from the outer periphery of the substrate, to 30 positions. The step difference landfillability was calculated by the following equation.

Maximum height = average value of the sum of the height of the step on the substrate and the thickness of the prebaked film covering the top

Film thickness of the buried portion = average value of the film thickness at the center of the buried portion

(%) = [Maximum height / thickness of buried portion] x 100

Here, the step-gap filling property is preferably 90 to 100%, more preferably 95 to 100%. The step-difference landfillability was evaluated as A when 95% or more and 100% or less, and when B was 90 or more but less than 95% was C, when C was less than 90%.

The substrate having the stepped portion used for evaluation was prepared in the following manner. A film of OFPR (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a photoresist was formed on an 8-inch silicon wafer, and a pattern was formed by photolithography. Using this pattern as a mask, an etching apparatus (Sanko RIE-10N ), And the pattern including OFPR was peeled off with acetone to form a step having a depth of 4 탆.

[Synthesis Example 1] Synthesis of diamine compound (HA)

164.8 g (0.45 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) was dissolved in 900 mL of acetone and 156.8 g (2.7 mol) And cooled to -15 ° C. A solution of 183.7 g (0.99 mole) of 3-nitrobenzoyl chloride in 900 ml of acetone was added dropwise thereto. After completion of dropwise addition, the mixture was allowed to react at -15 DEG C for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and vacuum-dried at 50 占 폚.

270 g of a solid was put in a 3 L stainless steel autoclave, dispersed in 2400 mL of methyl cellosolve, and 5 g of 5% palladium-carbon was added. Hydrogen was introduced thereinto as a balloon, and the reduction reaction was carried out at room temperature. After 2 hours, it was confirmed that the balloon was not disturbed further, and the reaction was terminated. After completion of the reaction, the mixture was filtered to remove the palladium compound serving as a catalyst, and then concentrated in a rotary evaporator to obtain a diamine compound represented by the following formula (hereinafter referred to as HA).

[Synthesis Example 2] Synthesis of polyimide resin (A-1)

62.04 g (0.2 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter referred to as ODPA) was dissolved in 1000 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) . (0.06 mole) of BAHF, 12.00 g (0.02 mole) of ED-600 (trade name, manufactured by HUNTSMAN) and 4.37 g (0.04 mole) of 3-aminophenol as a terminal sealing material were added together with 250 g of NMP, Deg.] C for 1 hour, and then reacted at 160 deg. C for 6 hours. After the completion of the reaction, the solution was cooled to room temperature, and then the solution was poured into 10 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 캜 for 40 hours to obtain a polyimide resin (A-1).

[Synthesis Example 3] Synthesis of polyimide resin (A-2)

The synthesis was conducted in the same manner as in Synthesis Example 2 except that the polymerization solvent of Synthesis Example 2 was changed from NMP to 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as DMI) to obtain a polyimide resin (A-2) . As a result of NMR analysis, the content of DMI was 3.0 parts by mass based on 100 parts by mass of the polyimide resin (A-2).

[Synthesis Example 4] Synthesis of polyimide resin (A-3)

The polyimide resin (A-3) was obtained in the same manner as in Synthesis Example 2 except that the polymerization solvent of Synthesis Example 2 was changed from NMP to 3-methoxy-N, N-dimethylpropionamide (hereinafter referred to as the & ≪ / RTI > As a result of NMR analysis, the content of the equamide M100 was 2.8 parts by mass based on 100 parts by mass of the polyimide resin (A-3).

[Synthesis Example 5] Synthesis of polyimide resin (A-4)

A polyimide resin (A-4) was obtained in the same manner as in Synthesis Example 2 except that the polymerization solvent of Synthesis Example 2 was changed from NMP to N, N-dimethylpropylene urea (hereinafter referred to as DMPU). As a result of NMR analysis, the content of DMPU was 3.1 parts by mass based on 100 parts by mass of the polyimide resin (A-4).

[Synthesis Example 6] Synthesis of polyimide resin (A-5)

The polyimide resin (A-5) was synthesized in the same manner as in Synthesis Example 2 except that the polymerization solvent of Synthesis Example 2 was changed from NMP to 3-butoxy-N, N-dimethylpropionamide (hereinafter referred to as " . As a result of NMR analysis, the content of the equamide B100 was 3.2 parts by mass based on 100 parts by mass of the polyimide resin (A-5).

[Synthesis Example 7] Synthesis of polyimide precursor resin (A-6)

In a dry nitrogen stream, 62.04 g (0.2 mole) of ODPA was dissolved in 1000 g of NMP. Then, 96.72 g (0.16 mol) of HA and 4.97 g (0.02 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added together with 100 g of NMP, reacted at 20 ° C for 1 hour, And reacted for 2 hours. Then, 4.37 g (0.04 mol) of 3-aminophenol was added as a terminal sealing agent together with 30 g of NMP, and the mixture was reacted at 50 DEG C for 2 hours. Thereafter, a solution obtained by diluting 47.66 g (0.4 mol) of N, N-dimethylformamide dimethylacetal with 50 g of NMP was added dropwise over 10 minutes. After dropwise addition, the mixture was stirred at 50 DEG C for 3 hours. After the completion of the stirring, the solution was cooled to room temperature, and then the solution was poured into 1 L of water to obtain a precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 DEG C for 20 hours to obtain a powder of the polyimide precursor resin (A-6).

[Synthesis Example 8] Synthesis of polyamide resin (A-7)

(0.18 mol) of dicarboxylic acid diester containing 4,4'-dicarboxy diphenyl ether and 1-hydroxybenzotriazole, 65.93 g (0.18 mol) of BAHF, ED-600 12.0 g (0.02 mol) of NMP (trade name, manufactured by HUNTSMAN CO., LTD.) And 800 g of NMP were reacted at 25 DEG C for 30 minutes, followed by heating in an oil bath and reaction at 80 DEG C for 8 hours. Subsequently, 12.31 g (0.075 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added as a terminal sealing agent, and the mixture was stirred for another 3 hours at 80 ° C to terminate the reaction. After completion of the reaction, the solution was cooled to room temperature, and the reaction mixture was filtered. The reaction mixture was poured into 2 L of a mixed solution of water / isopropanol = 3/1 (volume ratio) to obtain a precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C for 20 hours to obtain a polyamide resin (A-7) (polybenzoxazole precursor).

[Synthesis Example 9] Synthesis of quinone diazide compound (b-2-1)

(0.131 mol) of 5-naphthoquinonediazide sulfonyl chloride (NAC-5, manufactured by TOYO CHEMICAL CO., LTD.) Was added under a dry nitrogen flow to 20 g of TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Was dissolved in 1,4-dioxane (1000 g). While the reaction vessel was ice-cooled, 150 g of 1,4-dioxane and 14.53 g (0.14 mol) of triethylamine were added dropwise to the system so that the temperature was not higher than 35 ° C. After dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into 7 L of pure water to obtain a precipitate. The precipitate was collected by filtration and further washed with 2 L of 1 mass% hydrochloric acid. Thereafter, it was further washed twice with 5 L of pure water. This precipitate was dried in a vacuum dryer at 50 캜 for 24 hours, and a quinone diazide compound (b-2-1) represented by the following formula in which two on average in Q were esterified with 5-naphthoquinonediazide sulfonic acid was obtained.

The names and structures of the compounds shown in Tables 1 to 3 are also shown.

b-1-1: 1,9-nonanediol dimethacrylate

b-1-2: 1,2-Octanedione-1- [4- (phenylthio) phenyl] -2- (o- benzoyloxime) (OXE02)

C-1: Delta valerolactone (boiling point 230 ° C)

C-2: Diethylene glycol butyl ether (boiling point: 230 占 폚)

C-3: 2-phenoxyethanol (boiling point: 245 DEG C),

C-4: 1,3-dimethyl-2-imidazolidinone (boiling point: 220 占 폚)

C-5: 3-Methoxy-N, N-dimethylpropionamide (boiling point: 216 DEG C)

C-6: N, N-dimethylpropylene urea (boiling point 246 캜)

C-7: 3-Butoxy-N, N-dimethylpropionamide (boiling point: 252 캜)

C-8: N-cyclohexyl-2-pyrrolidone (boiling point: 154 DEG C / 7 mmHg, atmospheric pressure boiling point: 305 DEG C)

C-9: N, N-Dimethylformamide (boiling point: 153 캜)

D-1 to D-5:

E-1 and E-2:

F-1: HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), an alkoxymethyl compound having an acid group

[Examples 1 to 53, Comparative Examples 1 to 6]

Hereinafter, the first embodiment will be specifically described. 1.5 g of (B-1-1), 3.0 g of (b-1-2) and 0.30 g of (C-1) as the compound (C-1) were added to 10 g of the obtained resin (A- 20 g of? -Butyrolactone (GBL) was added thereto to prepare a varnish. Likewise, varnishes were prepared according to the compositions of Tables 1 to 3 for Examples 2 to 53 and Comparative Examples 1 to 6. The properties of the prepared varnish were measured by the above evaluation method. The obtained results are shown in Tables 4 to 6. Further, the solvents of Examples 1 to 53 and Comparative Examples 1 to 6 were all 20 g of GBL.

(C) compound was added, the improvement in coatability and adhesion was shown. On the other hand, C-9: N, N-dimethylformamide (boiling point: 153 占 폚) showed no improvement in coatability and adhesion.

Claims (18)

(A) an alkali-soluble resin having an organic group derived from an aliphatic diamine, (B) a photosensitizer, (C) a photosensitive resin composition containing 1013 hPa and a compound which is liquid at 25 DEG C and has a boiling point of 210 DEG C or higher,
(C) 0.1 to 15 parts by mass of a compound which is liquid at 1013 hPa at 25 캜 and has a boiling point of not less than 210 캜, relative to 100 parts by mass of an alkali-soluble resin having an organic group derived from an aliphatic diamine (A) Wherein the photosensitive resin composition is a photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin having an organic group derived from the aliphatic diamine (A) is at least one selected from the group consisting of polyimide, polybenzoxazole, polyamideimide and at least one resin selected from the precursors thereof . The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive agent (B) is a photo-crosslinking agent. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photosensitive agent is a photoacid generator. The liquid crystal display device according to any one of claims 1 to 4, wherein the compound (C) is liquid at 1013 hPa at 25 占 폚 and has a boiling point of 210 占 폚 or higher is a compound represented by the general formula (1) Wherein the photosensitive resin composition is at least one compound selected from the group consisting of:

(In the formulas (1) to (4), R ¹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, R ² represents a divalent organic group having 1 to 5 carbon atoms, R ⁵ represents hydrogen, R ³ , R ⁴ and R ⁶ each independently represent an organic group having 1 to 5 carbon atoms, and n represents an integer within a range of 1 to 3.) The photosensitive resin composition according to any one of claims 1 to 5, further comprising (D) a compound represented by the general formula (5).

(In the general formula (5), R ⁷ to R ^{9 each} represent an oxygen atom, a sulfur atom or a nitrogen atom, and at least one of R ⁷ to R ⁹ represents a sulfur atom. R ⁷ represents an oxygen atom or a sulfur atom when l is 0 and represents a nitrogen atom when l is 1. m and n represent 1 or 2. R ¹⁰ to R ¹² each independently represent hydrogen An atom or an organic group having 1 to 20 carbon atoms. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (E) a compound represented by the general formula (6).

(In the general formula (6), R ¹³ represents a hydrogen atom or an alkyl group having 1 or more carbon atoms, R ¹⁴ represents an alkylene group having 2 or more carbon atoms, R ¹⁵ represents an alkylene group having 2 or more carbon atoms, And k represents an integer of 1 to 4.) A photosensitive resin sheet formed from the photosensitive resin composition according to any one of claims 1 to 7. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 7 or the photosensitive resin sheet according to claim 8. The cured film according to claim 9, wherein said cured film (C) contains 0.005 mass% or more and 5 mass% or less of a compound which is liquid at a temperature of 1013 hPa at 25 캜 and has a boiling point of 210 캜 or more. A process for producing a photosensitive resin composition, comprising the steps of applying the photosensitive resin composition according to any one of claims 1 to 7 on a substrate, laminating the photosensitive resin sheet according to claim 8 on a substrate and drying to form a photosensitive resin film, A step of exposing the photosensitive resin film to light, a step of developing the exposed photosensitive resin film with an alkali solution, and a step of heat-treating the developed photosensitive resin film. The method for producing a relief pattern of a cured film according to claim 11, comprising a step of coating the photosensitive resin composition on a substrate and drying to form a photosensitive resin film on a substrate using a slit nozzle. The organic EL display device according to claim 9 or 10, wherein the cured film is disposed on at least one of a flattening layer on the driving circuit and an insulating layer on the first electrode. 11. A semiconductor electronic component or a semiconductor device, wherein the cured film according to claim 9 or 10 is disposed as an interlayer insulating film between re-wiring lines. 15. The semiconductor electronic device or semiconductor device according to claim 14, wherein the rewiring line is a copper metal wiring, and a width of the copper metal wiring and a distance between adjacent wirings are 5 mu m or less. The semiconductor electronic device or semiconductor device according to claim 9 or 10, wherein the cured film is disposed as an interlayer insulating film between the rewiring lines on the encapsulating resin substrate on which the silicon chips are disposed. A method for manufacturing a semiconductor device, comprising the steps of arranging the cured film according to claim 9 or 10 as an interlayer insulating film between rewiring lines on a supporting substrate on which a mounting material is disposed, placing a silicon chip and a sealing resin thereon, A method for manufacturing a semiconductor electronic device or a semiconductor device, comprising the steps of: peeling a rewiring line and a supporting substrate on which a material is disposed. The semiconductor electronic device or semiconductor device according to claim 9 or 10, wherein the cured film is disposed as an interlayer insulating film of an adjacent substrate composed of two or more materials.