JP2009227697A - Cross-linking agent and photosensitive resin composition using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition exhibiting high sensitivity without respect to a standing time from exposure to post-exposure baking, causing little reduction in film thickness in development, and having excellent chemical resistance after curing, and to provide a thermal cross-linking agent used for the composition. <P>SOLUTION: In the cross-linking agent, a part or the whole of phenolic hydroxy groups in a compound having hydroxymethyl groups and/or alkoxymethyl groups, and the phenolic hydroxy groups is protected by a group separable by a reaction of heat, an acid or a base. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a crosslinking agent and a photosensitive resin composition using the same.

  In order to reduce the mounting area of an LSI (Large Scale Integration) package, a package is formed from a method in which pins are provided outside a package such as a conventional QFP (Quad Flat Package) and this is joined to a substrate. A method in which bumps are formed on the substrate and the package is directly bonded to the substrate has been used. For this reason, it is necessary to form solder bumps or the like when forming a package, and heat resistance and chemical resistance are required for an insulating material such as polyimide used for protecting an LSI chip. In particular, since the solder bump formation is performed at a high temperature using an organic acid called a flux treatment, chemical resistance higher than the conventional one is required.

So far, in order to improve chemical resistance, photosensitive resin compositions containing an alkali-soluble acrylic resin, a quinonediazide compound, and a crosslinking agent such as a melamine compound or an epoxy compound have been proposed (for example, patent documents). 1). Further, there has been proposed a photosensitive resin composition containing an alkali-soluble polyamic acid (or an ester thereof), a quinonediazide compound, and a thermally crosslinkable compound having a methylol group substituted with an organic group (for example, see Patent Document 2). ). In addition, a resin composition containing a phenolic hydroxyl group and a compound having a plurality of hydroxymethyl groups and / or alkoxymethyl groups in the molecule as a thermal crosslinking agent has been proposed (for example, see Patent Document 3). Chemical resistance is further improved by the resin composition containing such a thermal crosslinking agent. However, when these thermal crosslinking agents having a phenolic hydroxyl group are applied to a negative photosensitive resin composition, there is a problem in that the film loss during development increases as the sensitivity decreases, in particular, the standing time from exposure to post-exposure baking increases. was there.
JP 2002-328472 A (page 1-3) JP 2001-281853 A (page 1-2) JP 2007-16214 A (page 1-4)

  The present invention is a photosensitive resin composition having high sensitivity, small reduction in film thickness during development regardless of the standing time from exposure to post-exposure baking, and excellent chemical resistance after curing, and thermal cross-linking used therefor The purpose is to provide an agent.

The present invention is as indicated by 1 or 2 below.
1. A part or all of the phenolic hydroxyl group of a compound having a hydroxymethyl group and / or an alkoxymethyl group and a phenolic hydroxyl group is protected with a group which can be removed by the action of heat, acid or base. A crosslinking agent.
2. A photosensitive resin composition comprising (a) an alkali-soluble resin, (b) the crosslinking agent according to 1 above, (c) a photopolymerizable compound, and (d) a photopolymerization initiator.

  According to the present invention, it is possible to obtain a photosensitive resin composition having high sensitivity, small reduction in film thickness during development, and excellent chemical resistance after curing regardless of the standing time from exposure to post-exposure baking. . The photosensitive resin composition of the present invention can be suitably used for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, a wiring protective insulating film of a circuit board, and the like.

  Hereinafter, the present invention will be described in detail.

<Thermal crosslinking agent>
The crosslinking agent of the present invention is a group in which a part or all of the phenolic hydroxyl group of the compound having a hydroxymethyl group and / or alkoxymethyl group and a phenolic hydroxyl group is removable by the action of heat, acid or base. It is a crosslinking agent protected with When a conventionally known crosslinking agent having a hydroxymethyl group and / or alkoxymethyl group and a phenolic hydroxyl group is used in a negative photosensitive resin composition having a radical polymerizable compound, radicals generated by light irradiation are not generated. It is trapped by the phenolic hydroxyl group in the crosslinking agent and deactivated. For this reason, the sensitivity is lowered, and the film thickness reduction at the time of development is increased as the standing time from exposure to post-exposure baking is extended. In addition, when the content of the crosslinking agent is reduced to avoid this problem, sufficient chemical resistance cannot be obtained. On the other hand, the cross-linking agent of the present invention is a negative type having a radically polymerizable compound because part or all of the phenolic hydroxyl group is protected with a group that can be removed by the action of heat, acid, or base. When used in the photosensitive resin composition, the deactivation due to the radical trap described above is suppressed. Therefore, the photosensitive resin composition containing the cross-linking agent of the present invention can reduce the decrease in film thickness during development with high sensitivity regardless of the standing time from exposure to post-exposure baking. On the other hand, when this protecting group is adjacent to a hydroxymethyl group and / or an alkoxymethyl group, it can be an inhibiting factor of the thermal crosslinking reaction due to steric hindrance, but this protecting group is cured by the action of heat, acid or base. Alternatively, since it is desorbed in the previous step, the thermal crosslinking reaction proceeds sufficiently, and a cured film having excellent chemical resistance can be obtained.

  As the protecting group for the phenolic hydroxyl group, various conventionally known protecting groups can be used, for example, an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, or an alkoxycarbonylmethyl having 2 to 20 carbon atoms. Group, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkyl-substituted silyl group having 1 to 10 carbon atoms, a reaction residue of an enol ether having 3 to 20 carbon atoms and a phenolic hydroxyl group. Preferable examples include an acetyl group, a tetrahydropyranyl group, a tert-butoxycarbonyl group, and a tert-butoxycarbonylmethyl group. These protecting groups can be introduced by a conventionally known method (for example, Experimental Chemistry Course, edited by the Chemical Society of Japan (2005)). For example, when protecting a phenolic hydroxyl group with an acetyl group, it can be obtained by reacting a crosslinking agent having a phenolic hydroxyl group with acetic anhydride in pyridine.

  The protection rate of the phenolic hydroxyl group is preferably 50 mol% or more, more preferably 70 mol% or more. The protection rate can be determined by measuring the NMR of the protected crosslinking agent and calculating the integral ratio between the peak derived from the phenolic hydroxyl group and the peak derived from the other structure. By protecting 50 mol% or more, the photosensitive resin composition by photoradical polymerization has high sensitivity and can reduce the reduction in film thickness during development regardless of the standing time from exposure to post-exposure baking. .

  As the crosslinking agent of the present invention, a compound represented by the following general formula (1) is preferable.

In general formula (1), R ¹ represents a divalent to hexavalent organic group. R ² and R ³ may be the same or different and each represents a hydrogen atom or CH ₂ OR ⁵ (R ⁵ is a hydrogen atom or an organic group having 1 to 6 carbon atoms), and at least one in the molecule is CH ₂ OR ^5. It is. R ⁴ represents a protecting group for a phenolic hydroxyl group. R ⁵ is preferably a hydrogen atom, a methyl group or an ethyl group in terms of crosslinking reactivity, and more preferably a methyl group or an ethyl group in terms of storage stability. a shows the integer of 2-6.

Of the R ² , CH ₂ OR ⁵ is preferably 4 or more, and more preferably 6 or more, in that the crosslink density of the cured film is increased and the chemical resistance is further improved.

  Particularly preferred crosslinking agents represented by the general formula (1) are shown below.

  In the above formula, K may be the same or different and each represents a hydrogen atom, an acetyl group, a tetrahydropyranyl group, a tert-butoxycarbonyl group or a tert-butoxycarbonylmethyl group. However, 50 mol% or more of each compound is an acetyl group, a tetrahydropyranyl group, a tert-butoxycarbonyl group or a tert-butoxycarbonylmethyl group. L represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises (a) an alkali-soluble resin, (b) the crosslinking agent of the present invention, (c) a photopolymerizable compound, and (d) a photopolymerization initiator. To do. Such a photosensitive resin composition can form a negative pattern with high sensitivity regardless of the exposure time from exposure to post-exposure baking, and a small film thickness reduction during development, and also has good chemical resistance after curing. It becomes.

  The (a) alkali-soluble resin used in the present invention has an acidic group in the structural unit of the polymer and / or at the end of the main chain thereof. By having an acidic group in the structural unit and / or at the end of the main chain thereof, it is well dissolved in an alkaline aqueous solution before curing, so that development with an alkaline aqueous solution is possible. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. Preferable examples include resins having a structural unit represented by general formula (2) or general formula (3).

In General Formula (2), R ⁶ and R ⁷ represent a 2 to 6-valent organic group having 2 to 30 carbon atoms. A and B may be the same or different and each represents OR ⁸ , SO ₃ R ⁸ , CONR ⁸ R ⁹ , COOR ⁸ or SO ₂ NR ⁸ R ⁹ . R ⁸ and R ⁹ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. m and p show the integer of 0-4. However, m + p> 0.

In General Formula (3), R ¹⁰ represents a C 4-30 tetravalent organic group. R ¹¹ represents a divalent to hexavalent organic group having 2 to 30 carbon atoms. E and F may be the same or different and each represents OR ¹² , SO ₃ R ¹² , CONR ¹² R ¹³ , COOR ¹² or SO ₂ NR ¹² R ¹³ . R ¹² and R ¹³ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. X and Z represent CO, N, NH, O or S, and Y represents C or N. The bond between Z and Y is a single bond or a double bond. r and s are integers of 0 to 4, and q is an integer of 0 to 2. However, r + s> 0.

  The resin having the structural unit represented by the general formula (2) has an amide bond in the main chain. For example, polyamic acid or polyamic acid ester that is a polyimide precursor, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, etc. that are polybenzoxazole precursors can be mentioned, but other than these, the structure of the general formula (2) Any unit having a unit may be used. Among these, from the viewpoint of alkali developability, polyamic acid, polyamic acid ester, polyhydroxyamide and the like are preferably used. More preferred are polyamic acid and polyamic acid ester. In these resins, an imide ring is sufficiently formed even in low-temperature baking at 280 ° C. or lower, so that chemical resistance in low-temperature baking is further improved.

  Moreover, it can replace with the structural unit represented by General formula (2), or can use resin which has a structural unit represented by General formula (3) in combination. Examples of the resin having the structural unit represented by the general formula (3) include resins having a cyclic structure such as an imide ring, an oxazole ring, an imidazole ring, and a thiazole ring in the main chain structure. Specific examples include polyimide, polybenzoxazole, polybenzimidazole, and polybenzthiazole.

  Each of the structural units represented by the general formula (2) or (3) may be used alone, or a plurality of structural units may be mixed or copolymerized. The resin of component (a) in the present invention preferably has 10 to 100,000 structural units represented by the general formula (2) or (3).

  The polyimide preferably used in the present invention can be obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride and the like with diamine, corresponding diisocyanate compound, and trimethylsilylated diamine. Polyimide can be generally obtained by dehydrating and ring-closing polyamic acid, which is one of polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, by heating or chemical treatment such as acid or base. . In the present invention, not only polyamic acid and polyimide can be used, but also other polyimide precursors such as polyamic acid ester, polyamic acid amide, and polyisoimide can be used.

  The polybenzoxazole preferably used in the present invention can be obtained by reacting bisaminophenol with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester and the like. In general, polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting bisaminophenol compounds with dicarboxylic acids, is subjected to dehydration and ring closure by heating or chemical treatment of phosphoric anhydride, base, carbodiimide compounds, etc. Obtainable.

  Polybenzothiazole can be obtained by reacting bisaminothiophenol with dicarboxylic acid, the corresponding dicarboxylic acid chloride, dicarboxylic acid active ester and the like. In general, polythiohydroxyamide, which is one of the polybenzothiazole precursors obtained by reacting bisaminothiophenol compounds with dicarboxylic acids, is subjected to dehydration and ring closure by heating or chemical treatment of phosphoric anhydride, base, carbodiimide compounds, etc. Can be obtained.

  Polybenzimidazole can be obtained by reacting tetraamine with dicarboxylic acid, the corresponding dicarboxylic acid chloride, dicarboxylic acid active ester and the like. Generally, polyaminoamide, which is one of the polybenzimidazole precursors obtained by reacting bisaminophenol compounds with dicarboxylic acids, is obtained by dehydration and cyclization by heating or chemical treatment of phosphoric anhydride, base, carbodiimide compounds, etc. be able to.

R ^{6 in the} general formula (2) represents a divalent to hexavalent organic group having 2 to 30 carbon atoms, and preferably has an aromatic ring and / or an aliphatic ring.

As the acid component constituting —CO—R ⁶ (A) _m —CO— of the general formula (2), examples of dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, Examples of tricarboxylic acids such as biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. Examples of tetracarboxylic acids include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′- Benzophenone tetracarboxylic acid, 2,2 ', 3,3'-benzophenone tet Carboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-di Carboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4 -Dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5 , 6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid and other aromatic tetracarboxylic acids, butanetetracarboxylic acid, And aliphatic tetracarboxylic acids such as 3,4-cyclopentanetetracarboxylic acid. Among these, in tricarboxylic acid and tetracarboxylic acid, one or two carboxyl groups correspond to the A group in the general formula (2). In addition, 1 to 4 dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids exemplified above are substituted with the A group in the general formula (2), preferably a hydroxyl group, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group, or the like. It is more preferable to use what was done. These acids can be used alone or in combination of two or more as an acid anhydride and an active ester.

R ^{7 in the} general formula (2) represents a divalent to hexavalent organic group having 2 to 30 carbon atoms, and preferably has an aromatic ring and / or an aliphatic ring.

Examples of the diamine component constituting —NH—R ⁷ (B) _p —NH— in the general formula (2) include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4) -Hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino Hydroxyl group-containing diamines such as -4-hydroxy) biphenyl and bis (3-amino-4-hydroxyphenyl) fluorene, carboxyl groups such as 3,5-diaminobenzoic acid and 3-carboxy-4,4′-diaminodiphenyl ether Containing sulfonic acid such as diamine, 3-sulfonic acid-4,4′-diaminodiphenyl ether Diamine, dithiohydroxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4, 4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylene Diamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- ( 4-aminophenoxy) fe Nil} ether, 1,4-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'-di (trifluoromethyl) -4,4'-diaminobiphenyl, or an aromatic group with an alkyl group or halogen Mention may be made of compounds substituted with atoms. Moreover, you may use aliphatic cyclohexyl diamine, a methylene bis cyclohexyl amine, etc. 0-50 mol% of all the diamine components. Furthermore, these diamines are monovalent groups having 1 to 10 carbon atoms such as a methyl group and an ethyl group, fluoroalkyl groups having 1 to 10 carbon atoms such as a trifluoromethyl group, groups such as F, Cl, Br, and I. May be substituted. These diamines can be used alone or in combination of two or more as diamines or as corresponding diisocyanate compounds and trimethylsilylated diamines. 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 total diamine.

In the general formula (2), A and B represent OR ⁸ , SO ₃ R ⁸ , CONR ⁸ R ⁹ , COOR ⁸ or SO ₂ NR ⁸ R ⁹ . R ⁸ and R ⁹ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Particularly preferred as A and B is a hydroxyl group.

In the present invention, the resin represented by the general formula (3) represents a resin having a cyclic structure such as polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole. R ^{10 in the} general formula (3) represents a tetravalent to octavalent organic group having 2 to 30 carbon atoms, and preferably has 1 to 2 aromatic rings. Preferable examples of R ^{10 in} the general formula (3) include the following structures, or a part of them: an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, a cyano group, Examples include a structure in which 1 to 4 atoms are substituted with a fluorine atom or a chlorine atom.

R ^{11 in the} general formula (3) represents a divalent to hexavalent organic group having 2 to 30 carbon atoms, and preferably has 1 to 4 aromatic rings. Preferable examples of R ^11- (F) _s of the general formula (3) include the following structures, or a part of them: an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, nitro And a structure in which 1 to 4 groups are substituted with a group, a cyano group, a fluorine atom or a chlorine atom.

In the above formula, J represents a direct bond, —COO—, —CONH—, —CH ₂ —, —C ₂ H ₄ —, —O—, —C ₃ H ₆ —, —SO ₂ —, —S—, — _{Si (CH 3) 2 -,} - O-Si (CH 3) 2 -O -, - C 6 H 4 -, - C 6 H 4 -O-C 6 H 4 -, - C 6 H 4 -C 3 H ₆ -C ₆ H ₄ - or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - shows a.

In the general formula (3), E and F represent OR ¹² , SO ₃ R ¹² , CONR ¹² R ¹³ , COOR ¹² or SO ₂ NR ¹² R ¹³ . R ¹² and R ¹³ represent hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Among these, E and F are preferably a hydroxyl group, a carboxyl group, an ester group, a sulfonic acid group, a sulfonic acid amide group, or a sulfonic acid ester group.

  X and Z in the general formula (3) represent CO, N, NH, O or S. Y is N or C, and when Y is C, one bond of XY or YZ becomes a double bond. q represents an integer of 0 to 2, and q = 0 is particularly preferable.

  In addition, by sealing the end of these resins with a monoamine having a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group and a thiol group, the dissolution rate of the resin in an alkaline aqueous solution is adjusted to a preferred range. can do. Preferred examples of such monoamines include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy- 4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4- Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosa Tyric acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned. Two or more of these monoamines may be combined.

  Further, by sealing the end of the resin with an acid anhydride, acid chloride, or monocarboxylic acid, the dissolution rate with respect to the alkaline aqueous solution can be adjusted to a preferred range. Preferred examples of such acid anhydrides, acid chlorides, and monocarboxylic acids include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic acid anhydride. -Carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1- Monocarboxylic acids such as mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and their carboxyl groups Monochlorinated monoacid chloride compounds and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6- A monoacid chloride compound in which only a monocarboxyl group of a dicarboxylic acid such as dicarboxynaphthalene is acid chloride, a monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide The active ester compound obtained by reaction is mentioned. Two or more of these may be used.

  The content of the end-capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid described above is preferably 2 to 25 mol% when the total of the acid and amine components constituting the resin is 100 mol%. .

The end-capping agent introduced into the resin can be easily detected by the following method. For example, by dissolving a resin into which an end-capping agent has been introduced in an acidic solution and decomposing it into an amine component and an acid anhydride component, which are constituent units of the resin, this is measured by gas chromatography (GC) or NMR measurement. The end capping agent can be easily detected. Apart from this, it is possible to detect the resin into which the end-capping agent has been introduced by directly measuring by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ C-NMR spectrum.

  (B) The crosslinking agent of the present invention in the photosensitive resin composition of the present invention may be used in combination of two or more. The content of the (b) crosslinking agent is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, preferably 100 parts by weight or less, more preferably 60 parts by weight based on 100 parts by weight of the resin of the component (a). Less than parts by weight. (B) By setting the content of the crosslinking agent to 10 parts by weight or more, chemical resistance after curing is further improved, and by setting the content to 100 parts by weight or less, a tough cured film can be obtained.

  The photopolymerizable compound (c) in the photosensitive resin composition of the present invention has an unsaturated bond in the molecule. Examples of the unsaturated bond include unsaturated double bonds such as vinyl group, allyl group, acryloyl group, and methacryloyl group, and / or unsaturated triple bonds such as propargyl group. Among these, a conjugated vinyl group, an acryloyl group, and a methacryloyl group are preferable in terms of polymerizability. Further, the number of functional groups contained is preferably 1 to 6 from the viewpoint of stability, and may not be the same group.

  Preferred examples of such polymerizable compounds include, for example, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2, 2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl Chlorate, 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-vinyl pyrrolidone, N-vinyl caprolactam are mentioned. Two or more of these may be included.

  (C) The content of the photopolymerizable compound is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, preferably 200 parts by weight or less, based on 100 parts by weight of the resin of component (a). The amount is preferably 150 parts by weight or less. By setting the content to 3 parts by weight or more, elution of the exposed part during development can be prevented, and by setting the content to 200 parts by weight or less, whitening of the film during film formation can be suppressed.

  Examples of the photopolymerization initiator (d) in the photosensitive resin composition of the present invention include benzophenone, Michler's ketone, 4,4, -bis (diethylamino) benzophenone, 3,3,4,4, -tetra (t-butyl). Benzophenones such as peroxycarbonyl) benzophenone and benzylidenes such as 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone and 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 7-diethylamino-3-thenonylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylmethylbenzimidazolyl) coumarin, 3- (2-Benzothiazolyl) -7-diethyla Coumarins such as nocoumarin, anthraquinones such as 2-t-butylanthraquinone, 2-ethylanthraquinone and 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, ethylene glycol di (3 -Mercaptopropionate), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, mercapto such as 2-mercaptobenzimidazole, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- Glycines such as (p-chlorophenyl) glycine and N- (4-cyanophenyl) glycine, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propyl Pandione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) ) Oxime, bis (α-isonitrosopropiophenone oxime) isophthal, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), OXE01 (trade name, Ciba Specialty) Chemicals Co., Ltd.), OXE02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) and other oximes, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-2 Α-amino such as methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one Rukirufenon acids, 2,2'-bis (o-chlorophenyl) 4,4', 5,5'-tetraphenyl biimidazole, and the like. Of these, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (α-iso Nitrosopropiophenone oxime) isophthal, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), OXE01 and OXE02 are preferred. Two or more of these may be included.

  (D) The content of the photopolymerization initiator is usually preferably 0.1 to 40 parts by weight per one type with respect to 100 parts by weight of the resin of the component (a). 2 to 60 parts by weight is preferable. Furthermore, a sensitizer can also be contained as needed.

  Furthermore, it contains surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane as necessary. May be. By containing these, the wettability of the photosensitive resin composition and the substrate can be improved. Moreover, inorganic particles, such as silicon dioxide and titanium dioxide, can also be contained.

  Moreover, you may contain 0.5 to 10weight% of silane coupling agents, such as methylmethacryloxy dimethoxysilane and 3-aminopropyl trimethoxysilane, a titanium chelating agent, an aluminum chelating agent, etc. in the photosensitive resin composition. By containing these, adhesiveness with base substrates, such as a silicon wafer, can be improved.

  The photosensitive resin composition of the present invention is generally used in a state where the components (a) to (d) are dissolved or dispersed in an organic solvent. As the organic solvent, those having a boiling point of 80 ° C. to 250 ° C. under atmospheric pressure are preferably used.

  Specific examples of the organic solvent preferably used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Ethers such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, lactic acid Acetates such as butyl, acetylacetone, methyl propyl ketone, methyl butyl Ketones such as ruketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3- Alcohols such as methoxybutanol and diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethyl Examples include acetamide, dimethyl sulfoxide, and γ-butyrolactone. Two or more of these may be used.

  Among these, those that dissolve the component (a) and have a boiling point of 120 ° C. to 200 ° C. under atmospheric pressure are particularly preferable. If the boiling point is within this range, volatilization at the time of coating the composition is suppressed, and the heat treatment temperature of the composition does not have to be increased, so that the material of the base substrate is not restricted. Further, by using a solvent that dissolves the component (a), a uniform coating film can be formed on the base substrate. Specific examples of preferable organic solvents having such boiling point include cyclopentanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, methyl lactate, ethyl lactate, diacetone alcohol, 3-methyl- 3-methoxybutanol is mentioned.

  Further, the content of the organic solvent in the photosensitive resin composition of the present invention is preferably 20 parts by weight or more, particularly preferably 30 parts by weight or more, preferably 100 parts by weight or more of the resin of component (a), preferably 800 parts by weight or less, particularly preferably 500 parts by weight or less.

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

  A photosensitive resin composition is applied onto a substrate. A silicon wafer, ceramics, gallium arsenide, or the like is used as the substrate, but is not limited thereto. Alternatively, the substrate can be pretreated with a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, a titanium chelating agent, an aluminum chelating agent, or the like. For example, a solution obtained by dissolving 0.5 to 20% by weight of the coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate Is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. Depending on the case, reaction of a board | substrate and the said coupling agent can also be advanced by applying the temperature to 50 to 300 degreeC after that.

  Examples of the method for applying the photosensitive resin composition include spin coating using a spinner, spray coating, and roll coating. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity and the like, but it is usually applied so that the film thickness after drying becomes 1 to 150 μm.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 to 150 ° C. for 1 minute to several hours.

  Next, the photosensitive resin composition film is exposed to actinic radiation through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp are preferable.

  Next, post-exposure baking is performed. The baking temperature is preferably in the range of 50 to 180 ° C, more preferably in the range of 60 to 150 ° C. The time is not particularly limited, but is preferably 10 seconds to several hours from the viewpoint of subsequent developability.

  In order to form the pattern of the photosensitive resin composition, after exposure, an unexposed portion is removed using a developer. As the developer, for example, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide or the like alone or methanol , Ethanol, isopropyl alcohol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2 -Used in combination with organic solvents such as heptanone, ethyl acetate, tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate Potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, may be used an aqueous solution of a compound showing alkalinity, such as hexamethylenediamine. In particular, an aqueous solution of tetramethylammonium, an aqueous solution of an alkaline compound such as diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or triethylamine is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good. After development, rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, the film is heated at 120 to 400 ° C. to form a heat resistant resin composition film. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, a method of performing heat treatment at 130 ° C., 200 ° C., and 300 ° C. for 30 minutes each, or linearly raising the temperature from room temperature to 300 ° C. over 2 hours may be mentioned.

  The heat resistant resin film formed by the photosensitive resin composition of the present invention is used for a passivation film of a semiconductor element, a protective film of a semiconductor element, an interlayer insulating film of a multilayer wiring for high-density mounting, a wiring protective insulating film of a circuit board, etc. Can be suitably used. Further, a display device including a first electrode formed on a substrate and a second electrode provided to face the first electrode, specifically, for example, a liquid crystal display, an organic EL display, an electrochromic display, It can be used for an insulating layer of a display device (organic electroluminescent device) using an organic electroluminescent element.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In addition, evaluation of the photosensitive resin composition in an Example was performed with the following method.

Preparation of photosensitive resin composition film A 6-inch silicon wafer was coated with a photosensitive resin composition (hereinafter referred to as varnish) so that the film thickness after pre-baking was 10 μm, and then hot plate (Tokyo Electron Limited). A photosensitive resin composition film was obtained by prebaking at 100 ° C. for 3 minutes using Mark-7).

Measuring method of film thickness Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the refractive index was measured at 1.63.

Exposure A reticle with a pattern cut is set in an exposure machine (full wavelength stepper Spectrum 3e manufactured by Ultratech Co., Ltd.), and the exposure dose is 500 mJ / cm ² (i-line conversion) with respect to the photosensitive resin composition film. At all wavelengths.

Post-exposure baking The exposed photosensitive resin composition film was heat-treated at 100 ° C. for 1 minute using a hot plate (Mark-7, manufactured by Tokyo Electron Ltd.).

Development A 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed for 10 seconds at 50 rotations using a Mark-7 developing device manufactured by Tokyo Electron Co., Ltd., on the photosensitive resin composition film baked after exposure. Thereafter, the film was allowed to stand for 80 seconds at 0 rotation, then rinsed with water at 400 rotations, shaken and dried for 10 seconds at 3000 rotations, and a film after development was obtained.

Heat treatment (cure)
The developed film was heat-treated at 280 ° C. for 60 minutes under a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven INH-21CD (manufactured by Koyo Thermo System Co., Ltd.).

Measurement of remaining film ratio The remaining film ratio was calculated according to the following formula.
Residual film ratio (%) = film thickness after development / film thickness after pre-baking × 100.

Evaluation of decrease in film thickness by exposure time between exposure and post-exposure baking For the varnishes described in each Example and Comparative Example, three samples of the photosensitive resin composition film were prepared by the above method, and the exposure amount was 500 mJ / cm ² . After the exposure, the film was allowed to stand for 0 minutes, 15 minutes, and 60 minutes, and then subjected to post-exposure baking and development, and the remaining film ratio was measured. When the value of the remaining film ratio for 60 minutes was left to satisfy the condition of 80% or more, it was accepted, and when it did not, it was rejected.

As 60 minutes standing time until post exposure bake the evaluation exposure sensitivity, exposure exposure amount in the range of 40-1200mJ / cm ² at 40 mJ / cm ² increments to calculate the residual film rate after development, the residual film The exposure amount when the rate becomes constant was defined as the minimum exposure amount.

Evaluation of chemical resistance The exposure amount is 500 mJ / cm ² , the standing time from exposure to post-exposure baking is 0 minutes, and other conditions are 40 using a release liquid 106 manufactured by Tokyo Ohka Kogyo Co., Ltd. An immersion treatment was performed at 10 ° C. for 10 minutes, and the film thickness before and after the treatment was measured to determine the amount of film thickness reduction.

Synthesis Example 1 Synthesis of Hydroxyl Group-Containing Diamine Compound (I) Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) 18.3 g (0.05 mol) in 100 mL acetone It was dissolved in 17.4 g (0.3 mol) of propylene oxide and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white powder was filtered off and dried in vacuum at 50 ° C.

  30 g of the powder was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound (I) represented by the following formula.

Synthesis Example 2 Synthesis of Crosslinker (II) 4,4 ′, 4 ″ -Ethylidentris [2,6- (methoxymethyl) phenol] (Homshu Chemical Industries, Ltd., HMOM-TPHAP) in 20% ethyl lactate The solution was concentrated with an evaporator to obtain a 40% ethyl lactate solution, which was allowed to stand at room temperature for 5 days to obtain a light orange solid, which was washed with n-hexane and then dried with a vacuum dryer. Using high performance liquid chromatography manufactured by Seisakusho Co., Ltd., ODS was used as a column, acetonitrile / water = 90/10 was used as a developing solvent, and analysis was carried out at 254 nm. The purity of the obtained HMOM-TPHAP was 95%. The structure is shown below.

Synthesis Example 3 Synthesis of Crosslinking Agent (III) 11,4 g (0.4 mol) of 4,4′-1-phenylethylidenebisphenol (Honshu Chemical Industry Co., Ltd., BisP-AP) was added to 80 g of sodium hydroxide (2 0.0 mol) was dissolved in a solution of 800 g of pure water. After complete dissolution, 686 g of 36-38% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Thereafter, the mixture was stirred at 20 to 25 ° C. for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and allowed to stand for 2 days. Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. The white crystals were vacuum dried at 50 ° C. for 48 hours. This was analyzed by Shimadzu Corporation high performance liquid chromatography at 254 nm using ODS as the column and acetonitrile / water = 90/10 as the developing solvent. The starting material disappeared completely and the purity was 90%. It turned out that. Furthermore, when analyzed by NMR (GX-270 manufactured by JEOL Ltd.) using DMSO-d6 as a heavy solvent, it was found to be tetramethylolated BisP-AP.

  Next, the compound thus obtained was dissolved in 300 mL of methanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. To this solution, 15 g of an anionic ion exchange resin (Rumm and Haas, Amberlyst IRA96SB) was added and stirred for 1 hour, and the ion exchange resin was removed by filtration. Thereafter, 500 mL of ethyl lactate was added, and methanol was removed by a rotary evaporator to obtain an ethyl lactate solution. When this solution was allowed to stand at room temperature for 2 days, white crystals were formed. When the obtained white crystal was examined by a liquid chromatography method, it was a 98% pure BisP-AP tetramethoxymethylol compound. Its structure is shown below.

Synthesis Example 4 Synthesis of Cross-linking Agent (IV) 11.41 g (0.02 mol) of the cross-linking agent (II) powder obtained in Synthesis Example 2 and 50 g of pyridine were placed in an eggplant flask and dissolved at room temperature. Then 6.73 g (0.066 mol) of acetic anhydride was added dropwise. Thereafter, the mixture was stirred at 0 ° C. for 8 hours and then poured into 500 ml of pure water. The precipitated white powder was collected by filtration and further washed with 500 g of pure water three times. This precipitate was dried with a vacuum dryer. When the obtained compound was analyzed by NMR (GX-270 manufactured by JEOL Ltd.) using DMSO-d6 as a heavy solvent, the compound was found to have the following structure, and the protection rate of the phenolic hydroxyl group was 100. %Met. The NMR measurement results are shown in Table 1. In addition, the code | symbol ae in the following structural formula respond | corresponds to the attribution ae in Table 1.

Synthesis Example 5 Synthesis of Crosslinking Agent (V) Powdered 11.41 g (0.02 mol) of crosslinking agent (II) obtained in Synthesis Example 2 and 50 g of pyridine were placed in an eggplant flask and dissolved at room temperature. Then 4.59 g (0.045 mol) of acetic anhydride was added dropwise. Thereafter, the mixture was stirred at 0 ° C. for 8 hours and then poured into 500 ml of pure water. The precipitated white powder was collected by filtration and further washed with 500 g of pure water three times. This precipitate was dried with a vacuum dryer. When the obtained compound was analyzed by NMR (GX-270 manufactured by JEOL Ltd.) using DMSO-d6 as a heavy solvent, the peak derived from 8.38 ppm of phenolic hydroxyl group was reduced, and 2.28 ppm of A proton peak derived from an acetyl group was confirmed. The protection ratio of the phenolic hydroxyl group calculated from the integration ratio was 73%.

Synthesis Example 6 Synthesis of Cross-linking Agent (VI) 11.41 g (0.02 mol) of the cross-linking agent (II) powder obtained in Synthesis Example 2 and 50 g of pyridine were placed in an eggplant flask and dissolved at room temperature. Then, 3.57 g (0.035 mol) of acetic anhydride was added dropwise. Thereafter, the mixture was stirred at 0 ° C. for 8 hours and then poured into 500 ml of pure water, whereby a pale yellow liquid was obtained. This liquid was further washed three times with 500 g of pure water and then dissolved in acetone. Anhydrous magnesium sulfate was added thereto for dehydration, followed by filtration. Acetone was removed from the filtrate by a rotary evaporator. When the obtained compound was analyzed by NMR (GX-270 manufactured by JEOL Ltd.) using DMSO-d6 as a heavy solvent, the peak derived from 8.38 ppm of phenolic hydroxyl group was reduced, and 2.28 ppm of A proton peak derived from an acetyl group was confirmed. The protection ratio of the phenolic hydroxyl group calculated from the integration ratio was 59%.

Synthesis Example 7 Synthesis of Crosslinking Agent (VII) 11.41 g (0.02 mol) of the crosslinking agent (II) powder obtained in Synthesis Example 2 and 50 g of pyridine were placed in an eggplant flask and dissolved at room temperature. Then 2.65 g (0.026 mol) of acetic anhydride was added dropwise. Thereafter, the mixture was stirred at 0 ° C. for 8 hours and then poured into 500 ml of pure water, whereby a pale yellow liquid was obtained. This liquid was further washed three times with 500 g of pure water and then dissolved in acetone. Anhydrous magnesium sulfate was added thereto for dehydration, followed by filtration. Acetone was removed from the filtrate by a rotary evaporator. When analyzed by NMR (GX-270 manufactured by JEOL Ltd.) using DMSO-d6 as a heavy solvent, the peak derived from 8.38 ppm phenolic hydroxyl group decreased, and the proton derived from 2.28 ppm acetyl group decreased. A peak was confirmed. The protection ratio of phenolic hydroxyl group calculated from the integration ratio was 46%.

Synthesis Example 8 Synthesis of Cross-linking Agent (VIII) 7.81 g (0.02 mol) of cross-linking agent (IV) obtained in Synthesis Example 4 and 50 g of pyridine were dissolved in an eggplant flask and acetic anhydride at 0 ° C. 4.49 g (0.044 mol) was added dropwise. Thereafter, the mixture was stirred at 0 ° C. for 8 hours and then poured into 500 ml of pure water. The precipitated white powder was collected by filtration and further washed with 500 g of pure water three times. This precipitate was dried with a vacuum dryer. When the obtained compound was analyzed by NMR (GX-270 manufactured by JEOL Ltd.) using DMSO-d6 as a heavy solvent, the compound was found to have the following structure, and the protection rate of the phenolic hydroxyl group was 100. %Met. The NMR measurement results are shown in Table 2. In addition, the code | symbol ah in the following structural formula respond | corresponds to the attribution ah in Table 2.

Example 1
Under a dry nitrogen stream, BAHF 29.3 g (0.08 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1.24 g (0.005 mol), and 3-aminophenol as an end-capping agent 3.27 g (0.03 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 150 g of N-methyl-2-pyrrolidone (NMP). Bis (3,4-dicarboxyphenyl) ether dianhydride (manac Co., Ltd., ODPA) 31.0 g (0.1 mol) was added together with NMP 50 g, and the mixture was stirred at 20 ° C. for 1 hour, and then 50 Stir at 4 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried for 24 hours in a vacuum dryer at 80 ° C. to obtain a polyimide powder.

  Next, 10 g of this polyimide powder was weighed, and 3.0 g of the crosslinking agent (IV) obtained in Synthesis Example 4 was used as a crosslinking agent, and PDBE-250 (trade name, manufactured by NOF Corporation) as a photopolymerizable compound. ) 6.0 g, OXE-02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.0 g as a photopolymerization initiator was added to 20 g of diacetone alcohol to dissolve varnish A of the photosensitive resin composition. Obtained. Using the obtained varnish A, a photosensitive resin composition film is prepared on a silicon wafer as described above, and the film thickness is determined by exposure, post-exposure baking, development, and heat treatment, and the standing time from exposure to post-exposure baking. Reduction, sensitivity, and chemical resistance were evaluated.

Example 2
Varnish B of the photosensitive resin composition was obtained in the same manner as in Example 1 except that the amount of the crosslinking agent (IV) added was 2.0 g. Using the obtained varnish B, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking in the same manner as in Example 1.

Example 3
Varnish C of the photosensitive resin composition was obtained in the same manner as in Example 1 except that the amount of the crosslinking agent (IV) added was 1.4 g. Using the obtained varnish C, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Example 4
Varnish D of the photosensitive resin composition was obtained in the same manner as in Example 1 except that the amount of the crosslinking agent (IV) added was 0.9 g. Using the obtained varnish D, the film thickness reduction, sensitivity, and chemical resistance were evaluated in the same manner as in Example 1 depending on the standing time from exposure to post-exposure baking.

Example 5
Varnish E of the photosensitive resin composition was obtained in the same manner as in Example 1 except that the crosslinking agent (V) obtained in Synthesis Example 5 was used in place of the crosslinking agent (IV). Using the obtained varnish E, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Example 6
Varnish F of the photosensitive resin composition was obtained in the same manner as in Example 1 except that the crosslinking agent (VI) obtained in Synthesis Example 6 was used instead of the crosslinking agent (IV). Using the obtained varnish F, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Example 7
A varnish G of the photosensitive resin composition was obtained in the same manner as in Example 1 except that the crosslinking agent (VII) obtained in Synthesis Example 7 was used instead of the crosslinking agent (IV). Using the obtained varnish G, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Example 8
A varnish H of a photosensitive resin composition was obtained in the same manner as in Example 1 except that the crosslinking agent (VIII) obtained in Synthesis Example 8 was used instead of the crosslinking agent (IV). Using the obtained varnish H, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking in the same manner as in Example 1.

Example 9
Under a dry nitrogen stream, 48.4 g (0.08 mol) of the hydroxyl group-containing diamine compound (II) obtained in Synthesis Example 1 and 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0 0.005 mol), 3.27 g (0.03 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 150 g of NMP as a terminal blocking agent. ODPA 31.0g (0.1mol) was added here with NMP50g, and it stirred at 40 degreeC for 3 hours. Thereafter, a solution obtained by diluting 5.19 g (0.127 mol) of N, N-dimethylformamide dimethylacetal with 4 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a polyamic acid powder.

  Next, 10 g of this polyamic acid powder was weighed, 3.0 g of the crosslinking agent (IV) obtained in Synthesis Example 4 was used as a crosslinking agent, 6.0 g of PDBE-250 as a photopolymerizable compound, and a photopolymerization initiator. A varnish I of a photosensitive resin composition was obtained by dissolving 2.0 g of OXE-02 in 20 g of γ-butyrolactone. Using the obtained varnish I, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking in the same manner as in Example 1.

Example 10
Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to −15 ° C. A solution prepared by dissolving 14.7 g of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd., 0.050 mol) in 25 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the solution was poured into 3 L of water containing 10% by weight of methanol to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyhydroxyamide powder.

  Next, a varnish J of a photosensitive resin composition was obtained in the same manner as in Example 9 except that 10 g of polyhydroxyamide was used as a polymer instead of polyamic acid. Using the obtained varnish J, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Comparative Example 1
Varnish K of the photosensitive resin composition was obtained in the same manner as in Example 1 except that no crosslinking agent was added. Using the obtained varnish K, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking in the same manner as in Example 1.

Comparative Example 2
A varnish L of the photosensitive resin composition was obtained in the same manner as in Example 1 except that the crosslinking agent (II) obtained in Synthesis Example 2 was used in place of the crosslinking agent (IV) as the crosslinking agent. Using the obtained varnish L, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Comparative Example 3
A varnish M of a photosensitive resin composition was obtained in the same manner as in Example 1 except that the crosslinking agent (III) obtained in Synthesis Example 3 was used instead of the crosslinking agent (IV) as the crosslinking agent. Using the obtained varnish M, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

  The compositions and evaluation results of Examples 1 to 10 and Comparative Examples 1 to 3 are shown in Tables 3 to 4 below.

Claims (4)

A part or all of the phenolic hydroxyl group of a compound having a hydroxymethyl group and / or an alkoxymethyl group and a phenolic hydroxyl group is protected with a group which can be removed by the action of heat, acid or base. A crosslinking agent. The cross-linking agent according to claim 1, which is represented by the following general formula (1).

(In the general formula (1), R ¹ represents a divalent to hexavalent organic group. R ² and R ³ may be the same or different and are each a hydrogen atom or CH ₂ OR ⁵ (R ⁵ is a hydrogen atom or And at least one in the molecule is CH ₂ OR ^5. R ⁴ represents a protecting group for a phenolic hydroxyl group, and a represents an integer of 2 to 6.) A photosensitive resin composition comprising (a) an alkali-soluble resin, (b) the crosslinking agent according to claim 1, (c) a photopolymerizable compound, and (d) a photopolymerization initiator. The photosensitive resin composition according to claim 3, wherein the (a) alkali-soluble resin has a structural unit represented by the following general formula (2) or general formula (3).

(In General Formula (2), R ⁶ and R ⁷ represent a 2 to 6-valent organic group having 2 to 30 carbon atoms. A and B may be the same or different, and OR ⁸ , SO ₃ R ⁸ , CONR ⁸ R ⁹ , COOR ⁸ or SO ₂ NR ⁸ R ⁹ , R ⁸ and R ⁹ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and m and p are 0 to 4 Represents an integer, where m + p> 0.)

(In General Formula (3), R ¹⁰ represents a C 4-30 tetravalent organic group. R ¹¹ represents a C 2-30 bivalent organic group. E and F are Each may be the same or different and each represents OR ¹² , SO ₃ R ¹² , CONR ¹² R ¹³ , COOR ¹² or SO ₂ NR ¹² R ¹³ , wherein R ¹² and R ¹³ are each a hydrogen atom or a C 1-20 one; X and Z each represents CO, N, NH, O or S, and Y represents C or N. The bond between Z and Y is a single bond or a double bond. And s represents an integer of 0 to 4, and q represents an integer of 0 to 2, provided that r + s> 0.