JP2010229210A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition capable of obtaining a cured film excellent in mechanical properties even on firing at a low temperature of not higher than 200°C. <P>SOLUTION: The resin composition includes (a) a polyimide having an alkoxymethyl group or a methylol group, a polybenzoxazole, a polyamide-imide, a precursor thereof or a copolymer thereof and (b) a compound having at least two alkoxymethyl groups or methylol groups. The resin composition further contains (c) a thermal acid generator. Further incorporation of (d) a photoacid generator enables the formation of a positive-type or negative-type pattern or incorporation of (e) a compound having an unsaturated bond and (f) a photoinitiator enables the formation of a negative-type pattern. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  Conventionally, polyimide-based resins, polybenzoxazole-based resins, and polyamide-imide-based resins that are excellent in heat resistance, mechanical properties, and the like have been widely used for surface protective films and interlayer insulating films of semiconductor elements of electronic devices. When a thin film excellent in heat resistance and mechanical properties is obtained by thermally dehydrating and closing a coating film of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor, high-temperature baking at around 350 ° C. is usually required. However, for example, MRAM (Magnetic Resistive Random Access Memory), which is promising as a next generation memory, is vulnerable to high-temperature processes. Therefore, even in the surface protective film, it is about 250 ° C. or less, more preferably 200 ° C. or less. There is a need for polyimide resins, polybenzoxazole resins, and polyamideimide resins that can be cured by firing and can provide performances comparable to those fired at a high temperature of around 350 ° C.

  As a low-temperature curable resin composition, a resin composition containing 100 parts by weight of a resin such as polyimide, polybenzoxazole, polybenzimidazole, or polybenzothiazole and 10 to 100 parts by weight of a thermal crosslinking agent (for example, Patent Document 1) And a positive photosensitive polyamideimide resin composition containing an alkali-soluble polyamideimide, a photoacid generator, a solvent and a crosslinking agent (see, for example, Patent Document 2). By using a closed ring type resin instead of a precursor for these resin compositions, it was excellent in chemical resistance even at low temperature firing, and it was possible to suppress thermal shrinkage during curing. However, since these resin compositions are limited to closed ring type resins, compositions having a high degree of freedom in resin design have been demanded.

  On the other hand, as a resin composition from which a thin film having excellent mechanical properties can be obtained even at low-temperature firing, a photosensitive composition containing an alkali-soluble resin, a photoacid generator, and a compound capable of crosslinking with an end group of the alkali-soluble resin by the action of an acid Resin compositions (for example, see Patent Documents 3 to 4) have been proposed. However, this method has a problem that the mechanical properties are remarkably lowered due to insufficient curing of the film, particularly when firing at a low temperature of 200 ° C. or lower.

JP 2007-16214 A (page 1-4) JP 2007-240554 A (page 1-3) JP 2007-256525 A (page 1-2) JP 2008-33158 A (page 1-3)

  An object of this invention is to provide the resin composition which can obtain the cured film excellent in the mechanical characteristic also at the time of low temperature baking of 200 degrees C or less.

  In order to solve the above problems, the resin composition of the present invention has the following constitution. That is, (a) polyimide having an alkoxymethyl group or methylol group, polybenzoxazole, polyamideimide, a precursor or copolymer thereof, and (b) having at least two alkoxymethyl groups or methylol groups It is a resin composition containing a compound.

  With the resin composition of the present invention, a cured film having excellent mechanical strength can be obtained by low-temperature baking at 200 ° C. or lower.

  The resin composition of the present invention comprises (a) polyimide having an alkoxymethyl group or methylol group, polybenzoxazole, polyamideimide, a precursor or copolymer thereof, and (b) an alkoxymethyl group or methylol. Contains compounds having at least two groups. Alkoxymethyl groups and methylol groups cause a reaction with active ortho / para positions on the benzene ring contained in the phenol skeleton and the like, and a self-condensation reaction between the same functional groups even at a low temperature firing of 200 ° C. or less, and Crosslink. In the case of reducing the firing temperature from a commonly performed firing process of 300 ° C. or higher, there is a problem that the mechanical strength of the cured film is significantly reduced due to a reduction in crosslinking efficiency. In the present invention, (a) Since both the component and the component (b) have an alkoxymethyl group or a methylol group, the crosslinking reaction proceeds efficiently even at a low-temperature firing of 200 ° C. or lower, so that a cured film having excellent mechanical properties can be obtained. .

  The component (a) used in the present invention is polyimide, polybenzoxazole, polyamideimide, any precursor thereof or a copolymer thereof, and has an alkoxymethyl group or a methylol group. Hereinafter, the alkoxymethyl group and the methylol group are collectively referred to as “methylol group”. The component (a) may have two or more methylol groups and may have two or more methylol groups. Moreover, the resin composition of this invention may contain 2 or more types of (a) component, and may contain 2 or more types of (a) component which has a different methylol type | system | group group.

The methylol group is represented by the following general formula (1). However, in the following general formula (1), R ¹ represents a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, and may be linear or branched.

  The methylol group is preferably covalently bonded to a carbocyclic and / or heterocyclic aromatic ring or a nitrogen atom from the viewpoint of crosslinking reactivity. Hereinafter, a group in which a nitrogen atom and a methylol group are covalently bonded is referred to as an “N-methylol group”.

The N-methylol group is preferably represented by the following general formula. However, in the following general formula (2), R ¹ represents a hydrogen atom or an alkyl group, and R ² represents a hydrogen atom, a hydroxyl group or an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, and may be linear or branched. p represents an integer of 1 to 2, q represents an integer of 0 to 1, and p + q = 2.

  The component (a) used in the present invention is polyimide, polybenzoxazole, polyamideimide, any precursor thereof, or a copolymer thereof.

  Examples of the polyimide precursor preferably used in the present invention include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide. For example, polyamic acid 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. The polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid obtained by the above method by heating or chemical treatment such as acid or base.

  Examples of the polybenzoxazole precursor preferably used in the present invention include polyhydroxyamide. For example, polyhydroxyamide can be obtained by reacting bisaminophenol with dicarboxylic acid, corresponding dicarboxylic acid chloride, dicarboxylic acid active ester, and the like. Polybenzoxazole can be obtained, for example, by dehydrating and ring-closing the polyhydroxyamide obtained by the above method by heating or chemical treatment of phosphoric anhydride, base, carbodiimide compound or the like.

  The polyamideimide precursor preferably used in the present invention can be obtained, for example, by reacting diamine or diisocyanate with tricarboxylic acid, corresponding tricarboxylic acid anhydride, tricarboxylic acid anhydride halide or the like. Polyamideimide can be obtained, for example, by subjecting the precursor obtained by the above method to dehydration and ring closure by heating or chemical treatment such as acid or base.

  The component (a) used in the present invention preferably has a structural unit represented by any one of the general formulas (3) to (6). Two or more kinds of resins having these structural units may be contained, or two or more kinds of structural units may be copolymerized. The resin of component (a) in the present invention preferably has 3 to 1000 structural units represented by any one of the general formulas (3) to (6).

In General Formulas (3) to (6), R ³ and R ⁶ are tetravalent organic groups, R ⁴ , R ⁵ and R ⁸ are divalent organic groups, R ⁷ is a trivalent organic group, and R ⁹ is A divalent to tetravalent organic group, R ¹⁰ represents a divalent to divalent organic group. R ^{3 to} R ¹⁰ each preferably has an aromatic ring and / or an aliphatic ring. R ¹¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. r represents an integer of 0 to 2, and s represents an integer of 0 to 10.

In the general formulas (3) to (6), R ³ is a tetracarboxylic acid derivative residue, R ⁵ is a dicarboxylic acid derivative residue, R ⁷ is a tricarboxylic acid derivative residue, R ⁹ is di-, tri- or tetra- Represents a carboxylic acid derivative residue. Examples of the acid component constituting R ³ , R ⁵ , R ⁷ , and R ⁹ include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, and benzophenone dicarboxylic acid. Examples of tricarboxylic acids such as acid and triphenyldicarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyltricarboxylic acid, and tetracarboxylic acid as pyromellitic acid, 3,3 ′, 4,4′- Biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,2 ′, 3,3′-benzophenonetetracarboxylic acid, 2 2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) 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-pyridinetetra Aromatic tetracarboxylic acids such as carboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, butanetetracarboxylic acid, 1,2,3,4-cyclo Examples thereof include aliphatic tetracarboxylic acids such as pentanetetracarboxylic acid. In addition, 1 to 10, preferably 1 to 4 hydrogen atoms of the dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid exemplified above were substituted with a methylol group, a hydroxyl group, an alkoxyl group, a sulfonic acid group, or a thiol group. Things can be mentioned. Among these, in the general formula (6), one or two carboxyl groups of tricarboxylic acid and tetracarboxylic acid each correspond to a COOR ¹¹ group. These acid components can be used as they are or as acid anhydrides, active esters and the like. These two or more acid components may be used in combination.

In general formulas (3) to (6), R ⁴ , R ⁶ , R ⁸ and R ¹⁰ represent diamine derivative residues. Examples of the diamine component constituting R ⁴ , R ⁶ , R ⁸ , R ¹⁰ (OH) _s 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-4-) Hydroxyl) biphenyl, hydroxyl group-containing diamines such as bis (3-amino-4-hydroxyphenyl) fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4′-diaminodiphenyl ether, and thiol groups such as dimercaptophenylenediamine Containing diamine, 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 ' -Diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxy) Phenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} 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′-bis (trifluoro Methyl) -4,4'-diaminobiphenyl and other aromatic diamines, and some of these aromatic ring hydrogen atoms are methylol-based groups, alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc. And alicyclic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine. These diamines can be used as they are or as the corresponding diisocyanate compounds and trimethylsilylated diamines. Moreover, you may use combining these 2 or more types of diamine components. 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.

R ^{3 to} R ¹⁰ in the general formulas (3) to (6) can include a methylol group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and the like in the skeleton. Among these, having a methylol group is preferable because crosslinking efficiency in low-temperature firing at 200 ° C. or lower is further improved. On the other hand, a phenolic hydroxyl group, a sulfonic acid group or a thiol group is preferred from the viewpoint of alkali solubility. A resin composition containing a resin having a phenolic hydroxyl group, a sulfonic acid group or a thiol group in an appropriate amount has alkali solubility and is suitably used as a positive or negative photosensitive resin composition.

  When using the resin composition of this invention as an alkali-soluble photosensitive resin composition, it is preferable to have a fluorine atom in a structural unit. The fluorine atom imparts water repellency to the surface of the film during alkali development, and soaking in from the surface can be suppressed. The fluorine atom content in the component (a) is preferably 10% by weight or more in order to sufficiently obtain the effect of preventing the penetration of the interface, and is preferably 20% by weight or less from the viewpoint of solubility in an aqueous alkali solution.

In addition, an aliphatic group having a siloxane structure may be copolymerized with R ⁴ , R ^8, or R ¹⁰ as long as the heat resistance is not lowered, and the adhesion to the substrate can be improved. Specific examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.

  In addition, in order to improve the storage stability of the resin composition, the resin as the component (a) has an end-capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound at the main chain terminal. It is preferable to seal with. The introduction ratio of the monoamine used as the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50, based on the total amine component. It is less than mol%. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the end-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol%, relative to the diamine component. Or more, preferably 100 mol% or less, particularly preferably 90 mol% or less. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

  Monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 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-amino Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-amino Benzoic acid, 3-aminobenzoic acid, -Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxy Pyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be used.

  Acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc., as acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds Product, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene Monocarboxylic acids such as 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like; Mono-acid chloride compounds in which the carboxyl group is converted to acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene , Monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as 2,6-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3 -Active ester compounds obtained by reaction with dicarboximide are preferred. Two or more of these may be used.

  Moreover, a methylol group can be introduce | transduced into the resin terminal by sealing with the terminal blocker which has a methylol group. In the present invention, it is preferable to introduce the methylol group of the component (a) as a terminal group from the viewpoint of ease of terminal group introduction and high degree of design freedom.

  The structure of the end-capping agent having a methylol group is not particularly limited, but from the viewpoint of crosslinking reactivity of the methylol group, a methylol group, an N-methylolated amino group or a carbocyclic or heterocyclic aromatic ring is added. It preferably contains a structure in which an N-alkoxymethylated amino group is covalently bonded, an N-methylolated amide structure, an N-alkoxymethylated amide structure, an N-methylolated urea structure, or an N-alkoxymethylated urea structure. Among these, particularly preferred are aminobenzyl alcohol, methoxymethylaniline, bis (hydroxymethyl) aniline, bis (methoxymethyl) aniline, and (N, N-bis) as monoamines, including positional isomers on the aromatic ring. (Hydroxymethyl) amino) aniline, (N, N-bis (methoxymethyl) amino) aniline, as acid anhydride, hydroxymethyl phthalic anhydride, methoxymethyl phthalic anhydride, bis (hydroxymethyl) phthalic anhydride, bis ( Methoxymethyl) phthalic anhydride, (N, N-bis (hydroxymethyl) amino) phthalic anhydride, (N, N-bis (methoxymethyl) amino) phthalic anhydride and a part of hydrogen atoms of these aromatic rings C1-C4 alkyl group, fluoroalkyl group, hydroxyl group, C1-C4 alkyl It includes those substituted with such a hexyl group, but is not limited thereto.

  When a methylol group is introduced as a terminal group, two or more methylol groups can be introduced at one terminal by using a polyfunctional methylol group-containing terminal blocker. By having a plurality of these groups at the terminal, the crosslinking reaction proceeds efficiently even at low temperature baking of 200 ° C. or lower, and a cured film having more excellent mechanical properties can be obtained.

  In the present invention, the method for introducing a methylol group into the component (a) is not limited. For example, as described above, a method of polymerizing using a monomer having a methylol group as an acid component, a diamine component, or an end-capping agent, a method of introducing a methylol group by reacting a resin with formaldehyde under acidic or basic conditions And a method of reacting a resin with some methylol group after controlling the reaction with a compound having two or more methylol groups.

Moreover, the terminal blocker introduce | transduced into resin of (a) component can be easily detected with the following method. For example, a resin having a terminal blocking agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component as structural units, and this is measured by gas chromatography (GC) or NMR measurement. The end-capping agent used in the present invention can be easily detected. Apart from this, the resin component into which the end-capping agent has been introduced can also be easily detected by directly measuring it with a pyrolysis gas chromatograph (PGC), infrared spectrum and ¹³ C-NMR spectrum.

  In the resin having the structural unit represented by any one of the general formulas (3) to (5), the number of repeating structural units is preferably 3 or more and 200 or less. In the resin having the structural unit represented by the general formula (6), the number of repeating structural units is preferably 10 or more and 1000 or less. If it is this range, a thick film can be formed easily.

  The component (a) used in the present invention may consist only of the structural unit represented by any one of the general formulas (3) to (6), or may be a copolymer with another structural unit or A mixture may be sufficient. At that time, the structural unit represented by any one of the general formulas (3) to (6) is preferably contained in an amount of 10% by weight or more, more preferably 30% by weight or more based on the whole resin. The type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the mechanical properties of the thin film obtained by the final heat treatment. Examples of such a main chain skeleton include benzimidazole and benzothiazole.

  The component (a) used in the present invention preferably contains 1 to 4 mol of phenolic hydroxyl group in 1 kg of (a). By setting the amount of phenolic hydroxyl group within this range, it is possible to efficiently cause a crosslinking reaction with the methylol group contained in the resin and the crosslinkable compound of the component (b), thereby further improving the mechanical properties of the cured film. . In addition, by improving the solvent solubility of the resin, it is possible to suppress the precipitation and gelation of the resin during the polymerization reaction, to improve the storage stability of the resin composition, and to be suitable for alkali solubility when used as a photosensitive resin composition. Can be. More preferably, it is 1.5-3 mol / kg. The introduction site of the phenolic hydroxyl group may be a side chain or a terminal, but is preferably contained at least in the side chain, and the number of introductions is 0.00 per structural unit represented by any one of the general formulas (3) to (6). 5 or more is preferable.

The amount of phenolic hydroxyl group in component (a) can be determined by calculation from the molecular weight of each monomer and the number of phenolic hydroxyl groups and the theoretically generated polymer structure when the monomer composition at the time of polymerization is known. It can also be determined by measurement in the following manner. The resin of component (a) is dissolved in a suitable heavy solvent such as dimethyl sulfoxide-d ₆ and ¹ H-NMR measurement is performed. A peak derived from a phenolic hydroxyl group can be identified by adding a small amount of a base such as triethylamine. The amount of the phenolic hydroxyl group can be determined, for example, from an integration ratio with a peak derived from an aromatic ring or an appropriate internal standard peak.

  The resin composition of the present invention contains (b) a compound having at least two alkoxymethyl groups or methylol groups. By having at least two of these methylol groups, it is possible to obtain a crosslinked structure by condensation reaction with the resin and the same kind of molecule. In the resin composition of the present invention, by using the component (a) and the component (b), the crosslinking reaction efficiently proceeds even at a low temperature baking of 200 ° C. or lower, and a cured film having excellent mechanical properties can be obtained. .

  Preferred examples of such a compound include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML- PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM- MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM- BPA, TMOM-BPAF, TM M-BPAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), “NIKALAC (registered trademark)” MX-290, “NIKACALAC” MX- 280, "NIKACALAC" MX-270, "NIKACALAC" MX-279, "NIKACALAC" MW-100LM, "NIKACALAC" MX-750LM (trade name, manufactured by Sanwa Chemical Co., Ltd.). Two or more of these may be contained. These structures are shown below.

  The content of the compound (b) having at least two methylol-based groups is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, more preferably 100 parts by weight of the resin of the component (a). 30 parts by weight or more, preferably 300 parts by weight or less, more preferably 200 parts by weight or less. By setting the content of the component (b) within this range, sufficient crosslinking proceeds even at a low temperature, and the mechanical properties of the cured film are further improved.

  The resin composition of the present invention preferably contains (c) a thermal acid generator. (C) The thermal acid generator generates an acid by heating, promotes the crosslinking reaction of the resin of component (a) and the methylol-based group contained in component (b), and forms an unclosed imide ring or oxazole ring. Cyclization can be promoted and the mechanical properties of the cured film can be further improved.

  (C) The thermal decomposition starting temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 200 ° C. or less. Moreover, when using the resin composition of this invention as a photosensitive resin composition, an acid is not generated at the time of drying (prebaking: about 70-140 degreeC) after apply | coating a resin composition to a board | substrate, and exposure after that. It is preferable to select one that generates an acid at the time of final heating (cure: about 100 to 400 ° C.) after patterning by development, because a reduction in sensitivity at the time of development can be suppressed.

  The acid generated from the component (c) is preferably a strong acid. For example, arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, and trifluoromethyl. Haloalkyl sulfonic acids such as sulfonic acid are preferred. These are used as salts such as onium salts or as covalently bonded compounds such as imidosulfonates. Two or more of these may be contained.

  (C) The content of the thermal acid generator is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and 0.5 parts by weight or more with respect to 100 parts by weight of the resin (a). Further preferred. By containing 0.01 part by weight or more, the cross-linking reaction and the cyclization of the unclosed structure of the resin are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from a viewpoint of the electrical insulation of a cured film, 20 weight part or less is preferable, 15 weight part or less is more preferable, and 10 weight part or less is more preferable.

  The resin composition of the present invention may further contain (d) a photoacid generator. (D) By containing a photoacid generator, a positive or negative pattern can be formed. Since an acid is generated in the ultraviolet-exposed area and the solubility of the exposed area in an alkaline aqueous solution is increased, it is particularly preferably used as a positive photosensitive resin composition.

  Examples of the (d) photoacid generator used in the present invention include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among these, a quinonediazide compound is preferably used because it exhibits an excellent dissolution inhibiting effect and a photosensitive resin composition having high sensitivity and low film thickness can be obtained. Moreover, you may contain 2 or more types of photo-acid generators. Thereby, the ratio of the dissolution rate of an exposed part and an unexposed part can be enlarged more, and a highly sensitive photosensitive resin composition can be obtained.

  As quinonediazide compounds, quinonediazide sulfonic acid is bonded to a polyhydroxy compound with an ester, quinonediazide sulfonic acid is bonded to a polyamino compound with a sulfonamide bond, and a quinonediazide sulfonic acid is bonded to a polyhydroxypolyamino compound with an ester bond and / or sulfone. Examples include amide-bonded ones. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.

  In the present invention, the quinonediazide compound is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. A compound having both of these groups in the same molecule may be used, or a compound using different groups may be used in combination.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine can be mentioned. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  (D) Content of a photo-acid generator becomes like this. Preferably it is 3-40 weight part with respect to 100 weight part of resin of (a) component. By setting the content of the photoacid generator within this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.

  The resin composition of the present invention may further contain (e) a polymerizable compound having an unsaturated bond and (f) a photopolymerization initiator. (E) By containing a polymerizable compound having an unsaturated bond and (f) a photopolymerization initiator, the exposed portion is insolubilized in an alkali or organic developer by ultraviolet exposure and subsequent heat treatment. Pattern formation is possible.

  (E) In a polymerizable compound having an unsaturated bond, examples of the group containing an unsaturated bond include unsaturated double bond functional groups such as vinyl, allyl, acryloyl, and methacryloyl groups, and propargyl groups. Saturated triple bond functional groups are mentioned. You may have 2 or more types of these. Among these, a conjugated vinyl group, an acryloyl group, and a methacryloyl group are preferable in terms of polymerizability. Moreover, it is preferable to have 1-4 groups which have these unsaturated bonds in a molecule | numerator from a stability point.

  (E) Examples of the polymerizable compound having an unsaturated bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and trimethylol. Propanediacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate Hexyl acrylate, isooctyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-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 and the like.

  (E) The content of the polymerizable compound having an unsaturated bond is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the resin (a), and 5 to 150 parts by weight from the viewpoint of compatibility. More preferred.

  (F) Examples of the photopolymerization initiator include benzophenones such as benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone. , Benzylidenes such as 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone and 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 7-diethylamino-3-thenonyl Coumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylmethylbenzimidazolyl) coumarin, 3- (2-benzothiazolyl)- Coumarins such as 7-diethylaminocoumarin, -Anthraquinones such as t-butylanthraquinone, 2-ethylanthraquinone, 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, ethylene glycol bis (3-mercaptopropionate), Mercaptos such as 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p-chlorophenyl) glycine, N -Glycines such as-(4-cyanophenyl) glycine, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-me Xylcarbonyl) 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), OXE02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), etc. Oximes, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Α-aminoalkylphenones such as 1-one, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′- Such as tigers biimidazole and the like. Two or more of these may be contained.

  (F) The content of the photopolymerization initiator is preferably 0.1 to 40 parts by weight per 100 parts by weight of the resin (a). When combining 2 or more types, the total amount is preferably 0.2 to 60 parts by weight.

  The resin composition of the present invention may contain a resin having a phenolic hydroxyl group such as novolak or polyhydroxystyrene as long as the heat resistance and chemical resistance are not lowered. By containing these resins, the sensitivity can be improved.

  The novolac resin can be obtained by polycondensing phenols with aldehydes such as formalin by a known method.

  Examples of phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3 , 4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylene Bisphenol, methylenebis (p-cresol), resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butyl Alkoxy phenol, o- ethylphenol, m- ethylphenol, p- ethylphenol, 2,3-diethyl phenol, 2,5-diethyl phenol, p- isopropylphenol, alpha-naphthol, such as β- naphthol. Two or more of these may be used.

  Examples of aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like. Two or more of these may be used.

  Examples of the polyhydroxystyrene resin include vinylphenol homopolymers and copolymers with styrene.

  The preferable weight average molecular weight of these resins is 2000 to 50000 in terms of polystyrene by GPC (gel permeation chromatography), more preferably 3000 to 40000.

  The content of the novolak resin and / or polyhydroxystyrene resin is preferably 1 to 1000 parts by weight with respect to 100 parts by weight of the resin (a).

  Moreover, you may contain the low molecular compound which has a phenolic hydroxyl group in the range which does not make the shrinkage | contraction residual film ratio after hardening small as needed. Thereby, the development time can be shortened.

  As these compounds, for example, Bis-Z, BisP-EZ, TekP-4HBPA (tetrakis P-DO-BPA), TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP- IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC , BIR-PC, BIR-PTBP, BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.) and the like. Two or more of these may be contained.

  The content of the low molecular weight compound having a phenolic hydroxyl group is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the resin (a).

  The resin composition of the present invention preferably contains a solvent. As the solvent, polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, Ethers such as propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, etc. Esters, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene Etc., and the like. Two or more of these may be contained. As for content of a solvent, 100-1500 weight part is preferable with respect to 100 weight part of resin of (a) component.

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

  The resin composition of the present invention is a surfactant, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl isobutyl ketone for the purpose of improving the wettability with the substrate as necessary. And the like, and ethers such as tetrahydrofuran and dioxane.

  Moreover, the resin composition of the present invention may contain inorganic particles. Preferred specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, talc and the like. The primary particle diameter of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

  In addition, in order to enhance the adhesion to the substrate, the resin composition of the present invention includes, as a silicon component, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropyl as long as storage stability is not impaired. A silane coupling agent such as silane may be contained. A preferable content is 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin of component (a).

  Next, although the manufacturing method of the resin composition of this invention is demonstrated with an example, it is not limited to the following methods.

  The component (a) is dissolved in an organic solvent with stirring, or the resin solution obtained by polymerization reaction to obtain the component (a) is used as it is, and the component (b) is mixed with the resin solution at a predetermined ratio. Make a uniform solution. If necessary, other additives are mixed at an appropriate stage of the production process. When the additive is inorganic particles, a dispersion is obtained by using a stirring or dispersing machine. It is preferable to filter the resin composition thus obtained with a filter having a pore size of about 0.2 to 5 μm.

  Next, although the method of forming a pattern is demonstrated as a processing example of the resin composition of this invention, the processing example and use of this invention are not limited by this. First, a resin composition is applied on a substrate. As the substrate, a wafer made of silicon, ceramics, gallium arsenide or the like, or a substrate on which an electrode and / or wiring made of a metal material such as copper, gold, or titanium-based metal is used is used. It is not limited. Examples of the coating method 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 is usually applied so that the film thickness after drying becomes 0.1 to 150 μm.

  Next, the substrate coated with the resin composition is dried to obtain a resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours. If necessary, drying can be performed in two or more stages, such as heating at 80 ° C. for 2 minutes and then heating at 120 ° C. for 2 minutes.

  When photosensitivity is not given to the resin composition, a photoresist chemical solution is further applied thereon. Examples of the coating method 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 is usually applied so that the film thickness after drying becomes 0.1 to 150 μm.

  Next, the substrate coated with the photoresist is dried to obtain a two-layer coating of the photoresist and the resin of the present invention. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours. If necessary, drying can be performed in two or more stages, such as heating at 80 ° C. for 2 minutes and then heating at 120 ° C. for 2 minutes.

  Next, the two-layer coating is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. .

  In the case where photosensitivity is imparted to the resin composition, exposure can be performed by directly irradiating actinic radiation through a mask having a desired pattern without applying a photoresist.

  If photosensitivity is imparted to the resin composition, a bake process may be incorporated before development if the resolution of the pattern during development is improved or the allowable range of development conditions increases. Absent. As this temperature, the range of 50-180 degreeC is preferable, and the range of 60-150 degreeC is more preferable. The time is preferably 10 seconds to several hours. Within this range, there are advantages that the reaction proceeds satisfactorily and the development time can be shortened.

  In order to form a resin pattern, after exposure, an exposed portion is removed in the case of a positive type and a non-exposed portion is removed in the case of a negative type using a developer. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like 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, Add one or a combination of two or more alcohols such as isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone. May be. After development, it is common to 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 the development, a temperature of 100 ° C. to 400 ° C. is applied to promote the crosslinking reaction between the component (a) and the component (b). 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, heat treatment is performed at 130 ° C., 200 ° C., and 300 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 300 ° C. over 2 hours can be mentioned. The baking temperature in the present invention is preferably 150 ° C. or higher and 350 ° C. or lower. However, since the present invention provides a cured film particularly excellent in low-temperature curability, 180 ° C. or higher and 250 ° C. or lower is more preferable.

  The film formed from the resin composition of the present invention is suitably used for applications such as a semiconductor passivation film, a protective film for semiconductor elements, an interlayer insulating film for multilayer wiring for high-density mounting, and an insulating layer for organic electroluminescent elements. As an electronic device having a surface protective film, an interlayer insulating film and the like obtained by using the resin composition of the present invention, for example, MRAM having low heat resistance is preferable. That is, the resin composition of the present invention is suitable for a surface protective film of MRAM. In addition to MRAM, polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase RAM: PCRAM, or Ovonics Unified Memory: OUM), which are promising as next-generation memories, have lower heat resistance than conventional memories. There is a high possibility of using new materials. Therefore, the resin composition of the present invention is also suitable for these surface protective films. In addition, a display device including a first electrode formed on a substrate and a second electrode provided to face the first electrode, specifically, for example, an LCD, an ECD, an ELD, an organic electroluminescent element It can be used for an insulating layer of the display device (organic electroluminescence device) used. In particular, with recent miniaturization of electrodes, multilayer wiring, and circuit board wiring of semiconductor elements, copper electrodes and copper wiring have become mainstream, and the heat resistant resin formed by the resin composition of the present invention. When the coating film is used as a protective film for such an electrode or wiring, it is particularly preferably used because a pattern can be formed with high sensitivity without corroding the underlying copper electrode or copper wiring.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by these examples. First, a method for evaluating the mechanical properties of the cured film in each example and comparative example is described.

  The resin composition filtered through a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) on a 6-inch silicon wafer so that the film thickness after pre-baking at 120 ° C. for 3 minutes is 10 μm. After coating and pre-baking with a coating and developing apparatus Mark-7 (manufactured by Tokyo Electron Co., Ltd.) by a spin coating method, oxygen concentration using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) The temperature was raised to 200 ° C. at 3.5 ° C./min at 20 ppm or less, and heat treatment was performed at 200 ° C. for 1 hour. When the temperature became 50 ° C. or lower, the wafer was taken out and immersed in 45% by weight of hydrofluoric acid for 5 minutes to peel off the resin composition film from the wafer. This film was cut into strips having a width of 1 cm and a length of 9 cm, and using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) at a room temperature of 23.0 ° C. and a humidity of 45.0% RH, a tensile rate of 50 mm / The sample was pulled in minutes and the elongation at break was measured. The measurement was performed on 10 strips per specimen, and the average value of the top 5 points was obtained from the results. When the value of the elongation at break satisfies the condition of 10% or more, it was judged as acceptable, and when it did not satisfy it, it was judged as unacceptable.

  The amount of phenolic hydroxyl group in the resin of component (a) was determined by calculation from the molecular weight of each monomer, the number of phenolic hydroxyl groups, and the theoretically generated polymer structure.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) was added to 100 mL of acetone and 17 of propylene oxide. It was dissolved in 0.4 g (0.3 mol) 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 solid was filtered off and vacuum dried at 50 ° C.

  30 g of the solid 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 catalyst was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

Synthesis Example 2 Synthesis of quinonediazide compound Under a dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl chloride (NAC-5, Toyosei Co., Ltd.) 26.86 g (0.10 mol) (manufactured by Co., Ltd.) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration, and further washed with 1 L of 1 wt% hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound represented by the following formula in which two of Q on average were converted into 5-naphthoquinonediazidesulfonic acid ester.

  The compounds (b) having at least two alkoxymethyl groups or methylol groups used in Examples and Comparative Examples are shown below.

  The (c) thermal acid generator PAG-103 (pyrolysis start temperature 155 ° C .; differential scanning calorimetry) used in the examples is shown below.

  The polymerizable compound (e) having an unsaturated bond used in the examples is shown below.

  The photopolymerization initiator (f) used in the examples is shown below.

Example 1
Under a dry nitrogen stream, 29.30 g (0.08 mol) of BAHF and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were mixed with N-methyl-2-pyrrolidone (hereinafter referred to as NMP). This was dissolved in 120 g. Bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter referred to as ODPA, Manac Co., Ltd.) (21.72 g, 0.07 mol) was added together with NMP (10 g) and reacted at 20 ° C. for 1 hour. Then, the reaction was carried out at 50 ° 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. Thereafter, the mixture was cooled to 50 ° C. over 1 hour, 9.31 g (0.03 mol) of ODPA was added together with 10 g of NMP, stirred at 50 ° C. for 1 hour, and further 3.69 g of 4-aminobenzyl alcohol (end-capping agent) 0.03 mol) was added together with 5 g of NMP and stirred at 50 ° C. for 1 hour. After completion of the stirring, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried for 20 hours in a vacuum dryer at 80 ° C., and a polyimide resin having a methylol group at the end (A-1, phenolic hydroxyl group amount 2.6 mol / kg). ) Was obtained.

  1 g of NIKALAX MX-270 as component (b) and 10 g of γ-butyrolactone (hereinafter referred to as GBL) as a solvent were added to 5 g of the obtained resin (A-1), and a resin composition (hereinafter referred to as varnish) (W— 1) was prepared, and mechanical properties were evaluated by the above method.

Example 2
5 g of NIKALAC MX-270 as the component (b) and 17 g of GBL as the solvent were added to 5 g of the resin (A-1) obtained in Example 1 to prepare a varnish (W-2). Was evaluated.

Example 3
Under a dry nitrogen stream, 1.47 g (0.004 mol) of BAHF and 0.25 g (0.001 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 80 g of NMP. To this, 4.34 g (0.014 mol) of ODPA was added together with 10 g of NMP and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, 10 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. Thereafter, the mixture was cooled to 50 ° C. over 1 hour, 1.86 g (0.006 mol) of ODPA was added together with 10 g of NMP, and the mixture was stirred at 50 ° C. for 1 hour, and further 0.74 g of 4-aminobenzyl alcohol as a terminal blocking agent ( 0.006 mol) was added together with 5 g of NMP and stirred at 50 ° C. for 1 hour. After completion of the stirring, the solution was cooled to room temperature and then poured into 1 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 20 hours in a vacuum dryer at 80 ° C., and a polyimide resin having a methylol group at the end (A-2, phenolic hydroxyl group content 0.8 mol / kg). ) Was obtained.

  1 g of NIKALAX MX-270 as component (b) and 10 g of GBL as solvent are added to 5 g of the obtained resin (A-2) to prepare varnish (W-3), and mechanical properties are evaluated by the above method. It was.

Example 4
0.1 g of NIKALAC MX-270 as the component (b) and 1 PAG-103 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) as the thermal acid generator were added to 5 g of the resin (A-1) obtained in Example 1. 25 g and 10 g of GBL as a solvent were added to produce a varnish (W-4), and mechanical properties were evaluated by the above method.

Example 5
Under a dry nitrogen stream, 6.20 g (0.02 mol) of ODPA was dissolved in 100 g of NMP. Here, 9.07 g (0.015 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 and 0.25 g (0.001 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to 25 g of NMP. And reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Next, 0.99 g (0.008 mol) of 4-aminobenzyl alcohol as an end-capping agent was added together with 5 g of NMP, and reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 10 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 stirring, the solution was cooled to room temperature and then poured into 1 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 20 hours, and a resin containing a polyimide precursor having a methylol group at the end and a polybenzoxazole precursor structure (A- 3 and a phenolic hydroxyl group amount of 1.8 mol / kg) was obtained.

  1 g of NIKACAL MW-100LM as the component (b) and 10 g of GBL as the solvent are added to 5 g of the obtained resin (A-3) to prepare a varnish (W-5), and the mechanical properties are evaluated by the above method. It was.

Example 6
Diamine was added to 4.60 g (0.013 mol) of 4,4′-diaminodiphenyl ether, 0.28 g (0.002 mol) of 3,5-diaminobenzyl alcohol and 1,3-bis (3-aminopropyl) tetramethyldiamine. A polymerization reaction was carried out in the same manner as in Example 5 except that the terminal blocking agent was changed to 0.87 g (0.008 mol) of 4-aminophenol to 0.25 g (0.001 mol) of siloxane, and the side chain was changed. A powder of a polyimide precursor resin having a methylol group (A-4, phenolic hydroxyl group content 0.7 mol / kg) was obtained.

  1 g of NIKALAX MX-270 as component (b) and 10 g of GBL as solvent are added to 5 g of the obtained resin (A-4) to prepare varnish (W-6), and mechanical properties are evaluated by the above method. It was.

Example 7
Under a dry nitrogen stream, 5.86 g (0.016 mol) of BAHF and 0.25 g (0.001 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 80 g of NMP. To this, 4.34 g (0.014 mol) of ODPA was added together with 10 g of NMP and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, 10 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. Thereafter, the mixture was cooled to 50 ° C. over 1 hour, and 1.86 g (0.006 mol) of ODPA was added together with 10 g of NMP and stirred at 50 ° C. for 1 hour, and further 0.82 g of 4-methoxymethylaniline as a terminal blocking agent ( 0.006 mol) was added together with 5 g of NMP and stirred at 50 ° C. for 1 hour. After completion of the stirring, the solution was cooled to room temperature and then poured into 1 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a polyimide resin having a methoxymethyl group at the end (A-5, phenolic hydroxyl group amount 2.6 mol / kg) of powder was obtained.

  1 g of NIKACALAC MX-270 as component (b) and 10 g of GBL as solvent are added to 5 g of the obtained resin (A-5) to prepare a varnish (W-7), and mechanical properties are evaluated by the above method. It was.

Example 8
The polymerization reaction was carried out in the same manner as in Example 7 except that the end-capping agent was changed to 0.92 g (0.006 mol) of 3,5-bis (hydroxymethyl) aniline, and 2 methylol groups were added to one end. A powder of polyimide resin (A-6, phenolic hydroxyl group content 2.6 mol / kg) was obtained.

  1 g of NIKACAL MX MX-270 as component (b) and 10 g of GBL as a solvent were added to 5 g of the obtained resin (A-6) to prepare a varnish (W-8), and mechanical properties were evaluated by the above method. It was.

Example 9
5 g of the resin (A-1) obtained in Example 1, 1 g of NIKALAX MX-270 as component (b), 0.5 g of the quinonediazide compound obtained in Synthesis Example 2 as a photoacid generator, and vinyl as an adhesion improver A positive photosensitive varnish (W-9) was prepared by adding 0.05 g of trimethoxysilane and 12 g of GBL as a solvent, and mechanical properties were evaluated by the above-described method.

The obtained varnish (W-9) was applied onto a 6-inch silicon wafer by spin coating using a coating / developing apparatus Mark-7 so that the film thickness after baking at 120 ° C. for 4 minutes was 10 μm. And pre-baked. The film thickness was measured at a refractive index of 1.629 using an optical interference type film thickness measuring device Lambda Ace STM-602 (Dainippon Screen Mfg. Co., Ltd.). Set the reticle cut the pattern exposure machine i-line stepper DSW-8000 (GCA Corp.), was exposed at 50 mJ / cm ² step at an exposure amount of 50~1000mJ / cm ^2. After the exposure, using a Mark-7 developing device, a 2.38 wt% aqueous solution of tetramethylammonium (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D) is used for a developer discharge time of 10 seconds by the paddle method. Development with a paddle time of 50 seconds was repeated twice, then rinsed with pure water and then shaken and dried to obtain a positive pattern. When the pattern was observed with an optical microscope, a 5 μm pattern was resolved at 450 mJ / cm ² or more. Further, the film thickness after development was 8.9 μm.

Example 10
1 g of NIKALAC MX-270 as the component (b) and 5 g of the resin (A-1) obtained in Example 1, and PDBE-200 as a polymerizable compound having an unsaturated bond (trade name, manufactured by NOF Corporation) 2.0 g, dipentaerythritol hexaacrylate (trade name DPHA, manufactured by Nippon Kayaku Co., Ltd.) 0.5 g, photopolymerization initiator OXE02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.6 g, improved adhesion A negative photosensitive varnish (W-10) was prepared by adding 0.05 g of vinyltrimethoxysilane as an agent and 16 g of GBL as a solvent, and the mechanical properties were evaluated by the above method.

The obtained varnish (W-10) was coated on a 6-inch silicon wafer by spin coating using a coating and developing apparatus Mark-7 so that the film thickness after baking at 100 ° C. for 3 minutes was 10 μm. And pre-baked. The film thickness was measured at a refractive index of 1.629 using Lambda Ace STM-602. A reticle with a cut pattern was set in a full-wave exposure machine (Ultratech Co., Ltd., full-wavelength stepper Spectrum 3e), and full-wavelength exposure was performed with an exposure amount of 500 mJ / cm ² (i-line conversion). The exposed film was heat-treated at 100 ° C. for 1 minute using a Mark-7 hot plate. Using a development device of Mark-7, development is performed with a 2.38 wt% tetramethylammonium aqueous solution by a paddle method with a developer discharge time of 10 seconds and a paddle time of 80 seconds, and then rinsed with pure water. It was shaken and dried to obtain a negative pattern. When the pattern was observed with an optical microscope, a 10 μm pattern was resolved. The film thickness after development was 8.3 μm.

Comparative Example 1
Except for changing the end-capping agent to 4-aminophenol 0.65 g (0.006 mol), a polymerization reaction is carried out in the same manner as in Example 7, and a polyimide resin having no methylol group (A-7, A powder having a phenolic hydroxyl group content of 3.1 mol / kg) was obtained.

  1 g of NIKALAX MX-270 as component (b) and 10 g of GBL as solvent are added to 5 g of the obtained resin (A-7) to produce varnish (W-11), and mechanical properties are evaluated by the above method. It was.

Comparative Example 2
A polyimide precursor having no methylol group and polybenzoxazole was subjected to a polymerization reaction in the same manner as in Example 5 except that the terminal blocking agent was changed to 0.94 g (0.008 mol) of 4-ethynylaniline. A resin powder (A-8, phenolic hydroxyl group content 1.8 mol / kg) containing a precursor structure was obtained.

  1 g of NIKALAX MX-270 as component (b) and 10 g of GBL as solvent are added to 5 g of the obtained resin (A-8) to prepare varnish (W-12), and mechanical properties are evaluated by the above method. It was.

Comparative Example 3
8 g of GBL as a solvent was added to 5 g of the resin (A-1) obtained in Example 1 to prepare a varnish (W-13), and mechanical properties were evaluated by the above method.

Comparative Example 4
Under a dry nitrogen stream, BAHF 0.73 g (0.002 mol), 4,4′-diaminodiphenyl ether 2.80 g (0.014 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 0.25 g (0.001 mol) was dissolved in 80 g of NMP. To this, 4.34 g (0.014 mol) of ODPA was added together with 10 g of NMP and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, 10 g of xylene was added, and the mixture was stirred at 150 ° C. while azeotropically distilling water with xylene. After about 3 hours, the resin gelled in the flask, and the desired polyimide resin powder was not obtained. The amount of phenolic hydroxyl group in the system during high temperature polymerization was 0.4 mol / kg when the resin was converted to powder.

  The evaluation results are shown in Table 1. In Table 1, “PI” indicates polyimide, “PBO” indicates polybenzoxazole, and “nd” indicates that the film is brittle and cannot be measured.

Claims (6)

(A) a polyimide having an alkoxymethyl group or a methylol group, polybenzoxazole, polyamideimide, a precursor thereof or a copolymer thereof, and (b) a compound having at least two alkoxymethyl groups or methylol groups. A resin composition to contain. 2. The resin composition according to claim 1, wherein at least one of an alkoxymethyl group or a methylol group in the component (a) is at a terminal of the resin. The resin composition according to claim 1 or 2, wherein the component (a) contains 1 to 4 moles of phenolic hydroxyl group in 1 kg of (a). The resin composition according to any one of claims 1 to 3, further comprising (c) a thermal acid generator. The photosensitive resin composition according to claim 1, further comprising (d) a photoacid generator. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (e) a compound having an unsaturated bond and (f) a photopolymerization initiator.