JP5875209B2 - Thermosetting resin composition - Google Patents

Description

  The present invention relates to a thermosetting resin composition. More specifically, the present invention relates to a thermosetting resin composition suitable 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.

  Polyimide resins are known to be useful for applications such as heat resistant films and adhesives because of their excellent electrical properties, mechanical properties, and heat resistance. Conventionally, when producing a heat-resistant polyimide, there is a method in which a polyamic acid is polymerized from an aromatic tetracarboxylic acid anhydride and an aromatic diamine, molded from the polyamic acid, and then imidized by various methods. It was taken. However, when a polyamic acid is used, there is a problem that stress is generated with a large shrinkage due to imidization after molding. On the other hand, a solvent-soluble polyimide has also been proposed (see, for example, Patent Documents 1 to 3). As a method of obtaining a cured film with good insulation and chemical resistance using a solvent-soluble polyimide, the polyimide and the thermal cross-linking agent are dissolved in a solvent and then molded. There has been proposed a method for improving insulation and chemical resistance by causing it (see, for example, Patent Document 2). However, even if these methods are used, shrinkage stress is generated due to the difference in linear expansion coefficient from the substrate in the heat treatment step after molding, and substrate warpage or peeling between substrates may occur. As a method for solving this problem, there is a method of softening the cured film to relieve the shrinkage stress, but it was difficult to relieve the shrinkage stress without impairing the original insulation and chemical resistance of the polyimide.

Also, a resin such as polybenzoxazole was subjected to pattern processing in a precursor state and then subjected to a ring closure by heat treatment or the like, so that a large shrinkage stress was applied similarly to polyimide and the like.
Japanese Patent Laid-Open No. 3-121132 JP 2005-41936 A JP 2003-177515 A

  In order to solve the above-described problems, an object of the present invention is to provide a thermosetting resin composition in which the obtained cured film has good insulation and chemical resistance and has a small shrinkage stress during heat treatment.

That is, the present invention comprises (a) a resin having at least one structural unit selected from the following general formulas (1) to (3) and (b) a thermal crosslinking agent, and (b) the thermal crosslinking agent is an epoxy. A thermosetting resin composition comprising a compound and / or an oxetane compound or selected from thermal crosslinking agents represented by formulas (9) to (11) .

(In the formula, D independently represents a hexafluoropropylidene group, an isopropylidene group, a methylene group, an ether group, a thioether group or an SO ₂ group. X independently represents any group selected from the formula (8). Each group is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, a cyano group, and a nitro group. May be substituted with a group, amino group, hydroxyl group, carboxyl group or halogen atom, Z and A represent NH, O or S. m, n and p represent a range of 1 to 10,000. 'Represents an integer of 0 to 3, and β and β' each represents an integer of 0 to 4. However, α + α '+ β + β' is an integer of 1 to 10.)

  According to the present invention, a thermosetting resin composition having a small shrinkage stress during heat treatment can be obtained. Moreover, the cured film obtained by heat-treating this thermosetting resin composition has high insulation and good chemical resistance in fine wiring.

The thermosetting resin composition of the present invention contains (a) a resin having at least one structural unit selected from the general formulas (1) to (3), and (b) a thermal crosslinking agent. As the resin of the component (a), polyimide having a structural unit represented by the general formula (1), polyazole having a structural unit represented by the general formula (2), and a structural unit represented by the general formula (3) And polyamides having When the resin (a) has at least one structural unit selected from the following general formulas (1) to (3), a resin composition having excellent insulating properties can be obtained. Moreover, since it has a bulky substituent in the side chain, it is possible to improve the solubility of the resin in the organic solvent, and further suppress the excessive orientation of the resins during the heat treatment, thereby reducing the warpage due to the shrinkage stress. Furthermore, since it has a group having a small polarity in the side chain, there is an effect of reducing the water absorption rate. Since the thermosetting resin composition of the present invention contains such a resin and (b) a thermal cross-linking agent, it causes a thermal cross-linking reaction during heat treatment and obtains a cured film excellent in insulation and chemical resistance. Can do.

In the above formula, D independently represents a hexafluoropropylidene group, isopropylidene group, methylene group, ether group, thioether group or SO ₂ group. X independently represents any group selected from the formula (8), and each group is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. It may be substituted with an alkoxyl group, an ester group having 1 to 10 carbon atoms, a cyano group, a nitro group, an amino group, a hydroxyl group, a carboxyl group or a halogen atom. Z and A represent NH, O or S. m, n, and p show the range of 1-10000. α and α ′ each represent an integer of 0 to 3, and β and β ′ each represent an integer of 0 to 4. However, α + α ′ + β + β ′ is an integer of 1 to 10.

  The resin used in the present invention needs to have at least one structural unit selected from the above general formulas (1) to (3). It may consist only of the structural units represented by the general formulas (1) to (3), or may be a copolymer or a mixture with other structural units. The type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the cured product obtained by heat treatment. Furthermore, it is preferable to have 10 mol% or more of structural units selected from the general formulas (1) to (3), more preferably 20 mol% or more. In order to clarify the effects of the present invention, the structural unit is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more.

Such a resin can be synthesized, for example, by the following method. Dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids or derivatives or dianhydrides thereof having X—CH ₂ —O— groups, and diamines, triamines, tetraamines, and further substituted with hydroxyl, carboxyl, thiol, PO, silyl By reacting an amino compound or a derivative thereof in the range of −30 ° C. to 300 ° C., the resin as the component (a) can be synthesized. For example, polyimide can be obtained by reacting tetracarboxylic acid and diamine. Examples of polyazoles include polybenzoxazole, polybenzthiazole, and polybenzimidazole. Polybenzoxazole can be obtained by reacting the corresponding bisaminophenol and dicarboxylic acid, polybenzothiazole by reacting bisaminothiophenol and dicarboxylic acid, and polybenzimidazole by reacting tetraamine and dicarboxylic acid. Polyamide can be obtained by reacting diamine with dicarboxylic acid or a derivative thereof. In the synthesis of the resin, an amine compound such as an imidazole compound, triethylamine, pyridine, or quinoline, a phosphorus compound such as triphenylphosphine, or an acid such as p-toluenesulfonic acid can be added to accelerate the reaction. These reaction accelerators are generally used in an amount of 0.1 to 100% by weight based on the weight of the resulting resin. Alternatively, the reaction can be activated with a solvent using a phosphorus solvent such as polyphosphoric acid or HMPA as the reaction solvent.

Further, as another method, dicarboxylic acid having no X—CH ₂ —O— group, tricarboxylic acid, tetracarboxylic acid or a derivative or dianhydride thereof, and diamine, triamine, tetraamine, and further, hydroxyl, By adding a compound represented by the following general formula (5) to a resin obtained by reacting a carboxyl, thiol, PO, silyl-substituted amino compound or a derivative thereof in the same manner as described above, (a) Component resins can be synthesized. Even when this addition reaction is carried out, the above amine compound, phosphorus compound, acid or the like can be used as a reaction catalyst.

In the above formula, R ⁸ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, X is any group selected from the formula (8), and each group is an alkyl having 1 to 10 carbon atoms. Group, an alkenyl group having 2 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, a cyano group, a nitro group, an amino group, a hydroxyl group, a carboxyl group, or a halogen atom. Also good.

In the general formula (1) - (3), X represents any group selected from independently equation (8), each group 1-10 alkyl group having 1 to 10 carbon atoms, 2 carbon atoms It may be substituted with a 10 alkenyl group, an alkoxyl group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, a cyano group, a nitro group, an amino group, a hydroxyl group, a carboxyl group, or a halogen atom. By this steric hindrance, the orientation between the resins can be suppressed, and the effect of relaxing the shrinkage stress can be obtained. Further, the rigidity of the resin itself can be maintained, and the insulation and heat resistance can be maintained. X is shown below.

In the above formula, each group is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a cyano group. , A nitro group, an amino group, a hydroxyl group, a carboxyl group, or a halogen atom.

  Furthermore, X preferably has a mononuclear or polynuclear aromatic ring. By having a mononuclear or polynuclear aromatic ring, the orientation of the resins can be effectively suppressed and the shrinkage stress can be reduced while maintaining the rigidity of the resin.

  Examples of the compound represented by the general formula (5) include compounds having a structure as shown below.

In the above formula, R ⁹ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, R ¹⁰ is independently an organic group having 1 to 10 carbon atoms, a hydroxyl group, a thiol group, a chlorine atom, a fluorine atom or a nitro group. r shows the integer of 0-4.

In general formulas (1) to (3), α and α ′ each represent an integer of 0 to 3, and β and β ′ each represent an integer of 0 to 4. However, α + α ′ + β + β ′ is an integer of 1 to 10. By setting α + α ′ + β + β ′ to 1 to 10, it is possible to adjust the interaction between polyimides during heat treatment to an appropriate range, and maintain insulation and chemical resistance while suppressing shrinkage stress. .

In general formulas (1) to (3), D independently represents a hexafluoropropylidene group, an isopropylidene group, a methylene group, an ether group, a thioether group, or a SO ₂ group.

  The resin (a) used in the present invention preferably further has a structural unit represented by the following general formula (7). By having the structural unit represented by the general formula (7), the solubility in the solvent can be improved, and shrinkage during curing can be further suppressed.

In General Formula (7), R ¹¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ¹² is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, a cyano group, a nitro group, an amino group, Represents a hydroxyl group, a carboxyl group or a halogen atom. s shows the integer of 1-10, Preferably it is 1-2. By setting s to 1 or more, shrinkage during curing can be suppressed, and by setting it to 10 or less, insulation can be improved.

  The content of the structural unit represented by the general formula (7) is preferably 2 to 30% by weight in the resin. When the content is 2% by weight or more, the above effect can be obtained, and when the content is 30% by weight or less, the rigidity of the resin skeleton can be maintained, and heat resistance and insulation can be maintained.

  In order to obtain a resin having the structural unit represented by the general formula (7), specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octa Methylpentasiloxane or the like may be used, or bis (3-carboxypropyl) tetramethyldisiloxane, α, ω-bis (phthalic acid) polydimethylsiloxane, or the like may be used as the carboxylic acid component.

  Furthermore, the resin (a) used in the present invention preferably has at least one group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group and a thiol group at the side chain and / or terminal. By having such a group, there are the following advantages. For one thing, the reaction efficiency at the time of adding the compound represented by General formula (5) to resin can be improved. Secondly, (b) when an epoxy compound is used as a thermal crosslinking agent, it can promote the ring-opening and crosslinking reaction of the epoxy compound at the time of thermal curing, and can form a finer stitch structure, Chemical resistance can be improved. Thirdly, when the thermosetting resin composition of the present invention is used as a photosensitive resin composition, having such a group improves solubility in an aqueous alkali solution and enables alkali development. it can. Alkali development is very preferable because it has a low environmental impact. Such a resin can be obtained, for example, by using a diamine component or an acid dianhydride component having a group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group, taking a polyimide resin as an example. . Alternatively, it is also preferable that the end capping is performed with an end capping agent having a group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Examples of the terminal blocking agent include primary monoamines, acid anhydrides, carboxylic acid derivatives, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds.

  Specific examples of the terminal blocking agent are shown below. Specific examples of the primary monoamine include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene and 1-hydroxy. -6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino- 2-hydroxynaphthalene, 1-carboxy-8-amino Phthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy 2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5- Aminosalicylic acid, 6-aminosalicylic acid, 3-a No-o-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3- Amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto- 2-aminonaphthalene, 1-amino-7-mercaptonaphthalene 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino -2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like.

  Of these, 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-aminosalicylic 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 are preferable.

  In particular 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, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2 -Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. These are used alone or in combination of two or more.

  Specific examples of acid anhydrides, carboxylic acid derivatives, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds include phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride. , 4-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxy Naphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1- Droxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxy Monocarboxylic acids such as naphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, and their carboxyl groups Monoacid chloride compound obtained by acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxyl Phthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, Monoacid chloride compounds, monoacid chloride compounds and N-hydroxy compounds in which only the monocarboxyl group of dicarboxylic acids such as 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and 2,7-dicarboxynaphthalene is converted to acid chloride Examples include active ester compounds obtained by reaction with -5-norbornene-2,3-dicarboximide.

  Among these, from the ease of introduction into the polymer, acid anhydrides such as phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7- Monocarboxylic acids such as carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid are preferably used. These are used alone or in combination of two or more.

  As the terminal blocking agent, the content of the primary monoamine is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total diamine component. The content of the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound component is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 55 mol%, based on the total diamine component. It is.

  The weight average molecular weight of the resin (a) used in the present invention is preferably 4,000 to 80,000, particularly preferably 5,000 to 50,000, in terms of polystyrene by gel filtration chromatography. When the weight average molecular weight is 4,000 or more, the composition viscosity is increased to enable thick film coating, and when the weight average molecular weight is 80,000 or less, the solubility in a solvent can be improved. .

The thermosetting resin composition of the present invention further contains (b) a thermal crosslinking agent, and (b) the thermal crosslinking agent contains an epoxy compound and / or an oxetane compound, or is represented by the formula (9). It is any one selected from thermal crosslinking agents . (B) By containing a thermal crosslinking agent, it is possible to cause a crosslinking reaction by heat treatment and to improve the insulation and chemical resistance after curing.

The (b) a thermal crosslinking agent, there is an epoxy compound and / or oxetane compound. By using an epoxy compound and / or an oxetane compound, curing proceeds even in an ultra-low temperature heat treatment at 80 ° C. to 220 ° C., and the insulation and chemical resistance of the cured film after curing can be improved.

  As the epoxy compound, those having two epoxy groups include Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 4000, Epolite 3002 (and above, trade names) , Manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-850L (above, trade name, manufactured by Nagase ChemteX Corporation), GAN, GOT (above, product) Name, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 828, Epicoat 1002, Epicoat 1750, Epicoat 1007, YX8100-BH30, E1256, E4250, E4275 (above, trade name, JA Epoxy EXA-9583, HP4032 (above, trade name, manufactured by Dainippon Ink & Chemicals, Inc.), 3 having Tepic S, Tepic G, Tepic P (above, trade name, Nissan Chemical Industries, Ltd.), Denacol EX-321L (trade name, manufactured by Nagase ChemteX Corporation), NC3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), EPPN502H, NC3000 (Above, trade name, manufactured by Nippon Kayaku Co., Ltd.), Epicron N695, HP7200 (above, trade name, manufactured by Dainippon Ink & Chemicals, Inc.) and the like. Two or more of these may be used in combination.

  In addition, Epolite M-1230, Epolite EHDG-L (above, trade name, manufactured by Kyoeisha Chemical Co., Ltd.), PP-101 (trade name, manufactured by Toto Kasei Co., Ltd.) having one epoxy group in the epoxy compound, NK oligo EA-1010 / ECA (trade name, Shin-Nakamura Chemical Co., Ltd.) can be blended to adjust the degree of crosslinking.

  Examples of the oxetane compound include etanacol EHO, etanacol OXBP, etanacol OXTP, etanacol OXMA (trade name, manufactured by Ube Industries, Ltd.), oxetaneated phenol novolak, and the like. Two or more of these may be used in combination.

  In the present invention, the epoxy compound and / or oxetane compound preferably has two or more epoxy groups or oxetane groups. By having two or more epoxy groups or oxetane groups, a crosslinked structure can be introduced into the resin after thermosetting, and solvent resistance can be further improved.

  The epoxy compound and / or oxetane compound preferably has an epoxy equivalent or oxetane equivalent of 100 to 500. By setting it to 100 or more, the toughness of the cured film after heat treatment can be improved, and by setting it to 500 or less, a high-density stitch structure can be introduced after heat treatment, so that the cured film after heat treatment is made highly insulating. be able to.

  The content of the (b) thermal crosslinking agent is preferably 1 to 250 parts by weight, more preferably 5 to 150 parts by weight with respect to 100 parts by weight of the resin (a). . By setting it to 250 parts by weight or less, the heat resistance when the thermosetting resin composition is made into a cured film can be improved, and by setting it to 1 part by weight or more, the effect of increasing the molecular weight by crosslinking is obtained, and the heat resistance of the cured film is increased. Can be improved.

  A curing accelerator can be further used in the thermosetting resin composition of the present invention. By combining an epoxy compound and / or oxetane compound and a curing accelerator, curing of the epoxy compound and / or oxetane compound can be promoted, and the solvent resistance can be improved even by heat treatment at 150 ° C. or lower. Examples of the curing accelerator include various imidazoles, imidazole silanes, imidazolines, acid anhydrides, phosphorus compounds such as triphenylphosphine, and the like. As various imidazoles, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and the like. As the imidazole silane, IS-1000, IS-1000D, IM-1000, SP-1000, IA-100A, IA-100P, IA-100F (trade name, manufactured by Nikko Materials Co., Ltd.), and other 1,8 -Diazabicyclo [5,4,0] undec-7-ene and the like. Examples of the acid anhydride include methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Adeka Hardener EH-3326, Adeka Hardner EH-703, Adeka Hardner EH-705A (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) , Epicron B-570, Epicron B-650 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), and the like, and phosphorus compounds such as triphenylphosphine and quaternary phosphonium salts. The content of the curing accelerator is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the (b) thermal crosslinking agent. By setting it as 0.01 weight part or more, hardening of a thermal crosslinking agent can be accelerated | stimulated effectively, and the insulation and heat resistance of hardened | cured material can be improved by setting it as 10 weight part or less.

The structures of (b) a thermal crosslinking agent used in the thermosetting resin composition of the present invention are shown below as formulas (9) to (11) .

  Moreover, by adding a crosslinkable compound and a photoacid generator or photobase generator to the resin composition of the present invention, the solubility of the exposed portion is reduced, and a negative photosensitive resin composition is obtained. You can also.

The thermosetting resin composition of the present invention contains (c) a polymerizable compound and (d) a photopolymerization initiator, and (c) the polymerizable compound is selected from a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. A compound having one or more unsaturated double bond functional groups and / or propargyl groups which are unsaturated triple bond functional groups is preferred. By containing (c) and (d), polymerization proceeds selectively by light irradiation, and photosensitivity can be imparted to the thermosetting resin composition of the present invention.

The (c) polymerizable compound thereof, a vinyl group, an allyl group, an acryloyl group, a compound having an unsaturated triple bond functionality Moto of unsaturated double bond functionality and / or propargyl the Hitoshi methacryloyl group is mentioned, the Korera Among them, a compound having a conjugated vinyl group, an acryloyl group, or a methacryloyl group is preferable in terms of polymerizability. Moreover, it is preferable that it is 1-4 from the point of stability as the number which the functional group contains, and it does not need to be the same group, respectively. The polymerizable compound referred to here preferably has a molecular weight of 30 to 800. When the molecular weight is in the range of 30 to 800, the compatibility with the resin of the component (a) is good, and the stability of the thermosetting resin composition is good.

  (C) Examples of the polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, triethylene glycol Methylolpropane 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, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol di Acrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclo Decane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate Relate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N -Methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidi Nyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like. These may be used alone or in combination of two or more.

  Of these, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6 , 6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6 -Tetramethylpiperidinyl acrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like.

  The content of the polymerizable compound (c) is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the resin (a), and more preferably 5 to 150 parts by weight from the viewpoint of compatibility. By setting the content of the component (c) to 5 parts by weight or more, it is possible to prevent elution of the exposed part during development, and to obtain a thermosetting resin composition having a high residual film ratio after development. By setting it as the weight part or less, the whitening of the film at the time of film formation can be suppressed.

  (D) Examples of the photopolymerization initiator include benzophenones such as benzophenone, Michler's ketone, 4,4, -bis (diethylamino) benzophenone, 3,3,4,4, -tetra (t-butylperoxycarbonyl) 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- Coumarins such as diethylaminocoumarin, 2-t-butyl Anthraquinones such as luanthraquinone, 2-ethylanthraquinone, 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, N-phenylglycine, N-methyl-N-phenylglycine, N -Glycines such as ethyl-N- (p-chlorophenyl) glycine and N- (4-cyanophenyl) glycine, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl- 1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2 -(O-benzoyl) oxime, bis (α-isoni) Trosopropiophenone oxime) oximes such as isophthal, and α-aminoalkylphenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

  Of these, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-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, etc. Oximes are preferred, particularly preferably 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, Bis (α-isonitrosopropiophenone oxime) isophthal.

  As for content of the said photoinitiator, 0.1-60 weight part is preferable normally with respect to 100 weight part of (a) resin.

  A colorant can be further used in the thermosetting resin composition of the present invention. The colorant has an effect of preventing stray light from the light emitting area in the insulating layer of the organic electroluminescent element, and has a blinding action to hide the circuit wiring on the substrate in the solder resist for the circuit board.

  Examples of the colorant used in the present invention include dyes, thermochromic dyes, inorganic pigments, and organic pigments. Moreover, what is soluble in the organic solvent which melt | dissolves the said (a) component and is compatible with resin is preferable. Among these colorants, examples of the dye include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes, and direct dyes. As the skeleton structure of the dye, anthraquinone series, azo series, phthalocyanine series, methine series, oxazine series, and metal complex complexes of these dyes can be used. Among them, phthalocyanine series and metal complex complexes are available. Excellent in heat resistance and light resistance, and more preferable. Specifically, Sumilan, Lanyl dye (manufactured by Sumitomo Chemical Co., Ltd.), Orasol, Oracet, Filamid, Irgasperse dye (manufactured by Ciba Specialty Chemicals Co., Ltd.), Zapon, Neozapon, Neptune, Acidol dye (BASF (stock) )), Kayaset, Kayakalan dye (Nippon Kayaku Co., Ltd.), Varifast colors dye (Orient Chemical Co., Ltd.), Savinyl, Sandoplast, Polysynthren, Lanasyn dye (Clariant Japan Co., Ltd.), Aizen Spilon And dyes (Hodogaya Chemical Co., Ltd.). These dyes are used alone or in combination.

  The thermosetting resin composition of the present invention can contain a filler. This is effective when the thermosetting resin composition of the present invention is used as a solder resist for a circuit board in order to develop thixotropy and maintain a predetermined size in the process of coating and drying in screen printing. is there. In addition, an effect of suppressing shrinkage of thermosetting can be expected.

  Examples of the filler used in the present invention include calcium carbonate, silica, alumina, aluminum nitride, titanium oxide, and silica-titanium oxide composite particles as examples of the insulating filler, and gold and silver as examples of the conductive filler. , Copper, nickel, aluminum, carbon and the like. A plurality of these may be mixed depending on the application. In the case of an insulating filler, silica, titanium oxide, and silica-titanium oxide composite particles are preferable in terms of reliability and cost, and in the case of a conductive filler, silver is preferable. The content is preferably 2 to 1000 parts by weight, more preferably 5 to 500 parts by weight with respect to 100 parts by weight of component (a). By setting it to 2 parts by weight or more, moisture resistance can be improved, and by setting it to 1000 parts by weight or less, an excessive increase in product viscosity can be prevented and good workability can be obtained. The filler preferably has an average particle size of 10 μm or less, and more preferably 2 μm or less. By setting the average particle size to 10 μm or less, fluidity can be maintained and coating can be facilitated. It is also preferable to use a mixture of two or more fillers having different average particle diameters from the viewpoint of imparting thixotropy and stress relaxation.

  Furthermore, if necessary, for the purpose of improving the wettability between the thermosetting resin composition and the substrate, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, Ketones such as methyl isobutyl ketone and ethers such as tetrahydrofuran and dioxane may be mixed. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

  Moreover, in order to improve the adhesiveness with a base substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent or the like is added to the thermosetting resin composition in an amount of 0.5 to 10% by weight, or the base substrate. Can also be pretreated with such a chemical solution.

  When added to the thermosetting composition, for example, a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, a titanium chelating agent, or an aluminum chelating agent is added to the polyimide in the thermosetting resin composition. In contrast, 0.5 to 10% by weight is added.

  When the substrate is treated, the coupling agent described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate and the like in an amount of 0.5-20. Surface treatment is performed by spin coating, dipping, spray coating, steam treatment, etc. on the solution in which the weight% is dissolved. Depending on the case, reaction of a board | substrate and the said coupling agent is advanced by applying temperature of 50-300 degreeC after that.

  However, it is not preferable that the thermosetting resin composition contains an onium salt, a diallyl compound, a tetraalkylammonium salt, or the like as a compound having an effect of inhibiting the dissolution of the component (a) in the alkaline aqueous solution. When these are contained, the compound decomposition occurs in the subsequent heat treatment, and an acid or a base is generated. This causes the heat resistance of the cured film to be lowered, the mechanical properties are lowered, the adhesiveness is lowered, etc. Problems can arise.

  The thermosetting resin composition of the present invention preferably contains an organic solvent for the purpose of adjusting the viscosity of the composition or improving applicability. Specific examples of the organic solvent 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 diethylene glycol methyl ethyl ether, 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 , Acetates such as ethyl lactate and butyl lactate, acetylacetone, Ketones such as butyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutyl alcohol, pentaanol, 4-methyl-2-pentanol, 3-methyl-2-butanol , Alcohols such as 3-methyl-3-methoxybutanol and diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, and other examples include N, N-dimethylformamide, N, N-dimethylacetamide and dimethyl sulfoxide. . Among these, those that dissolve the component (a) and have a boiling point of 110 ° C. to 190 ° C. under atmospheric pressure are particularly preferable. By setting the boiling point to 110 ° C. or higher, the solvent is volatilized at the time of coating the composition and the coating property is prevented from being lowered. By setting it to 190 ° C. or lower, the residual solvent at the time of heat treatment at low temperature is reduced, and the cured film Insulation properties and heat resistance can be improved. Further, by using a solvent that dissolves the component (a), a uniform coating film can be formed on the base substrate. These may be used alone or in combination.

  Specifically, among alcohol solvents having a boiling point of 110 ° C. to 190 ° C. under atmospheric pressure, particularly propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol, which are safe for the human body, are particularly preferable. Examples include monobutyl ether, diethylene glycol methyl ethyl ether, methyl lactate, ethyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, butyl acetate, and 3-methoxybutyl acetate.

  Moreover, the organic solvent contained in the thermosetting resin composition of the present invention is preferably 20 to 800 parts by weight, particularly preferably 30 to 500 parts by weight with respect to 100 parts by weight of component (a). .

  Next, a method for forming a cured film using the thermosetting resin composition of the present invention will be described.

  A thermosetting resin composition is applied on the substrate. As the substrate, polyimides, silicon wafers, ceramics, glass substrates, gallium arsenide, and the like are used, but not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and screen printing coating. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is normally applied so that the film thickness after drying becomes 1 to 150 μm.

  Next, you may include the process of drying the board | substrate which apply | coated the thermosetting resin composition. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at 50 to 150 ° C. for 1 minute to several hours.

  When using as a photosensitive resin, pattern processing can be performed after this. The coating film 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 order to form the pattern of the thermosetting 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, dimethylsulfoxide, γ-butyrolaclone, dimethylacrylamide, methanol, ethanol, Contains 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 alone or in combination of several kinds 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.

  Also, a step of baking before development may be incorporated. As this temperature, the range of 50-180 degreeC is preferable, and the range of 60-150 degreeC is especially more preferable. The time is not particularly limited, but is preferably 10 seconds to several hours from the viewpoint of subsequent developability.

  Next, a curing process is performed to form a cured film. The curing treatment is preferably performed at a temperature of 80 to 280 ° C. for 2 minutes to 5 hours. This heat treatment may be performed by selecting the temperature and raising the temperature stepwise, or by selecting a certain temperature range and continuously raising the temperature, but the thermosetting resin composition of the present invention can be easily heated even at a low temperature. Since it hardens | cures, a stepwise and continuous temperature rising process can also be skipped. Examples include heat treatment at 130 ° C., 160 ° C., and 180 ° C. for 30 minutes each, linear temperature increase from room temperature to 280 ° C. over 1 hour, or heat treatment at 120 ° C. for 90 minutes. It is done. Among these heat treatments, it is preferable to treat at 80 to 160 ° C. when the base substrate is made of plastic or contains a material that is easily thermally oxidized.

  The cured film formed from the thermosetting resin composition of the present invention is 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 a wiring protective insulating film for circuit boards. It is done.

  The insulating layer formed on the display device using the thermosetting resin composition of the present invention includes a first electrode formed on a substrate and a second electrode provided to face the first electrode. Specifically, for example, LCDs, ECDs, ELDs, display devices using organic electroluminescent elements (organic electroluminescent devices), and the like are applicable.

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

<Preparation of thermosetting resin film>
As the substrate, (A) a substrate in which a copper wiring having a thickness of 10 μm was arranged by plating on a 38 μm thick Kapton film, and (B) a 6-inch silicon wafer were prepared. On each substrate, a thermosetting resin composition (hereinafter referred to as “varnish”) was applied with a screen printer MEC-2400 (manufactured by Mitani Electronics Co., Ltd.) so that the film thickness after drying was 10 μm.

<Measuring method of film thickness>
The film thickness was measured at a refractive index of 1.628 using Dainippon Screen Mfg. Co., Ltd. Lambda Ace STM-602.

<Exposure>
The mask from which the pattern was cut | disconnected was set to exposure machine (Canon Co., Ltd. full wavelength aligner PLA-501F), and full wavelength exposure was performed with the exposure amount of 700-1500 mJ / cm < ² > (i line conversion).

<Development>
Using a Mark-7 developing device manufactured by Tokyo Electron Ltd., a 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed for 10 seconds at 50 revolutions. Thereafter, the mixture was allowed to stand for 30 seconds at 0 rpm, sprayed again for 10 seconds, and allowed to stand for 30 seconds, then rinsed with water at 400 rpm, shaken and dried for 10 seconds at 3000 rpm.

<Curing (heat treatment)>
Using an inert oven INH-21CD (manufactured by Koyo Thermo System Co., Ltd.), heat treatment was performed at the temperature and time described in each Example and Comparative Example.

<Warpage amount>
For the measurement of the amount of warpage, (A) a substrate in which a copper wiring with a thickness of 10 μm was arranged on a Kapton film with a thickness of 38 μm by a plating method with line / space = 10 μm / 10 μm was used. The thermosetting resin film produced above was heat-treated under the conditions described in each example, and then left on a flat desk, and the height of the highest point from the desk was measured.

<Chemical resistance>
In the chemical resistance test, (B) a sample on a silicon wafer was used. After heat-treating the thermosetting resin film prepared above under the conditions described in each example, the film was immersed in N-methylpyrrolidone (NMP) at 50 ° C. for 60 minutes at room temperature, and the film thickness after solvent treatment / film before solvent treatment The thickness was calculated.

<Insulation reliability (HAST) test>
In the insulation reliability test, a comb-like sample having a line width of 10 μm and a space of 20 μm was used. A thermosetting resin composition was applied on a comb-like sample so as to have a thickness of 10 μm, heat-treated under the conditions described in each example, and then treated for 100 hours under the conditions of 85 ° C., 85% RH, 50 V, and insulated. The resistance value was measured. Judgment of the quality of insulation reliability was good when the insulation resistance value after the 100-hour test was 1.0 × 10 ⁹ Ω or higher and less than 1.0 × 10 ⁹ Ω.

<Pattern processability evaluation>
For pattern workability evaluation, (B) a sample on a silicon wafer was used. The thermosetting resin film produced above was subjected to full-wavelength exposure at 1500 mJ / cm ² (i-line conversion) through a mask with a pattern with a line width of 50 μm and a space of 50 μm, and then developed. The case where the pattern was formed was good, and the case where the pattern could not be formed was rejected.

Synthesis Example (1) Synthesis of Polyimide (I) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) 25.46 g (0.07 mol) under a dry nitrogen stream 1,3-bis (3-aminopropyl) tetramethyldisiloxane (hereinafter referred to as SiDA) 4.97 g (0.02 mol), as a terminal blocking agent, 3-aminophenol (hereinafter referred to as 3-Aph) 2.18 g (0.02 mol) was dissolved in 80 g of NMP. Here, 31.02 g (0.1 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter referred to as ODPA) was added together with 20 g of NMP and reacted at 20 ° C. for 1 hour, and then at 50 ° C. Stir for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 180 ° C. for 5 hours while azeotropically distilling water with xylene. Thereafter, 4M26XL was added (trade name, Honshu Chemical Industries (Ltd.)) 6.36 g, and stirred for 1 hours at 180 ° C.. After stirring, 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 in a vacuum dryer at 80 ° C. for 20 hours. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. When the molecular weight was measured by gel filtration chromatography, the weight average molecular weight in terms of polystyrene was 27000.

Synthesis Example (2) Synthesis of Polyimide (II) Under a dry nitrogen stream, 18.13 g (0.05 mol) of BAHF, 7.46 g (0.03 mol) of SiDA, and 4.37 g of 3-Aph (0.3. 04 mol) was dissolved in 150 g of NMP. Here, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) propane dianhydride (hereinafter referred to as BSAA) 5.20 g (0.01 mol), 2,2-bis (3, 4-Dicarboxyphenyl) ethylene dianhydride (hereinafter referred to as TMEG-100) 36.93 g (0.09 mol) was added together with 30 g of NMP, reacted at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 4 hours. . Then, it stirred at 180 degreeC for 5 hours. Here, 6M24XL was added (trade name, Honshu Chemical Industries (Ltd.)) 7.21 g, and stirred for 1 hours at 180 ° C.. After stirring, 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 in a vacuum dryer at 80 ° C. for 20 hours. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. When the molecular weight was measured by gel filtration chromatography, the weight average molecular weight was 14,000 in terms of polystyrene.

Synthesis Example (2), by changing the amount of 6M24XL from 7.21g to 3.60 g, was synthesized. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. When the molecular weight was measured by gel filtration chromatography, the weight average molecular weight in terms of polystyrene was 13000.

Synthesis Example (4) Synthesis of Polyimide (IV) 34.74 g (0.067 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (hereinafter referred to as HFBAPP) under a dry nitrogen stream ), 4.97 g (0.02 mol) of SiDA, and 1.88 g (0.02 mol) of aniline as an end-capping agent were dissolved in 80 g of NMP. Here, 31.02 g (0.1 mol) of ODPA was added together with 20 g of NMP, and reacted at 60 ° C. for 1 hour. Thereafter, 15 g of xylene was added, and the mixture was stirred at 180 ° C. for 5 hours while azeotropically distilling water with xylene. Here, 6M24XL was added (trade name, Honshu Chemical Industries (Ltd.)) 8.60 g, and stirred for 1 hours at 180 ° C.. 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 in a vacuum dryer at 80 ° C. for 20 hours. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. When the molecular weight was measured by gel filtration chromatography, the weight average molecular weight was 29000 in terms of polystyrene.

Synthesis Example (5) Synthesis of Diamine I Bis (4-hydroxyphenyl) hexafluoropropane 40.3 g (0.12 mol, manufactured by Central Glass Co., Ltd.), 200 mL of acetic acid (manufactured by Kanto Chemical Co., Ltd.) and sulfuric acid 20 g ( In addition to a concentration of 96% or more, manufactured by Kanto Chemical Co., Inc., it was heated to 70 ° C. 20 mL of nitric acid (specific gravity 1.38, manufactured by Kanto Chemical Co., Inc.) was added dropwise over 5 minutes. Stirring was continued at 70 ° C. for 2 hours, and after cooling to room temperature, it was poured into 3000 mL of water. After the addition, filtration was performed with a tetrafluoroethylene filter, and the precipitate was collected. Further, it was thoroughly washed with water, and when the pH of the cleaning liquid reached 4 or more, it was dried for 48 hours with a vacuum dryer at 50 ° C.

  The dried 42.6 g (0.1 mol) of the solid was dissolved in 300 mL of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.). To this, 24.6 g of potassium t-butoxy (0.22 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Thereafter, 2 g of copper iodide (manufactured by Kanto Chemical Co., Inc.) and 44.2 g of 2-iodobutane (0.24 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 150 ° C. for 4 hours under a nitrogen stream. Thereafter, filtration was performed when the solution temperature returned to room temperature, and the filtrate was poured into 500 mL of water. The deposited precipitate was collected and further washed with water. Then, it dried for 48 hours with a 50 degreeC vacuum dryer.

Dried solid 43.0g of (0.08 mol) 2-methoxy ethanol 300 mL (manufactured by Wako Pure Chemical Co.), was dissolved in tetrahydrofuran 300 mL (manufactured by Wako Pure Chemical Co.), 5% palladium - carbon 1.5 g (Wako Pure Chemical Industries, Ltd.) was added. The temperature of the solution to 70 ° C., saturated with water hydrazine 25g diluted solution was added dropwise over 10 minutes (0.3 mole, Kanto Chemical Co., Ltd.) of 2-methoxy-ethanol 30 mL. After completion of the dropwise addition, stirring was further continued at 70 ° C. for 2 hours. When the temperature of the solution returned to room temperature, 1 g of acetic acid was added and stirring was continued for 1 hour. Thereafter, filtration was performed, and the filtrate was concentrated to about half by a rotary evaporator. This solution was poured into 3000 mL of water. Thereafter, the precipitate was collected by filtration, dried at room temperature, recrystallized with ethanol, and dried in a vacuum dryer at 50 ° C. for 48 hours to obtain the following diamine (I).

Synthesis Example (6) Synthesis of Polyimide (V) Under a dry nitrogen stream, 31.07 g (0.065 mol) of diamine (I) obtained in Synthesis Example 5 and 4.97 g (0.02 mol) of SiDA, end-capping As an agent, 3.27 g (0.03 mol) of 3-Aph was dissolved in 80 g of NMP. To this, 31.02 g (0.1 mol) of ODPA was added together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 180 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried in a vacuum dryer at 80 ° C. for 72 hours. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. When the molecular weight was measured by gel filtration chromatography, the weight average molecular weight was 24,000 in terms of polystyrene.

Synthesis Example (7) Synthesis of Polyimide (VI) Synthesis Example (1) was repeated except that 4M26XL was not added in Synthesis Example (1). When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. When the molecular weight was measured by gel filtration chromatography, the weight average molecular weight was 23,000 in terms of polystyrene.

Synthesis Example (8) Synthesis of Polybenzoxazole (I) 36.6 g (0.1 mol) of BAHF was dissolved in 100 g of polyphosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.). To this was added 25 g of diphenyl ether dicarboxylic acid, and the mixture was heated at 180 ° C. with stirring for 6 hours. Thereafter, the temperature of the solution was set to 70 ° C., hydroxybenzoic acid (0.02 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then the solution temperature was set to 180 ° C. and stirred for 2 hours. Thereafter, the solution was cooled to 70 ° C., and 5 g of 4MOM-P-MF (manufactured by Honshu Chemical Industry Co., Ltd.) was added. Thereafter, the mixture was stirred at 150 ° C. for 4 hours, and then lowered to room temperature, and poured into 10 L of water to obtain a target polybenzoxazole precipitate. The polymer precipitate was collected by filtration and further washed with water. Then, it dried for 72 hours with the 80 degreeC vacuum dryer, and obtained the powder of polybenzoxazole (I). When the molecular weight was measured by gel filtration chromatography, the weight average molecular weight was 22,000 in terms of polystyrene.

Synthesis Example (9) Synthesis of Polybenzoxazole (II) Polybenzoxazole (II) was obtained in the same manner as in Synthesis Example (8) except that 4MOM-P-MF was not added in Synthesis Example (8). When the molecular weight was measured by gel filtration chromatography, the weight average molecular weight in terms of polystyrene was 20000.

Synthesis Example (10) Synthesis of Polyimide (VII) 15.5 g of bis (3,5-diethyl-4-aminophenyl) ethane (0.05 mol, Nippon Kayaku Kogyo Co., Ltd., MDEA) was dissolved in 50 g of NMP. . Here, 22.2 g of 4,4′-hexafluoropropylidenebisphthalic dianhydride (0.05 mol, manufactured by Daikin Industries, Ltd., 6FDA) was added together with 30 g of NMP. This solution was reacted under nitrogen flow at 40 ° C. for 2 hours, and then 30 mL of toluene was added and water was removed at 180 ° C. for 4 hours. When this solution dropped to room temperature, it was poured into 4 L of water to obtain a brown precipitate. This precipitate was collected by filtration. Further, it was washed with 3 L of water and then dried in a vacuum dryer at 80 ° C. for 72 hours. The weight average molecular weight of this polymer was 45000.

  The structures of the compounds used in Examples and Comparative Examples are shown below.

Example 1
10 g of polyimide (I), 5 g of epoxy compound NC6000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), 5 g of Epicoat 828 (trade name, manufactured by Japan Epoxy Co., Ltd.), VG3101 of colorant (trade name, Mitsui Chemicals) 2 g, 1 g vinyltrimethoxysilane as an adhesion improver, 2E4MZ (trade name, manufactured by Shikoku Chemicals) 0.1 g, 20 g 3-methoxy-3-methylbutanol, It was dissolved to obtain a varnish. Using the obtained varnish, a thermosetting resin film was prepared as described above, heat-treated at 150 ° C. for 60 minutes, and evaluated for warpage, insulation reliability, and chemical resistance.

Reference example 1
10 g of polyimide (II), 2 g of epoxy compound NC6000, 8288 g of epicoat, 1 g of vinyltrimethoxysilane as an adhesion improver, 0.5 g of IS-1000 (trade name, manufactured by Nikko Materials Co., Ltd.), VB2620 of colorant ( 0.2 g of a trade name, manufactured by Orient Chemical Industry Co., Ltd. and 10 g of 3-methoxybutyl acetate were added and dissolved to obtain a varnish. Using the obtained varnish, a thermosetting resin film was prepared as described above, heat-treated at 120 ° C. for 90 minutes, and evaluated for warpage, insulation reliability, and chemical resistance.

Reference example 2
The amount of warpage, insulation reliability, and chemical resistance were evaluated in the same manner as in Reference Example 1 except that polyimide (III) was used as the polyimide.

Reference example 3
Polyimide (IV), OXBP of oxetane compound (trade name, manufactured by Ube Industries, Ltd.) 7.5 g, curing accelerator SI-110L (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) 0.4 g, lactic acid 15 g of ethyl was added and dissolved to obtain a varnish. Using the obtained varnish, a thermosetting resin film was prepared as described above, heat-treated at 180 ° C. for 90 minutes, and evaluated for warpage, insulation reliability, and chemical resistance.

Reference example 4
The amount of warpage, insulation reliability, and chemical resistance were evaluated in the same manner as in Reference Example 1 except that polyimide (V) was used as the polyimide.

Comparative Example 1
The amount of warpage, insulation reliability, and chemical resistance were evaluated in the same manner as in Reference Example 1 except that polyimide (VI) was used as the polyimide.

Comparative Example 2
The amount of warpage, insulation reliability, and chemical resistance were evaluated in the same manner as in Reference Example 1 except that the epoxy compound NC6000 and Epicoat 828 were not added.

Example 2
Polyimide (I) 10 g, photopolymerization initiator 4,5-diphenyl-2- (2-methylphenyl) biimidazole 0.5 g, thermal crosslinking agent Nicalac MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) ) 0.2 g, 1.5 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 4.0 g of the polymerizable compound PDBE-250 (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) into 12 g of ethyl lactate By dissolving, a varnish of a negative photosensitive polyimide composition was obtained. Using the obtained varnish, a thermosetting resin film was prepared as described above, heat-treated at 220 ° C. for 90 minutes, and evaluated for warpage, insulation reliability, and chemical resistance. Moreover, the photosensitive resin composition film was produced on the silicon wafer, exposure and alkali development were performed, and pattern workability was evaluated.

Reference Example 5
Photopolymerization initiator CGI-242 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1 g, polyimide (II) 10 g, thermal crosslinking agent Nicarak MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1.5 g of a polymerizable compound, 2EG (trade name, Kyoeisha Chemical Co., Ltd.) (4.0 g) was dissolved in 12 g of ethyl lactate to obtain a varnish of a negative photosensitive polyimide composition. Using the obtained varnish, a thermosetting resin film was prepared as described above, heat-treated at 200 ° C. for 60 minutes, and evaluated for warpage, insulation reliability, and chemical resistance. Moreover, the photosensitive resin composition film was produced on the silicon wafer, exposure and alkali development were performed, and pattern workability was evaluated.

Reference Example 6
The amount of warpage, insulation reliability, chemical resistance, and pattern processability were evaluated in the same manner as in Reference Example 5 except that polyimide (IV) was used as the polyimide.

Comparative Example 3
The amount of warpage, insulation reliability, chemical resistance, and pattern processability were evaluated in the same manner as in Reference Example 5 except that polyimide (VI) was used as the polyimide.

Comparative Example 4
The amount of warpage, insulation reliability, chemical resistance, and pattern processability were evaluated in the same manner as in Reference Example 5 except that the thermal crosslinking agent Nicalac MW-100LM was not added.

Example 3
10 g of polybenzoxazole (I) synthesized in Synthesis Example 8, 2 g of thermal crosslinking agent HMOM, and 2 g of naphthoquinone diazide compound were dissolved in 10 g of gamma butyrolactone, 10 g of propylene glycol monomethyl ether, and 10 g of ethyl lactate to obtain a varnish. Using the obtained varnish, a thermosetting resin film was prepared as described above, heat-treated at 200 ° C. for 60 minutes, and the amount of warpage, insulation reliability, and chemical resistance were evaluated.

Comparative Example 5
The amount of warpage, insulation reliability, and chemical resistance were the same as in Example 3 except that 10 g of polybenzoxazole (II) synthesized in Synthesis Example 9 was used instead of polybenzoxazole (I) synthesized in Synthesis Example 8. Evaluated.

Comparative Example 6
The amount of warpage, insulation reliability, and chemical resistance were evaluated in the same manner as in Example 3 except that the thermal crosslinking agent HMOM was not added.

Comparative Example 7
The amount of warpage, insulation reliability, and chemical resistance were evaluated in the same manner as in Reference Example 4 except that polyimide (VII) synthesized in Synthesis Example 10 was used instead of polyimide (V).

The evaluation results of Examples 1 and 3, Reference Examples 1 to 4 and Comparative Examples 1 to 2 and 5 to 7 are shown in Table 1, and the evaluation results of Example 2, Reference Examples 5 to 6 and Comparative Examples 3 to 4 are shown in Table 1. It is shown in 2.

Claims (3)

(A) a resin having at least one structural unit selected from the following general formulas (1) to (3) and (b) a thermal crosslinking agent, and (b) the thermal crosslinking agent being an epoxy compound and / or oxetane A thermosetting resin composition comprising a compound or selected from thermal crosslinking agents represented by formulas (9) to (11) .

(In the formula, D independently represents a hexafluoropropylidene group, an isopropylidene group, a methylene group, an ether group, a thioether group or an SO ₂ group. X independently represents any group selected from the formula (8). Each group is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, a cyano group, and a nitro group. May be substituted with a group, amino group, hydroxyl group, carboxyl group or halogen atom, Z and A represent NH, O or S. m, n and p represent a range of 1 to 10,000. 'Represents an integer of 0 to 3, and β and β' each represents an integer of 0 to 4. However, α + α '+ β + β' is an integer of 1 to 10.) The thermosetting resin composition according to claim 1, wherein X in the general formulas (1) to (3) contains a mononuclear or polynuclear aromatic ring. Furthermore, it contains (c) a polymerizable compound and (d) a photopolymerization initiator, and (c) one or more unsaturated double bond functional groups selected from a vinyl group, an allyl group, an acryloyl group and a methacryloyl group. And / or a compound having a propargyl group which is an unsaturated triple bond functional group.