Isocyanate-modified polyimide resin, resin composition, and cured product thereof

Abstract

An isocyanate-modified polyimide resin which is a reaction product of a diisocyanate compound (a) having an isocyanate group and a polyimide resin having an amino group and / or an acid anhydride group, said polyimide resin being a reaction product of an aliphatic diamino compound (b), a tetrabasic acid dianhydride (c) and an aromatic diamino compound (c), and which has an amino group and / or an acid anhydride group on both ends. This isocyanate-modified polyimide resin is a resin material having a novel structure, and is suitable for use in a printed wiring board. A cured product which is obtained using this resin material has a low dielectric loss tangent, while being excellent in terms of adhesiveness, heat resistance and mechanical characteristics.

Description

[Technical Field]

[0001] The present invention relates to an isocyanate-modified polyimide resin having a novel structure, a resin composition containing the polyimide resin, and a cured product of the resin composition. [Background technology]

[0002] Printed wiring boards are essential components for mobile communication devices such as smartphones and tablets, communication base station equipment, and electronic devices such as computers and car navigation systems. Various resin materials with excellent properties such as adhesion to low-roughness metal foils, heat resistance, and flexibility are used for printed wiring boards. Furthermore, in recent years, development has been underway for high-speed, high-capacity printed wiring boards for next-generation high-frequency wireless applications, and in addition to the above-mentioned characteristics, resin materials are required to have low transmission loss, i.e., low dielectric constant and low dielectric dissipation factor.

[0003] Polyimide resins, which have excellent properties such as heat resistance, flame retardancy, flexibility, electrical properties, and chemical resistance, are widely used in electrical and electronic components, semiconductors, communication devices and their circuit components, peripheral devices, etc. On the other hand, hydrocarbon compounds such as petroleum and natural oils are known to exhibit high insulating properties and low dielectric constants, and Patent Documents 1 to 4 describe polyimide resins that take advantage of both of these properties and have a long-chain alkylene skeleton derived from dimer diamine introduced into their structure. However, although the polyimide resins described in these patent documents are excellent in terms of low dielectric tangent, they are poor in balance with various properties such as processability, flexibility, heat resistance, adhesiveness, and mechanical properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5534378 [Patent Document 2] Patent No. 6488170 [Patent Document 3] Patent No. 6635403 [Patent Document 4] Patent No. 6082439 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin material having a novel structure that can be suitably used for printed wiring boards, and a resin composition containing the resin material, which has excellent processability, and the cured product thereof has a low dielectric constant and dielectric dissipation factor, and is excellent in adhesion, heat resistance, and mechanical properties. [Means for solving the problem]

[0006] As a result of extensive investigations, the present inventors have found that a resin composition containing a novel polyimide resin having a specific structure can solve the above problems, and have thus completed the present invention. That is, the present invention is (1) An isocyanate-modified polyimide resin which is a reaction product of an aliphatic diamino compound (b), a tetrabasic acid dianhydride (c) and an aromatic diamino compound (d), and which has an amino group and / or an acid anhydride group, and a diisocyanate compound (a) having an isocyanate group, and which has an amino group and / or an acid anhydride group at both ends; (2) The isocyanate-modified polyimide resin according to the above item (1), wherein the diisocyanate compound (a) comprises at least one selected from the group consisting of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate. (3) The isocyanate-modified polyimide resin according to the above item (1) or (2), wherein the aliphatic diamino compound (b) contains at least one aliphatic diamino compound having 6 to 36 carbon atoms. (4) The tetrabasic acid dianhydride (c) is represented by the following formulas (1) to (4):

[0007] [ka]

[0008] (In formula (4), Y represents C(CF3)2, SO2, CO, O, a direct bond, or a group represented by the following formula (5):

[0009] [ka]

[0010] represents a divalent linking group represented by the formula: The isocyanate-modified polyimide resin according to any one of items (1) to (3), which contains at least one selected from the group consisting of: (5) The aromatic diamino compound (d) is represented by the following formulas (6) and (8):

[0011] [ka]

[0012] In formula (6), R1 represents a methyl group or a trifluoromethyl group, and in formula (8), Z represents CH(CH3), C(CF3)2, SO2, CH2, O-C6H4-O, O, a direct bond, or a group represented by the following formula (9):

[0013] [ka]

[0014] and R3 represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a trifluoromethyl group. The isocyanate-modified polyimide resin according to any one of items (1) to (4), which contains at least one selected from the group consisting of: (6) A terminal-modified isocyanate-modified polyimide resin, which is a reaction product of the isocyanate-modified polyimide resin having an amino group and / or an acid anhydride group at both ends according to any one of the preceding items (1) to (5) with a compound having one functional group reactive with the amino group or the acid anhydride group. (7) A resin composition containing the isocyanate-modified polyimide resin according to any one of (1) to (5) above and a compound that reacts with the isocyanate-modified polyimide resin. (8) A resin composition containing the terminal-modified isocyanate-modified polyimide resin according to the above item (6) and a compound that reacts with the terminal-modified isocyanate-modified polyimide resin. (9) The resin composition according to the above item (7) or (8), wherein the compound reactive with the isocyanate-modified polyimide resin or the compound reactive with the terminal-modified isocyanate-modified polyimide resin contains at least one compound having a maleimide group. (10) A resin composition containing the isocyanate-modified polyimide resin according to any one of (1) to (5) above and a compound that does not react with the isocyanate-modified polyimide resin. (11) A resin composition containing the terminal-modified isocyanate-modified polyimide resin according to the above item (6) and a compound that does not react with the terminal-modified isocyanate-modified polyimide resin. (12) A cured product of the resin composition according to any one of (7) to (11). (13) A substrate having the cured product according to the preceding item (12). Regarding. [Effects of the Invention]

[0015] By using a resin composition containing the isocyanate-modified polyimide resin of the present invention, it is possible to provide printed wiring boards and the like that are excellent in heat resistance, mechanical properties, low dielectric properties, adhesiveness, and the like. DETAILED DESCRIPTION OF THE INVENTION

[0016] The isocyanate-modified polyimide resin of the present invention is a polyimide resin that is a reaction product of an aliphatic diamino compound (b) (hereinafter, also simply referred to as the “component (b)”), a tetracarboxylic dianhydride (c) (hereinafter, also simply referred to as the “component (c)”), and an aromatic diamino compound (d) (hereinafter, also simply referred to as the “component (d)”) (hereinafter, the polyimide resin that is a reaction product of the components (b) to (d) is referred to as an “intermediate polyimide resin”), and is a reaction product of the amino groups and / or acid anhydride groups at both ends thereof and the isocyanate groups of the diisocyanate compound (a) (hereinafter, also simply referred to as the “component (a)”), and is a polyimide resin having amino groups and / or acid anhydride groups at both ends.

[0017] [Intermediate polyimide resin] First, the intermediate polyimide resin will be described. The reaction of the components (b) to (d) includes a step of obtaining a polyamic acid by a copolymerization reaction between the amino groups in the components (b) and (d) and the acid anhydride groups in the component (c), and a step of obtaining an intermediate polyimide resin by a dehydration cyclization reaction (imidization reaction) of the polyamic acid. The above two steps may be carried out separately, but it is efficient to carry them out continuously in one batch. When the molar number MB of the component (b), the molar number MC of the component (c), and the molar number MD of the component (d) used in the copolymerization reaction satisfy the relationship MB + MD>MC, the both ends of the obtained intermediate polyimide resin will be amino groups. When the relationship MB + MD<MC is satisfied, the both ends of the obtained intermediate polyimide resin will be acid anhydride groups. Also, when the relationship MB + MD = MC is satisfied, the obtained intermediate polyimide resin will theoretically have an infinite molecular weight and will have one amino group and one acid anhydride group at both ends.

[0018] Although there are no particular restrictions on the amount of component (b) used in the copolymerization reaction, it is preferably an amount that is within the range of 10 to 50 mass% of the total mass of components (b) to (d) used in the synthesis of the intermediate polyimide resin and component (a) used in the synthesis of the isocyanate-modified polyimide resin described below, minus the mass of water produced in the dehydration cyclization reaction step during the synthesis of the intermediate polyimide resin (this mass is substantially equal to the mass of the final isocyanate-modified polyimide resin). If the amount of component (b) is below this range, the proportion of aliphatic chains derived from component (b) in the intermediate polyimide resin will be too low, resulting in a high dielectric constant and dielectric loss tangent. If the amount of component (b) is above this range, the proportion of aliphatic chains derived from component (b) in the intermediate polyimide resin will be too high, resulting in a low heat resistance of the cured product.

[0019] The component (b) used in the synthesis of the intermediate polyimide resin is not particularly limited as long as it is an aliphatic compound having two amino groups in one molecule, but an aliphatic diamino compound having 6 to 36 carbon atoms is preferred. Specific examples of the component (b) include hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, C14 branched diamine, C18 branched diamine, dimer diamine, and diaminopolysiloxane. These may be used alone or in combination of two or more.

[0020] In this specification, the dimer diamine described as a specific example of component (b) is a compound in which two carboxy groups of a dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, have been substituted with primary amino groups (see, for example, JP-A-9-12712). Specific examples of commercially available dimer diamines include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.), and Versamine 551 (manufactured by Cognis Japan Co., Ltd.). These may be used alone or in combination of two or more.

[0021] The component (c) used in the synthesis of the intermediate polyimide resin is not particularly limited as long as it has two acid anhydride groups in one molecule. Specific examples of the component (c) include pyromellitic anhydride, ethylene glycol bis(anhydrotrimellitate), glycerin bis(anhydrotrimellitate) monoacetate, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3- Examples include methylcyclohexene-1,2-dicarboxylic anhydride, 3a,4,5,9b-tetrahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-1,3-dione, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, and 5,5'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione). Among these, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-diphenylethertetracarboxylic dianhydride are preferred in terms of solvent solubility, adhesion to substrates, and photosensitivity. These may be used alone or in combination of two or more.

[0022] The component (c) used in the synthesis of the intermediate polyimide resin preferably contains at least one compound selected from the group consisting of the following formulae (1) to (4):

[0023] [ka]

[0024] In formula (4), Y represents C(CF3)2, SO2, CO, O, a direct bond, or a divalent linking group represented by the following formula (5): The two linking moieties represented by formula (5) are each bonded to 2-benzofuran.

[0025] [ka]

[0026] The component (d) used in the synthesis of the intermediate polyimide resin is not particularly limited as long as it is an aromatic compound having two amino groups in one molecule. Specific examples of the component (d) include m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether, 3,3'-dimethyl-4,4'-diaminodiphenyl thioether, 3,3'-diethoxy-4,4'-diaminodiphenyl thioether, and 3,3 '-Diaminodiphenyl thioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenyl thioether, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-diamino Diphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 2,2'-bis(3-aminophenoxyphenyl)propane, 2,2'-bis(4-aminophenoxyphenyl)propane, 1,3-bis(4 bis(4-aminophenoxyphenyl)benzene, 1,3'-bis(3-aminophenoxyphenyl)propane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-propylphenyl)methane, and bis(4-amino-3,5-dipropylphenyl)methane. These may be used alone or in combination of two or more.

[0027] The component (d) used in the synthesis of the intermediate polyimide resin preferably contains at least one compound selected from the group consisting of the following formulae (6) and (8).

[0028] [ka]

[0029] In formula (6), R1 represents a methyl group or a trifluoromethyl group, and in formula (8), Z represents CH(CH3), SO2, CH2, O-C6H4-O, O, a direct bond, or a divalent linking group represented by formula (9) below, and R3 represents a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group. Note that the two linking moieties represented by formula (9) are each bonded to 2-benzofuran.

[0030] [ka]

[0031] The intermediate polyimide resin can be synthesized by a known method. For example, a solvent, dehydrating agent, and catalyst are added to a mixture of components (b) to (d) used in the synthesis, and the mixture is heated and stirred at 100 to 300°C under an inert gas atmosphere such as nitrogen. This causes an imidization reaction (a ring-closing reaction accompanied by dehydration) via polyamic acid, yielding an intermediate polyimide resin solution. During this process, water generated during imidization is distilled out of the system, and after the reaction is complete, the dehydrating agent and catalyst are also distilled out of the system, allowing for the production of a highly pure intermediate polyimide resin without the need for washing. Examples of dehydrating agents include toluene and xylene, and examples of catalysts include pyridine and triethylamine.

[0032] Solvents that can be used in the synthesis of the intermediate polyimide resin include methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetylacetone, γ-butyrolactone, diacetone alcohol, cyclohexen-1-one, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, ethyl isoamyl ether, ethyl-t-butyl ether, ethyl benzyl ether, cresyl methyl ether, anisole, phenetole, methyl acetate, ethyl acetate, propyl acetate, and isoacetate. Propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, butyl propionate, benzyl propionate, methyl butyrate, ethyl butyrate, isopropyl butyrate, butyl butyrate, isoamyl butyrate, methyl lactate, ethyl lactate, butyl lactate, ethyl isovalerate, isoamyl isovalerate, diethyl oxalate, dibutyl oxalate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, etc. These may be used alone or in combination of two or more.

[0033] [Isocyanate-modified polyimide resin] Next, the isocyanate-modified polyimide resin of the present invention will be described. The isocyanate-modified polyimide resin of the present invention is obtained by the reaction of an intermediate polyimide resin with component (a). The reaction between the intermediate polyimide resin and component (a) is a copolymerization reaction between an amino group or an acid anhydride group at the terminal of the intermediate polyimide resin and an isocyanate group of component (a), and the reaction between the amino group and the isocyanate group forms a urea bond, and the reaction between the acid anhydride and the isocyanate group forms an imide bond. The amount of component (a) used in the copolymerization reaction between the intermediate polyimide resin and component (a) is preferably less than 1 equivalent of the isocyanate group of component (a) relative to 1 equivalent of the terminal functional group of the intermediate polyimide resin, more preferably 0.50 to 0.99 equivalents, and even more preferably 0.67 to 0.98 equivalents. By using component (a) in this range relative to the intermediate polyimide resin, the isocyanate-modified polyimide resin is sufficiently polymerized, the residual rate of unreacted raw materials is reduced, and various properties such as heat resistance and flexibility are improved after curing of the resin composition containing the isocyanate-modified polyimide resin and the polyimide resin, etc. The terminal functional equivalent of the intermediate polyimide resin referred to here means a value calculated from the amounts of each raw material used when synthesizing the intermediate polyimide resin.

[0034] The component (a) used in the synthesis of the isocyanate-modified polyimide resin of the present invention can be any compound having two isocyanate groups in the molecule, and multiple diisocyanate compounds can be reacted simultaneously. Preferred examples of component (a) include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tridenediisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, allylene sulfone ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, and norbornane-diisocyanatemethyl. Among these, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, or isophorone diisocyanate is more preferred, as they have an excellent balance between flexibility, adhesiveness, and the like.

[0035] The reaction between the intermediate polyimide resin and component (a) may be carried out by a known synthesis method. Specifically, the isocyanate-modified polyimide resin of the present invention can be obtained by adding component (a) to the intermediate polyimide resin solution obtained by the above synthesis method and heating and stirring at 80 to 150° C. The reaction time for the synthesis reaction of the intermediate polyimide resin and the reaction of the intermediate polyimide resin with component (a) is greatly affected by the reaction temperature, but it is preferable to carry out the reaction until the increase in viscosity accompanying the progress of the reaction reaches equilibrium and the maximum molecular weight is obtained, which is usually several tens of minutes to 20 hours.

[0036] The isocyanate-modified polyimide resin solution obtained above can be poured into a poor solvent such as water, methanol, or hexane to separate the resulting polymer, and then the solid content of the isocyanate-modified polyimide resin of the present invention can be obtained by a reprecipitation method.

[0037] [Terminal-modified isocyanate-modified polyimide resin] Since the isocyanate-modified polyimide resin of the present invention has amino groups and / or acid anhydride groups at both terminals, the terminals can be modified by reacting it with a compound having a functional group reactive with these functional groups to prepare a terminal-modified isocyanate-modified polyimide resin. Examples of compounds reactive with amino groups and / or acid anhydride groups include compounds having an acid anhydride group such as maleic anhydride, compounds having an alcoholic hydroxyl group such as hydroxyethyl acrylate, compounds having a phenolic hydroxyl group such as phenol, compounds having an isocyanate group such as 2-methacryloyloxyethyl isocyanate, and compounds having an epoxy group such as glycidyl methacrylate. By modifying the terminals, both terminals of the isocyanate compound of the present invention can be changed to functional groups other than amino groups and acid anhydride groups (for example, when terminal modification is performed with hydroxyethyl acrylate, the terminals of the isocyanate-modified polyimide resin can be changed to acryloyl groups), so it is also possible to prepare a composition in which the compound is combined with a compound that reacts with functional groups other than amino groups or acid anhydride groups.

[0038] [Resin composition] The resin composition of the present invention can be broadly divided into a first embodiment containing the isocyanate-modified polyimide resin of the present invention and a compound other than the isocyanate-modified polyimide resin, and a second embodiment containing the terminal-modified isocyanate-modified polyimide resin of the present invention and a compound other than the terminal-modified isocyanate-modified polyimide resin. First, the resin composition according to the first aspect of the present invention, which contains an isocyanate-modified polyimide resin and a compound other than the isocyanate-modified polyimide resin, will be described.

[0039] The compound other than the isocyanate-modified polyimide resin contained in the resin composition of the first embodiment is not limited to either a compound that reacts with the isocyanate-modified polyimide resin (hereinafter referred to as the "reactive compound of the first embodiment") or a compound that does not react with the isocyanate-modified polyimide resin (hereinafter referred to as the "non-reactive compound of the first embodiment"). The reactive compound of the first embodiment is a compound that reacts with an acid anhydride group and / or an amino group at the terminal of the isocyanate-modified polyimide resin. Examples of the reactive compound of the first aspect that reacts with an acid anhydride group include a compound having an epoxy group, a compound having a thiol group, and a compound having an amino group, and a compound having an epoxy group is preferred.

[0040] The compound having an epoxy group is not particularly limited as long as it has one or more epoxy groups in one molecule, but a compound having two or more epoxy groups in one molecule is preferred, and examples thereof include novolac epoxy resins, bisphenol epoxy resins, biphenyl epoxy resins, triphenylmethane epoxy resins, and phenol aralkyl epoxy resins. Specific examples include NC-3000, NC-7000, XD-1000, EOCN-1020, EPPN-502H (all manufactured by Nippon Kayaku Co., Ltd.), jER828 (manufactured by Mitsubishi Chemical Corporation), and jER807 (manufactured by Mitsubishi Chemical Corporation), with NC-3000 or XD-1000 being preferred.

[0041] The resin composition of the present invention, which contains a compound having an epoxy group as the reactive compound of the first embodiment, may optionally contain various heat-curing catalysts to promote the curing reaction between the acid anhydride group and the compound having an epoxy group. Examples of heat-curing catalysts include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octoate. The amount of heat-curing catalyst added to the resin composition of the present invention containing a compound having an epoxy group is 0.1 to 10% by mass relative to the compound having an epoxy group. The resin composition of the present invention containing a compound having an epoxy group as the reactive compound of the first aspect may also contain a compound reactive with an epoxy group, such as a compound having a phenolic hydroxyl group, a compound having an amino group, or a compound having an acid anhydride group.

[0042] The compound having a thiol group is not particularly limited as long as it is a compound having one or more thiol groups in one molecule, but a compound having two or more thiol groups in one molecule is preferred, and examples thereof include pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, ethylene glycol bis(3-mercaptobutyrate), and the like. thioglycolate, 1,4-butanediol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, di(2-mercaptoethyl)ether, 1,4-butanedithiol, 1,3,5-trimercaptomethylbenzene, 1,3,5-trimercaptomethyl-2,4,6-trimethylbenzene, polyethers containing terminal thiol groups, polythioethers containing terminal thiol groups, thiol compounds obtained by reacting an epoxy compound with hydrogen sulfide, and thiol compounds having terminal thiol groups obtained by reacting a polythiol compound with an epoxy compound. Commercially available compounds having a thiol group include Karenz MT PE1, Karenz MT NR1, Karenz MT BD1 (all manufactured by Showa Denko KK), and the like.

[0043] The compound having an amino group is not particularly limited as long as it has one or more amino groups in one molecule, but a compound having two or more amino groups in one molecule is preferred. Specific examples of the compound having an amino group include hexamethylenediamine, naphthalenediamine, 1,3-bis(aminomethyl)cyclohexane, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), and norbornanediamine.

[0044] Examples of the reactive compound of the first aspect that reacts with an amino group include a compound having a maleimide group, a compound having an epoxy group, and a compound having a carboxy group, and a compound having a maleimide group is preferred.

[0045] The compound having a maleimide group is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, but a compound having two or more maleimide groups in one molecule is preferred, and examples thereof include polyfunctional maleimide compounds obtained by reacting 3,4,4'-triaminodiphenylmethane, triaminophenol, or the like with maleic anhydride, maleimide compounds obtained by reacting tris-(4-aminophenyl)-phosphate, tris(4-aminophenyl)-phosphate, or tris(4-aminophenyl)-thiophosphate with maleic anhydride, trismaleimide compounds such as tris(4-maleimidophenyl)methane, bis(3,4-dimaleimidophenyl)methane, tetrahydrofuran ... Examples of suitable phenylmaleimide compounds include tetramaleimide compounds such as tetramaleimide benzophenone, tetramaleimide naphthalene, and maleimides obtained by reacting triethylenetetramine with maleic anhydride; phenol novolac-type maleimide resins; isopropylidenebis(phenoxyphenylmaleimide)phenylmaleimide aralkyl resins; and biphenylene-type phenylmaleimide aralkyl resins. Commercially available products include MIR-3000 and MIR-5000 (all manufactured by Nippon Kayaku Co., Ltd.), BMI-70 and BMI-80 (all manufactured by K.I. Kasei Co., Ltd.), BMI-1000, BMI-2000, and BMI-3000 (all manufactured by Daiwa Kasei Kogyo Co., Ltd.).

[0046] A compound having a maleimide group undergoes self-crosslinking between maleimide groups due to the action of a radical initiator. Therefore, when a resin composition using an isocyanate-modified polyimide resin having an amino group at its terminal, a compound having a maleimide group, and a radical initiator is heated, the maleimide groups undergo self-crosslinking and the polyimide resin and maleimide resin are copolymerized to form a cured product. Radical initiators that can be used for self-crosslinking between maleimide groups include peroxides such as dicumyl peroxide and dibutyl peroxide, and azo compounds such as 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile). The amount of radical initiator added to the resin composition of the present invention containing a compound having a maleimide group is 0.1 to 10% by mass relative to the compound having a maleimide group.

[0047] Examples of the compound having an epoxy group include the same as the above-mentioned "compound having an epoxy group as the reactive compound of the first aspect that reacts with an acid anhydride group," and the catalysts, compounds, etc. that can be used in combination are also the same. The compound having a carboxy group is not particularly limited as long as it has one or more carboxy groups in one molecule, but a compound having two or more carboxy groups in one molecule is preferred. Specific examples of the compound having a carboxy group include linear alkyl diacids such as butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, and malic acid, alkyl tricarboxylic acids such as 1,3,5-pentanetricarboxylic acid and citric acid, phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid, and methylnadic acid.

[0048] The content of the reactive compound of the first embodiment in the resin composition of the present invention is preferably an amount such that the reactive group equivalent of the reactive compound of the first embodiment is 0.1 to 500 equivalents per equivalent of the terminal functional group of the isocyanate-modified polyimide resin. By setting the reactive group equivalent of the reactive compound of the first embodiment within this range, a cured resin composition having good physical properties and crosslink density can be obtained. The equivalent weight here is a value calculated from the amounts of each raw material used when synthesizing the isocyanate-modified polyimide resin. In addition, when the isocyanate-modified polyimide resin has both an acid anhydride group and an amino group at both ends, both the reactive compound of the first embodiment that reacts with the acid anhydride group and the reactive composition of the first embodiment that reacts with the amino group may be used in combination.

[0049] The non-reactive compound of the first embodiment is not limited in any way as long as it is a compound that does not react with the isocyanate-modified polyimide resin. Organic solvents and the like are also included in this category, but resin compositions containing organic solvents are also called "varnishes," and this is a preferred embodiment in applications where dilution with an organic solvent improves the handleability of the resin composition. Specific examples of organic solvents include amide-based solvents such as γ-butyrolactones, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone; sulfones such as tetramethylene sulfone; ether-based solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, and propylene glycol monobutyl ether; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic solvents such as toluene and xylene. The organic solvent is used in such a range that the solid content concentration in the resin composition excluding the organic solvent is generally 10 to 80% by mass, preferably 20 to 70% by mass.

[0050] The compound having a thiol group and the compound having an amino group described in the section "Reactive Compound of First Aspect Reacting with Acid Anhydride Group" do not react with amino groups, and therefore, a resin composition may be prepared in which these compounds are used in combination with an isocyanate-modified polyimide resin having an amino group at its terminal as the non-reactive compound of the first aspect. The compound having a maleimide group and the compound having a carboxy group described in the section "Reactive Compound of First Aspect Reacting with Amino Group" do not react with acid anhydride groups, and therefore, a resin composition may be prepared in which these compounds are used in combination with an isocyanate-modified polyimide resin having an acid anhydride group at its terminal as the non-reactive compound of the first aspect.

[0051] As described in the section on the compound having a maleimide group and the section on the compound having an epoxy group in the reactive compound of the first embodiment, self-crosslinking of the non-reactive compound of the first embodiment or copolymerization of multiple non-reactive compounds of the first embodiment are also preferred embodiments of the resin composition of the present invention. By self-crosslinking or copolymerizing the non-reactive compound of the first embodiment in the resin composition, a cured product of the non-reactive compound containing an unbonded isocyanate-modified polyimide resin can be obtained.

[0052] Next, a resin composition according to a second embodiment of the present invention containing a terminally modified isocyanate-modified polyimide resin and a compound other than the terminally modified isocyanate-modified polyimide resin will be described. The compound other than the terminal-modified isocyanate-modified polyimide resin contained in the resin composition of the second embodiment is not limited to either a compound that reacts with the terminal-modified isocyanate-modified polyimide resin (hereinafter referred to as the "reactive compound of the second embodiment") or a compound that does not react with the terminal-modified isocyanate-modified polyimide resin (hereinafter referred to as the "non-reactive compound of the second embodiment").

[0053] The reactive compound of the second embodiment is a compound that reacts with a functional group that the terminal-modified isocyanate-modified polyimide resin has at its terminal. Since the functional group that the terminal-modified isocyanate-modified polyimide resin has at its terminal depends on the compound used for terminal modification, the reactive compound of the second embodiment can be selected in consideration of the terminal functional group of the terminal-modified isocyanate-modified polyimide resin, and a compound that reacts with this terminal functional group can be selected. For example, when both terminals of an isocyanate-modified polyimide resin having an amino group are modified with a tetrabasic acid dianhydride, both terminals of the terminally modified isocyanate-modified polyimide resin become acid anhydride groups, and therefore examples of the reactive compound of the second aspect that reacts with this include the same compounds as the reactive compound of the first aspect that reacts with the terminal acid anhydride groups of the isocyanate-modified polyimide resin, and the catalysts, compounds, etc. that can be used in combination with this are also the same. Furthermore, when both terminals of an isocyanate-modified polyimide resin having an acid anhydride group are modified with a diamino compound, both terminals of the terminally modified isocyanate-modified polyimide resin become amino groups, and therefore examples of the reactive compound of the second aspect that reacts with this include the same compounds as the reactive compound of the first aspect that reacts with the terminal amino groups of the isocyanate-modified polyimide resin.

[0054] As another example, terminal-modified isocyanate-modified polyimide resins obtained by using an epoxy resin, a compound having a maleimide group (including a maleimide resin), an isocyanate resin, an allyl resin, a benzoxazine resin, or an acryloyl resin to modify the terminals of an isocyanate-modified polyimide resin will have terminals that are epoxy groups, maleimide groups, isocyanate groups, allyl groups, benzoxazine groups, or acryloyl groups, respectively. Therefore, if a compound that reacts with these terminal functional groups is used as the reactive compound of the second embodiment, a catalyst or the like that is typically used in the reaction of the terminal functional group with the reactive compound may be used in combination.

[0055] For the terminally modified isocyanate-modified polyimide resin having an acryloyl group at the end, it is preferable to use a compound having an acryloyl group as the reactive compound of the second embodiment in combination. Specific examples thereof include alkyl (meth)acrylates such as 2-ethylhexyl (meth)acrylate and cyclohexyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; mono- or di(meth)acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethyl isocyanurate. Examples of such an initiator include polyhydric (meth)acrylates of alcohols or their ethylene oxide or propylene oxide adducts; (meth)acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth)acrylate and polyethoxydi(meth)acrylate of bisphenol A; (meth)acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; and melamine (meth)acrylate. These initiators may be used in combination with a polymerization initiator that can be used for (co)polymerization of a compound having an acryloyl group.

[0056] The content of the reactive compound of the second aspect in the resin composition of the present invention is preferably an amount such that the reactive group equivalent of the reactive compound of the second aspect is 0.1 to 500 equivalents per equivalent of the terminal functional group of the terminal-modified isocyanate-modified polyimide resin. By setting the reactive group equivalent of the reactive compound of the second aspect within the above range, a cured resin composition having good physical properties and crosslink density can be obtained. The equivalent weight here is a value calculated from the amount of each raw material used when synthesizing the terminal-modified isocyanate-modified polyimide resin. When the terminally modified isocyanate-modified polyimide resin has different functional groups at both ends, a plurality of reactive compounds of the second embodiment that react with the respective functional groups may be used in combination.

[0057] The non-reactive compound of the second embodiment is not limited in any way as long as it is a compound that does not react with the terminally modified isocyanate-modified polyimide resin. Organic solvents and the like are also included in this category, but resin compositions containing organic solvents are also called "varnishes," and this is a preferred embodiment in applications where dilution with an organic solvent improves the handleability of the resin composition. Specific examples of the organic solvent and the content thereof in the resin composition are the same as those of the organic solvent and the content thereof described in the section on the non-reactive compound of the first embodiment.

[0058] The resin composition of the present invention may optionally contain known additives. Specific examples of such additives include epoxy resin curing agents, polybutadiene and its modified products, modified acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds, silicone gel, silicone oil, inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, and glass powder, surface treatment agents for fillers such as silane coupling agents, release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green. The amount of these additives to be added is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, per 100 parts by mass of the resin composition.

[0059] The curing temperature and curing time of the resin composition of the present invention may be selected taking into consideration the combination of the functional groups at both ends of the (terminally modified) isocyanate-modified polyimide resin and the reactive group of the reactive compound, and for example, the curing temperature of a resin composition containing a maleimide resin or a resin composition containing an epoxy resin is preferably 120 to 250°C, and the curing time is generally from several tens of minutes to several hours.

[0060] The method for preparing the resin composition of the present invention is not particularly limited, but the components may be simply mixed uniformly, or may be prepolymerized. For example, the (terminally modified) isocyanate-modified polyimide resin of the present invention and a reactive compound may be heated in the presence or absence of a catalyst and in the presence or absence of a solvent to form a prepolymer. The components may be mixed or prepolymerized using, for example, an extruder, kneader, or roll in the absence of a solvent, or in a reaction vessel equipped with a stirrer in the presence of a solvent.

[0061] The resin composition of the present invention can be heated and melted to reduce the viscosity, and then impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, alumina fibers, etc. to obtain a prepreg. Alternatively, a prepreg can be obtained by impregnating reinforcing fibers with the varnish and drying them by heating. The prepreg is cut into a desired shape and laminated with copper foil or the like as needed. The resin composition is then heated and cured while applying pressure to the laminate using a press molding method, autoclave molding method, sheet winding molding method, or the like, to obtain the substrate of the present invention, such as an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material. Alternatively, the substrate of the present invention can be obtained by coating the composition on copper foil, drying the solvent, laminating a polyimide film or LCP (liquid crystal polymer), hot pressing, and then heat curing. In some cases, the substrate of the present invention can be obtained by coating the composition on the polyimide film or LCP side and laminating it on copper foil. [Example]

[0062] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the examples, "parts" means parts by mass, and "%" means % by mass.

[0063] Example 1 (Synthesis of isocyanate-modified polyimide resin of the present invention) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 5.28 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 13.28 parts of PRIAMINE 1075 (C36 dimer diamine, manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 14.89 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g / mol), 74.45 parts of anisole, 0.97 parts of triethylamine, and 19.80 parts of toluene, and heated to 120 ° C. to dissolve the raw materials. The reaction was carried out at 135 ° C. for 4 hours, while removing the water generated by ring closure of the amic acid by azeotropy with toluene. After the production of water had ceased, the remaining triethylamine and toluene were subsequently removed at 140°C to obtain an intermediate polyimide resin solution. The molar ratio (moles of acid anhydride component / moles of diamine component) of the diamine components (components (b) and (d)) and acid anhydride component (component (c)) used in the synthesis of the intermediate polyimide resin was 1.20. Next, 1.48 parts of TMDI (trimethylhexamethylene diisocyanate, manufactured by Degussa Huels, molecular weight 210.28 g / mol) and 3.30 parts of anisole were added to the intermediate polyimide resin solution obtained above, and the mixture was heated at 130°C for 3 hours to obtain an isocyanate-modified polyimide resin solution (A-1) (non-volatile content 30.1%). The final molar ratio of the raw material components of the isocyanate-modified polyimide resin obtained above (moles of acid anhydride component / (moles of diamine component + moles of diisocyanate component)) was 1.02.

[0064] Example 2 (Synthesis of isocyanate-modified polyimide resin of the present invention) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 5.37 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 13.14 parts of PRIAMINE 1075 (C36 dimer diamine, manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 14.89 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g / mol), 74.35 parts of anisole, 0.97 parts of triethylamine, and 19.79 parts of toluene, and heated to 120 ° C. to dissolve the raw materials. The reaction was carried out at 135 ° C. for 4 hours, while removing the water generated by ring closure of the amic acid by azeotropy with toluene. After the production of water had ceased, the remaining triethylamine and toluene were subsequently removed at 140°C to obtain an intermediate polyimide resin solution. The molar ratio (moles of acid anhydride component / moles of diamine component) of the diamine components (components (b) and (d)) and acid anhydride component (component (c)) used in the synthesis of the intermediate polyimide resin was 1.20. Next, 1.19 parts of HDI (hexamethylene diisocyanate, manufactured by Asahi Kasei Corporation, molecular weight 168.20 g / mol) and 2.64 parts of anisole were added to the intermediate polyimide resin solution obtained above, and the mixture was heated at 130°C for 3 hours to obtain an isocyanate-modified polyimide resin solution (A-2) (non-volatile content 30.0%). The final molar ratio of the raw material components of the isocyanate-modified polyimide resin obtained above (moles of acid anhydride component / (moles of diamine component + moles of diisocyanate component)) was 1.02.

[0065] Example 3 (Synthesis of isocyanate-modified polyimide resin of the present invention) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 5.25 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 13.32 parts of PRIAMINE 1075 (C36 dimer diamine, manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 14.89 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g / mol), 74.48 parts of anisole, 0.97 parts of triethylamine, and 19.80 parts of toluene, heated to 120 ° C. to dissolve the raw materials. The reaction was carried out at 135 ° C. for 4 hours, while removing the water generated by ring closure of the amic acid by azeotropy with toluene. After the production of water had ceased, the remaining triethylamine and toluene were subsequently removed at 140°C to obtain an intermediate polyimide resin solution. The molar ratio (moles of acid anhydride component / moles of diamine component) of the diamine components (components (b) and (d)) and acid anhydride component (component (c)) used in the synthesis of the intermediate polyimide resin was 1.20. Next, 1.57 parts of IPDI (isophorone diisocyanate, manufactured by Degussa Huels, molecular weight 222.29 g / mol) and 3.49 parts of anisole were added to the intermediate polyimide resin solution obtained above, and the mixture was heated at 130°C for 3 hours to obtain an isocyanate-modified polyimide resin solution (A-3) (non-volatile content 30.0%). The final molar ratio of the raw material components of the isocyanate-modified polyimide resin obtained above (moles of acid anhydride component / (moles of diamine component + moles of diisocyanate component)) was 1.02.

[0066] Example 4 (Synthesis of isocyanate-modified polyimide resin of the present invention) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 10.16 parts of BAPP (2,2-bis[4-(4-aminophenoxy)phenyl]propane, manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 410.52 g / mol), 12.42 parts of PRIAMINE 1075 (C36 dimer diamine, manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 8.73 parts of PMDA (pyromellitic dianhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight 218.12 g / mol), 69.69 parts of anisole, 0.81 parts of triethylamine, and 19.16 parts of toluene. The raw materials were dissolved by heating to 120 ° C. The reaction was carried out at 135 ° C. for 4 hours while removing the water generated by ring closure of the amic acid by azeotropy with toluene. After the production of water had ceased, the remaining triethylamine and toluene were subsequently removed at 140°C to obtain an intermediate polyimide resin solution. The molar ratio (moles of diamine component / moles of acid anhydride component) of the diamine components (components (b) and (d)) and acid anhydride component (component (c)) used in the synthesis of the intermediate polyimide resin was 1.20. Next, 1.19 parts of HDI (hexamethylene diisocyanate, manufactured by Asahi Kasei Corporation, molecular weight 168.20 g / mol) and 2.64 parts of anisole were added to the intermediate polyimide resin solution obtained above, and the mixture was heated at 130°C for 3 hours to obtain an isocyanate-modified polyimide resin solution (A-4) (non-volatile content 30.1%). The final molar ratio of the raw material components of the isocyanate-modified polyimide resin obtained above (moles of diamine component / (moles of acid anhydride component + moles of diisocyanate component)) was 1.02.

[0067] Example 5 (Synthesis of terminally modified isocyanate-modified polyimide resin of the present invention) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 9.13 parts of BAPP (2,2-bis[4-(4-aminophenoxy)phenyl]propane, manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 410.52 g / mol), 13.76 parts of PRIAMINE 1075 (C36 dimer diamine, manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 11.77 parts of BPDA (biphenyltetracarboxylic dianhydride, manufactured by Mitsubishi Chemical Corporation, molecular weight 294.22 g / mol), 77.15 parts of anisole, 0.81 parts of triethylamine, and 20.14 parts of toluene, and heated to 120 ° C. to dissolve the raw materials. The reaction was carried out at 135 ° C. for 4 hours, while removing the water generated by ring closure of the amic acid via azeotropy with toluene. After the production of water had ceased, the remaining triethylamine and toluene were subsequently removed at 140°C to obtain an intermediate polyimide resin solution. The molar ratio (moles of diamine component / moles of acid anhydride component) of the diamine components (components (b) and (d)) and acid anhydride component (component (c)) used in the synthesis of the intermediate polyimide resin was 1.20. Next, 1.19 parts of HDI (hexamethylene diisocyanate, manufactured by Asahi Kasei Corporation, molecular weight 168.20 g / mol) and 2.64 parts of anisole were added to the intermediate polyimide resin solution obtained above and heated at 130 ° C for 3 hours to obtain an isocyanate-modified polyimide resin solution (A-5). The final molar ratio of the raw material components of the isocyanate-modified polyimide resin obtained above (moles of diamine component / (moles of acid anhydride component + moles of diisocyanate component)) was 1.02. Next, 0.08 parts of maleic anhydride (molecular weight 98.06 g / mol), 0.3 parts of triethylamine, and 5.2 parts of toluene were added to the isocyanate-modified polyimide resin solution (A-5), and the mixture was allowed to react at 135 ° C for 4 hours. After the production of water stopped, the remaining triethylamine and toluene were removed at 140°C to obtain a terminal-modified isocyanate-modified polyimide resin solution (B-5) (non-volatile content 30.2%) in which both terminals of the isocyanate-modified polyimide resin were modified with maleic anhydride.

[0068] Example 6 (Synthesis of isocyanate-modified polyimide resin of the present invention) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 1.22 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 10.38 parts of Diamine 18 (C18 diamine, manufactured by Okamura Oil Mills, molecular weight 284.53 g / mol), 14.89 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), 58.98 parts of anisole, 0.97 parts of triethylamine, and 17.78 parts of toluene, and heated to 120 ° C. to dissolve the raw materials. The reaction was carried out at 135 ° C. for 4 hours, while the water generated by the ring closure of the amic acid was removed azeotropically with toluene. After the production of water had ceased, the remaining triethylamine and toluene were subsequently removed at 140°C to obtain an intermediate polyimide resin solution. The molar ratio (moles of acid anhydride component / moles of diamine component) of the diamine components (components (b) and (d)) and acid anhydride component (component (c)) used in the synthesis of the intermediate polyimide resin was 1.20. Next, 1.19 parts of HDI (hexamethylene diisocyanate, manufactured by Asahi Kasei Corporation, molecular weight 168.20 g / mol) and 2.64 parts of anisole were added to the intermediate polyimide resin solution obtained above, and the mixture was heated at 130°C for 3 hours to obtain an isocyanate-modified polyimide resin solution (A-6) (non-volatile content 30.0%). The final molar ratio of the raw material components of the isocyanate-modified polyimide resin obtained above (moles of acid anhydride component / (moles of diamine component + moles of diisocyanate component)) was 1.02.

[0069] Comparative Example 1 (Synthesis of Comparative Polyimide Resin) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 7.53 parts of BAPP (2,2-bis[4-(4-aminophenoxy)phenyl]propane, manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 410.52 g / mol), 12.43 parts of PRIAMINE 1075 (C36 dimer diamine, manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g / mol), 72.37 parts of anisole, 0.81 parts of triethylamine, and 19.51 parts of toluene, and heated to 120 ° C. to dissolve the raw materials. The reaction was carried out at 135 ° C. for 4 hours, while removing the water generated by ring closure of the amic acid by azeotropy with toluene. After the production of water had ceased, the remaining triethylamine and toluene were subsequently removed at 140°C to obtain a comparative polyimide resin solution (R-1) (non-volatile content 30.0%). The final molar ratio of the raw material components of the comparative polyimide resin obtained above (moles of acid anhydride component / moles of diamine component) was 1.05.

[0070] Comparative Example 2 (Synthesis of Comparative Polyimide Resin) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 6.45 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 11.71 parts of PRIAMINE 1075 (C36 dimer diamine, manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g / mol), 68.34 parts of anisole, 0.81 parts of triethylamine, and 18.99 parts of toluene, and heated to 120 ° C. to dissolve the raw materials. The reaction was carried out at 135 ° C. for 4 hours, while removing the water generated by ring closure of the amic acid by azeotropy with toluene. After the production of water had ceased, the remaining triethylamine and toluene were subsequently removed at 140°C to obtain a comparative polyimide resin solution (R-2) (non-volatile content 30.2%). The final molar ratio of the raw material components of the comparative polyimide resin obtained above (moles of acid anhydride component / moles of diamine component) was 1.02.

[0071] Examples 7 to 12 and Comparative Examples 3 and 4 (Preparation of Resin Compositions) The polyimide resin solutions (A-1) to (A-4), (B-5), and (A-6) obtained in Examples 1 to 6, the comparative polyimide resin solutions (R-1) and (R-2) obtained in Comparative Examples 1 and 2, MIR3000-70MT (biphenyl skeleton-containing maleimide resin, non-volatile content 70.0%) manufactured by Nippon Kayaku Co., Ltd. as a compound having a maleimide group, dicumyl peroxide (DCP) as a radical initiator, NC-3000 (biphenyl skeleton-containing epoxy resin, epoxy equivalent 277 g / eq, softening point 60°C) manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin, and C11Z-A (Shikoku Chemicals Corporation) as a curing accelerator were mixed in the amounts shown in Table 1 (unit: "parts"; the parts of the polyimide resin and the compound having a maleimide group are the parts of the solution including the solvent), to obtain resin compositions of the present invention and comparative resin compositions.

[0072] [Table 1]

[0073] (Evaluation of adhesive strength) Using the resin compositions obtained in Examples 7 to 12 and Comparative Examples 3 and 4, the adhesive strength to copper foil and thermal properties of the cured products of the resin compositions were evaluated. The resin compositions obtained above were applied to the rough surface of CF-T4X-SV-18 copper foil (Fukuda Metal Foil & Powder Co., Ltd.) using an automatic applicator and dried by heating at 120°C for 10 minutes. The thickness of the dried coating was 30 μm. The rough surface of T4X was placed on the coating on the copper foil obtained above, and the resulting foil was vacuum-pressed at 200°C for 60 minutes under 3 MPa. The resulting test specimens were cut into 10 mm widths and measured for 90° peel strength (peel speed: 50 mm / min) between the copper foils using an autograph AGS-X-500N (Shimadzu Corporation) to evaluate the adhesive strength of the copper foils. Visual inspection of the samples after testing revealed cohesive failure in all cases. The results are shown in Tables 2 and 3.

[0074] (Evaluation of thermal properties) Test pieces prepared in the same manner as in the "Evaluation of adhesive strength" above were floated in a solder bath heated to 288°C using a POT-200C (manufactured by Taiyo Electric Industry Co., Ltd.), and the thermal properties were evaluated based on the time until blisters appeared. The results are shown in Tables 2 and 3.

[0075] (Evaluation of mechanical and dielectric properties) Using the same method as described above for "Evaluation of Adhesion Strength," except for varying the coating thickness of the automatic applicator, coatings with a dry thickness of 100 μm were formed on the rough surface of T4X and cured at 200°C for 60 minutes. The copper foil was removed by etching with an iron(III) chloride solution with a liquid specific gravity of 45 Baumé, followed by rinsing with ion-exchanged water and drying at 105°C for 10 minutes to obtain cured films. The stress at break, elongation at break, and modulus of elasticity of the cured films were measured using an AGS-X-500N Autograph (Shimadzu Corporation), and the dielectric properties at 10 GHz were measured using a 8719ET Network Analyzer (Agilent Technologies) by cavity resonance. The results are shown in Tables 2 and 3.

[0076] [Table 2]

[0077] [Table 3]

[0078] From the results in Tables 2 and 3, the resin compositions of the present invention are excellent in all of adhesive strength, mechanical properties, thermal properties and dielectric constant, whereas the resin compositions of the comparative examples are inferior in mechanical properties, have high dielectric tangents and are also inferior in either adhesive strength or thermal properties.

[0079] Example 13 (Synthesis of isocyanate-modified polyimide resin of the present invention) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 7.70 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 10.64 parts of PRIAMINE 1075 (C36 dimer diamine, manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g / mol), 68.43 parts of anisole, 0.81 parts of triethylamine, and 19.00 parts of toluene, heated to 120 ° C. to dissolve the raw materials. The reaction was carried out at 135 ° C. for 4 hours, while removing the water generated by ring closure of the amic acid by azeotropy with toluene. After the production of water had ceased, the remaining triethylamine and toluene were subsequently removed at 140°C to obtain an intermediate polyimide resin solution. The molar ratio (moles of diamine component / moles of acid anhydride component) of the diamine components (components (b) and (d)) and acid anhydride component (component (c)) used in the synthesis of the intermediate polyimide resin was 1.05. Next, 0.26 parts of IPDI (isophorone diisocyanate, manufactured by Degussa Huels, molecular weight 222.29 g / mol) and 0.58 parts of anisole were added to the intermediate polyimide resin solution obtained above, and the mixture was heated at 130°C for 3 hours to obtain an isocyanate-modified polyimide resin solution (A-7) (non-volatile content 30.1%). The final molar ratio of the raw material components of the isocyanate-modified polyimide resin obtained above (moles of diamine component / (moles of acid anhydride component + moles of diisocyanate component)) was 1.02.

[0080] Examples 14 to 19 (Preparation of Resin Compositions) The polyimide resin solutions (A-1), (A-3), and (A-7) obtained in Examples 1, 3, and 13, MIR3000-70MT (biphenyl skeleton-containing maleimide resin, non-volatile content 70.0%) and MIR5000-60T (novolac-type maleimide resin, non-volatile content 60.0%) manufactured by Nippon Kayaku Co., Ltd. as compounds having maleimide groups, and dicumyl peroxide (DCP) as a radical initiator were mixed in the amounts shown in Table 4 (unit: "parts," the number of parts of the polyimide resin and maleimide resin being the number of parts of the solution including the solvent), to obtain a resin composition of the present invention.

[0081] [Table 4]

[0082] (Evaluation of adhesive strength, thermal properties, mechanical properties and dielectric properties) Using the resin compositions obtained in Examples 14 to 19, evaluation samples were prepared in the same manner as above, and the adhesive strength, thermal properties, mechanical properties, and dielectric properties were evaluated in the same manner as above. The results are shown in Table 5.

[0083] [Table 5]

[0084] The results in Table 5 show that the resin composition of the present invention was excellent in all of adhesive strength, mechanical properties, thermal properties and dielectric constant. [Industrial Applicability]

[0085] By using a resin composition containing the isocyanate-modified polyimide resin of the present invention having a specific structure or a terminally modified isocyanate-modified polyimide resin, it is possible to provide a printed wiring board or the like having excellent properties such as heat resistance, mechanical properties, low dielectric properties, and adhesiveness.

Claims

1. An isocyanate-modified polyimide resin is a reaction product of a polyimide resin having acid anhydride groups at both ends, which is a reaction product of an aliphatic diamino compound (b), a tetrabasic acid dianhydride (c), and an aromatic diamino compound (d), with a diisocyanate compound (a) having an isocyanate group, wherein the aromatic diamino compound (d) is a compound represented by the following formulas (6) and (8): 【Chemical 1】 (In formula (6), R １ represents a methyl group, and in formula (8), Z represents a group represented by the following formula (9): 【Chemistry 2】 and a divalent linking group represented by R ３ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a trifluoromethyl group. and at least one compound selected from the group consisting of: the diisocyanate compound (a) having an isocyanate group includes at least one selected from the group consisting of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate; the aliphatic diamino compound (b) contains at least one aliphatic diamino compound having 6 to 36 carbon atoms; The tetrabasic acid dianhydride (c) is represented by the following formulas (1) to (4): 【Chemistry 3】 In formula (4), Y represents C(CF 3 ) 2 , SO 2 , CO, O, a direct bond, or a group represented by the following formula (5): 【Chemistry 4】 represents a divalent linking group represented by the formula: At least one selected from the group consisting of Isocyanate-modified polyimide resin with acid anhydride groups at both ends.

2. 2. A terminal-modified isocyanate-modified polyimide resin, which is a reaction product of the isocyanate-modified polyimide resin according to claim 1 with a compound having one functional group reactive with said acid anhydride group.

3. A resin composition comprising the isocyanate-modified polyimide resin according to claim 1 and a compound that reacts with the isocyanate-modified polyimide resin.

4. A resin composition comprising the terminally modified isocyanate-modified polyimide resin according to claim 2 and a compound that reacts with the terminally modified isocyanate-modified polyimide resin.

5. The resin composition according to claim 3 or 4, wherein the compound that reacts with the isocyanate-modified polyimide resin or the compound that reacts with the terminal-modified isocyanate-modified polyimide resin comprises at least one compound having a maleimide group.

6. A resin composition comprising the isocyanate-modified polyimide resin according to claim 1 and a compound that does not react with the isocyanate-modified polyimide resin.

7. A resin composition comprising the terminally modified isocyanate-modified polyimide resin according to claim 2 and a compound that does not react with the terminally modified isocyanate-modified polyimide resin.

8. A cured product of the resin composition according to any one of claims 3 to 7.

9. A substrate having the cured product according to claim 8.

Images