Polyimide resin, resin composition containing said polyimide resin, and cured product thereof

Abstract

To provide a resin material having a new structure which can be suitably used for a printed wiring board and a resin composition comprising the resin material, which has excellent coating properties on a substrate, where the cured product thereof has excellent adhesion, mechanical properties, heat resistance, and dielectric properties to a metal foil and the substrate having low roughness.SOLUTION: There is provided an isocyanate-modified polyimide resin, which is a reaction product of amino groups and / or acid anhydride groups at both ends possessed by a polyimide resin which is a reaction product of a diamino compound (A) containing a linear aliphatic diamino compound (a1) having 17 to 24 carbon atoms in the main chain which has amino groups at both ends and 1 to 4 methyl groups and / or ethyl groups in the side chain and an aromatic diamino compound (a2) and tetrabasic acid dianhydride (B) and an isocyanate group possessed by a diisocyanate compound (C) and has amino groups and / or acid anhydride groups at both ends.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to polyimide resins having novel structures, resin compositions containing the same, and cured products of the resin compositions. [Background technology]

[0002] Printed wiring boards are essential components for mobile communication devices such as smartphones and tablets, communication base station equipment, computers, car navigation systems, etc. Printed wiring boards are made of various resin materials that have excellent properties such as adhesion to metal foil, heat resistance, and flexibility. 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. Patent Documents 1 and 2 describe examples in which long-chain alkyl chains are introduced into polyimide resins, while Patent Document 3 describes examples in which a dimer diamine skeleton, an alkyl with a longer carbon chain, is introduced into polyimide resins. However, although these polyimide resins excel in terms of low dielectric loss tangent, they have high melt viscosities and poor embedding ability in substrate irregularities. As a result, they are prone to the inclusion of air bubbles and reduced adhesion to the substrate, and their heat resistance is insufficient. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-308551 [Patent Document 2] WO2021 / 049503A1 [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-119361 Summary of the Invention [Problem to be solved by the invention]

[0005] The 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 coatability onto substrates, and when cured, has excellent adhesion to metal foils with low roughness and substrates, mechanical properties, heat resistance, and dielectric properties. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that the above problems can be solved by using a polyimide resin having a specific structure, 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 a polyimide resin which is a reaction product of a diamino compound (A) containing a linear aliphatic diamino compound (a1) and an aromatic diamino compound (a2) having 17 to 24 carbon atoms in the main chain, the diamino compound (A) having amino groups at both terminals and 1 to 4 methyl and / or ethyl groups in the side chain, and a tetrabasic acid dianhydride (B), and the polyimide resin has amino groups and / or acid anhydride groups at both terminals, and an isocyanate group of a diisocyanate compound (C), the isocyanate-modified polyimide resin having amino groups and / or acid anhydride groups at both terminals; (2) The isocyanate-modified polyimide resin according to the above item [1], wherein the diisocyanate compound (C) contains a compound selected from the group consisting of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate. (3) The tetrabasic acid dianhydride (B) is represented by the following formulas (1) to (9):

[0007] [ka]

[0008] (In formula (4), Y represents C(CF3)2, SO2, CO, an oxygen atom, a direct bond, or a group represented by the following formula (10):

[0009] [ka]

[0010] represents a divalent linking group represented by the formula: The isocyanate-modified polyimide resin according to the above item (1) or (2), which contains a compound selected from the group consisting of: (4) The aromatic diamino compound (a2) is represented by the following formulas (11) to (14):

[0011] [ka]

[0012] In formula (13), R2 independently represents a methyl group or a trifluoromethyl group, and in formula (14), Z represents CH(CH3), SO2, CH2, O-C6H4-O, an oxygen atom, a direct bond, or a group represented by the following formula (10):

[0013] [ka]

[0014] and R3 independently represents a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group. The isocyanate-modified polyimide resin according to any one of claims 1 to 3, which contains a compound selected from the group consisting of: (5) A terminal-modified isocyanate-modified polyimide resin, which is a reaction product of an amino group and / or an acid anhydride group at both ends of the isocyanate-modified polyimide resin according to any one of the preceding items (1) to (4) with the functional group of a compound (D) having one functional group capable of reacting with an amino group or an acid anhydride group. (6) A resin composition containing the isocyanate-modified polyimide resin according to any one of (1) to (4) above and a compound having a functional group capable of reacting with the polyimide resin. (7) A resin composition containing the terminally modified isocyanate-modified polyimide resin according to the above item (5) and a compound having a functional group capable of reacting with the polyimide resin. (8) The resin composition according to the above item (6) or (7), wherein the compound capable of reacting with the polyimide resin contains a maleimide resin. (9) A cured product of the resin composition according to any one of (6) to (8), and (10) A substrate having the cured product according to the preceding item (9). Regarding. [Effects of the Invention]

[0015] The polyimide resin of the present invention has a low melt viscosity, good embedding properties for irregularities in a substrate, and high adhesiveness. Furthermore, by using the polyimide resin of the present invention, it is possible to provide a printed wiring board or the like that is excellent in heat resistance, mechanical properties, low dielectric properties, etc.

[0016] The polyimide resin of the present invention comprises a diamino compound (A) (hereinafter simply referred to as "component (A)") containing a linear aliphatic diamino compound (a1) (hereinafter simply referred to as "component (a1)") and an aromatic diamino compound (a2) (hereinafter simply referred to as "component (a2)"), the diamino compound having 17 to 24 carbon atoms in the main chain and having amino groups at both ends and 1 to 4 methyl and / or ethyl groups in the side chain, and a tetrabasic acid dianhydride (B) (hereinafter simply referred to as "component (B)"). The polyimide resin (hereinafter simply referred to as "intermediate polyimide resin") is a reaction product (polymerization and cyclodehydration reaction product) of (C) (hereinafter simply referred to as "component (C)"), and the polyimide resin (hereinafter simply referred to as "intermediate polyimide resin") is a reaction product (polymerization and cyclodehydration reaction product) of (C) (hereinafter simply referred to as "component (C)"), and the polyimide resin is a reaction product of (C) (hereinafter simply referred to as "component (C)"), and the polyimide resin (hereinafter simply referred to as "intermediate polyimide resin") is a reaction product of (C) (polymerization and cyclodehydration reaction product) ...polymerization and cyclodehydration reaction product) of (C) (polymerization and cyclodehydration reaction product) of (C) (polymerization and cyclodehydration reaction product) of (C) (polymerization and cyclodehydration reaction product) of (C) (polymerization and cyclodehydration reaction product) of (C) (polymerization and cyclo First, the intermediate polyimide resin will be described.

[0017] The component (A) used in the synthesis of the intermediate polyimide resin contains the components (a1) and (a2) as essential components. Component (a1) is not particularly limited as long as it is a straight-chain aliphatic hydrocarbon compound having 17 to 24 carbon atoms in its main chain, has amino groups at both terminals of the main chain, and has 1 to 4 methyl and / or ethyl groups in its side chains. The straight-chain aliphatic hydrocarbon having 17 to 24 carbon atoms that forms the main chain of component (a1) may be either saturated or unsaturated. Specific examples of the (a1) component include 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine, 8,13-dimethyloctadecanediamine, 8-methylnonadecanediamine, 9-methylnonadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, and 8,13-dimethyloctadecanediamine-8,12-ene. These may be used alone or in combination of two or more. A commercially available product, Diamine H20 (manufactured by Okamura Oil Mills, Ltd.), is preferably used. The main chain of component (a1) is preferably a saturated aliphatic hydrocarbon, i.e., alkylene, and the number of carbon atoms is preferably 17 to 22, and more preferably 17 to 20. The number of methyl and / or ethyl groups in the side chain is preferably 1 to 3, and more preferably 1 or 2.

[0018] Although there are no particular restrictions on the amount of component (a1) used in synthesizing the intermediate polyimide resin, it is preferable for the amount to be within the range of 10 to 50 mass% of the total mass of components (A), (B), and (C) used in the synthesis, minus the mass of water produced in the dehydration cyclization reaction step during the synthesis of the intermediate polyimide resin (≒ the mass of the final isocyanate-modified polyimide resin). If the amount of component (a1) is below this range, the polyimide resin will contain too few aliphatic chains derived from component (a1), resulting in a high dielectric constant and dielectric loss tangent. If the amount is above this range, the polyimide resin will contain too many aliphatic chains derived from component (a1), resulting in a low heat resistance of the cured product.

[0019] The component (a2) 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 (a2) 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, 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'-diaminodiphenyl Sulfoxide, 3,3'-diaminodiphenylsulfone sulfone, 4,4'-diaminodiphenylsulfone 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-biphenyl Examples of the bis(4-aminophenoxyphenyl)benzene include 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.

[0020] The component (a2) used in the synthesis of the intermediate polyimide resin preferably contains a compound selected from the group consisting of the following formulae (11) to (14).

[0021] [ka]

[0022] In formula (13), R2 independently represents a methyl group or a trifluoromethyl group; in formula (14), Z independently represents CH(CH3), SO2, CH2, O-C6H4-O, an oxygen atom, a direct bond, or a divalent linking group represented by formula (10) above; and R3 independently represents a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group.

[0023] Although there are no particular restrictions on the amount of component (a2) used in synthesizing the intermediate polyimide resin, it is preferable for the amount to be within the range of 10 to 50 mass% of the total mass of components (A), (B), and (C) used in the synthesis, minus the mass of water generated in the dehydration cyclization reaction step during the synthesis of the intermediate polyimide resin (≒ the mass of the final isocyanate-modified polyimide resin). If the amount of component (a2) is below this range, the heat resistance of the cured product will be reduced, and if it is below this range, the dielectric properties of the cured product will be reduced.

[0024] The component (A) used in the synthesis of the intermediate polyimide resin may be used in combination with a diamino compound (a3) ​​other than the components (a1) and (a2) (hereinafter simply referred to as "component (a3)"). The component (a3) ​​is not particularly limited as long as it is a compound other than the components (a1) and (a2) and has two amino groups in one molecule, but an aliphatic diamino compound other than the component (a1) is preferred, and an aliphatic diamino compound having 6 to 36 carbon atoms other than the component (a1) is preferred, as this will result in a polyimide resin with a low dielectric constant and dielectric dissipation factor, and dimer diamine is more preferred. Specific examples of the component (a3) ​​include, in addition to the above-mentioned dimer diamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,3-bisaminomethylcyclohexane, norbornanediamine, isophoronediamine, dimer diamine, 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebiscyclohexylamine, and diaminopolysiloxanes having 6 to 36 carbon atoms. These may be used alone or in combination of two or more.

[0025] The dimer diamines described in the section on specific examples of component (a3) ​​are dimers in which two carboxyl 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, Japanese Patent Application Laid-Open No. 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. Non-limiting general formulas of dimer diamines are shown below (in each formula, m+n=6 to 17, and p+q=8 to 19, respectively; the dashed lines represent carbon-carbon single or double bonds).

[0026] [ka]

[0027] The amount of component (a3) ​​used in synthesizing the intermediate polyimide resin is not particularly limited as long as it does not impair the effects of the invention, but is usually 50% by mass or less, preferably 10 to 30% by mass, of component (A).

[0028] The component (B) 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 component (B) 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-methylcyclohexane Examples thereof include hexene-1,2-dicarboxylic anhydride, 3a,4,5,9b-tetrahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-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.

[0029] Component (B) used in the synthesis of the intermediate polyimide resin preferably contains a compound selected from the group consisting of the following formulas (1) to (7).

[0030]

Chemical formula

[0031] In formula (4), Y represents C(CF3)2, SO2, CO, an oxygen atom, a direct bond or a divalent linking group represented by the following formula (10).

[0032]

Chemical formula

[0033] The reaction between component (A) and component (B) includes a step of obtaining a polyamic acid by a copolymerization reaction between the amino group in component (A) and the acid anhydride group in component (B), 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 MA of component (A) and the molar number MB of component (B) used in the copolymerization reaction satisfy the relationship MA > MB, both ends of the obtained intermediate polyimide resin are amino groups. When the relationship MA < MB is satisfied, both ends of the obtained intermediate polyimide resin are acid anhydride groups. Also, when the relationship MA = MB is satisfied, the obtained intermediate polyimide resin theoretically has an infinite molecular weight and has one amino group and one acid anhydride group at both ends.

[0034] The intermediate polyimide resin can be synthesized by a known method. For example, by adding a solvent, a dehydrating agent, and a catalyst to the components (A) and (B) used in the synthesis and heating and stirring at 100 to 300°C under an inert gas atmosphere such as nitrogen, an imidization reaction (a ring-closing reaction accompanied by dehydration) occurs via the polyamic acid, yielding an intermediate polyimide resin solution. During this process, the 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.

[0035] 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.

[0036] Next, the isocyanate-modified polyimide resin of the present invention will be described. The reaction between the intermediate polyimide resin and component (C) is a copolymerization reaction between the amino group or acid anhydride group at the terminal of the intermediate polyimide resin and the isocyanate group of component (C). 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.

[0037] The component (C) used in the synthesis of the isocyanate-modified polyimide resin can be any compound having two isocyanate groups in the molecule, and multiple diisocyanate compounds can be reacted simultaneously. Preferred examples of component (C) 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(isocyanatomethyl)cyclohexane, and norbornane-diisocyanatomethyl. Among these, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate are more preferred, as they offer an excellent balance of flexibility, adhesiveness, and the like.

[0038] The amount of component (C) used in the copolymerization reaction between the intermediate polyimide resin and component (C) is not particularly limited as long as the amount of isocyanate groups in component (C) is less than 1 equivalent per equivalent of terminal functional groups in the intermediate polyimide resin, but is preferably 0.50 to 0.99 equivalents, more preferably 0.67 to 0.98 equivalents. By using component (C) in this range relative to the intermediate polyimide, 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 of the resin composition containing the polyimide resin, etc. after curing are improved. 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.

[0039] The reaction between the intermediate polyimide resin and the component (C) 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 (C) 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 (C) 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.

[0040] 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.

[0041] The isocyanate-modified polyimide resin of the present invention has amino groups and / or acid anhydride groups at both terminals, and therefore, can be modified at the terminals by reacting it with a compound (D) (hereinafter simply referred to as "component (D)") having one functional group reactive with these functional groups to form the terminal-modified isocyanate-modified polyimide resin of the present invention. Examples of component (D) 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-modified polyimide resin of the present invention can be converted 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 converted to acryloyl groups), so it is also possible to prepare a composition in which the isocyanate-modified polyimide resin is combined with a compound that can react with functional groups other than amino groups or acid anhydride groups.

[0042] The resin composition of the present invention contains the isocyanate-modified polyimide resin of the present invention and a compound capable of reacting with the polyimide resin. Furthermore, a resin composition of the present invention, which is different from the above, contains the terminal-modified isocyanate-modified polyimide resin of the present invention and a compound capable of reacting with the polyimide resin. Hereinafter, the compound capable of reacting with the isocyanate-modified polyimide resin and the compound capable of reacting with the terminal-modified isocyanate-modified polyimide resin will be referred to simply as a "reactive compound."

[0043] The reactive compound is not particularly limited as long as it is a compound (resin) having a reactive group that can react with an amino group, an acid anhydride group, or a functional group (for example, the above-mentioned acryloyl group) that the terminal-modified isocyanate-modified polyimide resin has at its terminal. Specific examples of the reactive compound include epoxy resins, maleimide resins, carbodiimide resins, benzoxazine compounds, and compounds having an ethylenically unsaturated group, etc. These resins or compounds can be used alone or in appropriate mixtures of two or more types depending on the physical properties and applications of the resulting cured product. In the resin composition of the present invention, by using a reactive compound in combination with the isocyanate-modified polyimide resin, it is possible to impart thermal stability and high adhesiveness to the cured product of the resin composition.

[0044] The reactive compound contained in the resin composition of the present invention is preferably a maleimide resin or a compound having an ethylenically unsaturated group, since the cured product of the resin composition has particularly excellent heat resistance and adhesiveness. In addition, when the number of moles of component (A) used in synthesizing the polyimide resin of the present invention is MA, the number of moles of component (B) is MB, and the number of moles of component (C) is MC, for polyimide resins having a value of (MA+MC) / MB exceeding 1, it is also preferable to use an epoxy resin as the thermosetting resin.

[0045] In addition, from the viewpoint of suppressing an increase in the viscosity of the varnish, the reactive compound preferably has a molecular weight of 100 to 50,000. Note that the molecular weight in this specification means the weight average molecular weight of a polystyrene standard determined by gel permeation chromatography (GPC).

[0046] The maleimide resin (maleimide compound) as a reactive compound is not particularly limited as long as it has a maleimide group, but one having two or more maleimide groups in one molecule is preferred. Furthermore, maleimide resins having an aromatic ring such as a benzene ring, biphenyl ring, or naphthalene ring are preferred because the cured product of the resin composition has excellent properties such as mechanical strength and flame retardancy. Specific examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.) and MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.). The maleimide resin is added for the purpose of reacting with the terminal amino group of the isocyanate-modified polyimide resin or the terminal ethylenically unsaturated double bond group of the terminal-modified isocyanate-modified polyimide resin, thereby increasing the crosslink density of the cured product, improving resistance to polar solvents, and improving adhesion to substrates and heat resistance. The curing temperature of the resin composition containing the maleimide resin is preferably 150 to 250° C. The curing time depends on the curing temperature, but is generally from several minutes to several hours. The content of the maleimide resin in the resin composition of the present invention containing a maleimide resin is preferably an amount such that the maleimide group equivalent of the maleimide resin is 0.1 to 500 equivalents relative to 1 equivalent of the terminal amino group of the polyimide resin or 1 equivalent of the terminal ethylenically unsaturated double bond group of the terminally modified isocyanate-modified polyimide resin.

[0047] To the resin composition of the present invention containing a maleimide resin, various radical initiators can be added as a curing agent, if necessary, for the purpose of accelerating the curing reaction of the maleimide resin. Examples of radical initiators 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 maleimide resin is 0.1 to 10% by mass relative to the maleimide resin.

[0048] The epoxy resin (epoxy compound) as a reactive compound is not particularly limited as long as it has an epoxy group, but one having two or more epoxy groups in one molecule is preferred. In addition, epoxy resins having aromatic rings such as benzene rings, biphenyl rings, and naphthalene rings are preferred because the cured product of the resin composition has excellent properties such as mechanical strength and flame retardancy, and specific examples thereof include jER828 (manufactured by Mitsubishi Chemical Corporation), NC-3000, and XD-1000 (all manufactured by Nippon Kayaku Co., Ltd.). The epoxy resin is added for the purpose of reacting with the terminal amino groups or acid anhydride groups of the isocyanate-modified polyimide resin, thereby increasing the crosslink density of the cured product, improving resistance to polar solvents, and improving adhesion to substrates and heat resistance. The curing temperature of the resin composition containing the epoxy resin is preferably 150 to 250° C. The curing time depends on the curing temperature, but is generally from several minutes to several hours.

[0049] The content of the epoxy resin in the resin composition of the present invention containing an epoxy resin is preferably an amount such that the epoxy group equivalent of the epoxy resin is 0.1 to 500 equivalents per equivalent of the active hydrogen and acid anhydride in the phenolic hydroxyl group and terminal amino group of the isocyanate-modified polyimide resin. Since the epoxy groups of the epoxy resin are reactive with the terminal functional groups of the isocyanate-modified polyimide resin, it is a preferred embodiment to add an epoxy resin in an amount such that the epoxy equivalent of the epoxy resin is 0.1 to 500 equivalents per equivalent of the terminal functional group of the polyimide resin, as needed.

[0050] A curing agent may be added to the resin composition of the present invention containing an epoxy resin, if necessary, to promote the curing reaction of the epoxy resin. Examples of the curing agent 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 the curing agent added to the resin composition of the present invention containing an epoxy resin is 0.1 to 10% by mass relative to the epoxy resin.

[0051] The compound having an ethylenically unsaturated group as the reactive compound is not particularly limited as long as it has an ethylenically unsaturated group. Specific examples of the compound having an ethylenically unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, glycol di(meth)acrylate, diethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, and polypropylene glycol di(meth)acrylate. , adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone-modified hydroxypivalic acid neopen glycol di(meth)acrylate, ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone-modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate, and ethylene oxide adducts thereof; pentaerythritol tri(meth)acrylate, and ethylene oxide adducts thereof; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide adducts thereof.

[0052] Other specific examples of the compound having an ethylenically unsaturated group include urethane (meth)acrylates having multiple (meth)acryloyl groups and urethane bonds in the same molecule; polyester (meth)acrylates having multiple (meth)acryloyl groups and ester bonds in the same molecule; epoxy (meth)acrylates derived from epoxy resins and having multiple (meth)acryloyl groups; and reactive oligomers having multiple (meth)acryloyl groups in which these bonds are used in combination.

[0053] Examples of urethane (meth)acrylates include reaction products of a hydroxyl group-containing (meth)acrylate with a polyisocyanate and other alcohols used as needed. Examples include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; glycerin (meth)acrylates such as glycerin mono(meth)acrylate and glycerin di(meth)acrylate; pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate; and the like. Examples of the urethane (meth)acrylates include those obtained by reacting sugar alcohol (meth)acrylates such as methyl methacrylate with polyisocyanates such as toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and their isocyanurates and biuret reaction products.

[0054] Examples of polyester (meth)acrylates include monofunctional (poly)ester (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth)acrylate, ethylene oxide-modified succinic acid (meth)acrylate, and caprolactone-modified tetrahydrofurfuryl (meth)acrylate; di(poly)ester (meth)acrylates such as hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, and epichlorohydrin-modified phthalic acid di(meth)acrylate; and mono-, di-, or tri(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of trimethylolpropane or glycerin.

[0055] Other examples include mono-, di-, tri-, or tetra(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane; mono- or poly(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of dipentaerythritol, or mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols, or hexaols.

[0056] Further examples include polyfunctional (poly)ester (meth)acrylates such as (meth)acrylates of polyester polyols which are reaction products of diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, and hexanediol with polybasic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, and 5-sodium sulfoisophthalic acid, and their anhydrides; and (meth)acrylates of cyclic lactone-modified polyester diols formed from diol components, polybasic acids, and their anhydrides with ε-caprolactone, γ-butyrolactone, δ-valerolactone, and the like.

[0057] Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. Examples include phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, trishydroxyphenylmethane epoxy (meth)acrylate, dicyclopentadienephenol epoxy (meth)acrylate, bisphenol A epoxy (meth)acrylate, bisphenol F epoxy (meth)acrylate, biphenol epoxy (meth)acrylate, bisphenol A novolac epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, and acid anhydride-modified epoxy acrylates thereof.

[0058] Specific examples of the compound having an ethylenically unsaturated group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; and compounds having a vinyl group such as triallyl isocyanurate, trimethallyl isocyanurate, and bisallylnadimide.

[0059] The compound having an ethylenically unsaturated group may be a commercially available product, and examples thereof include KAYARAD (registered trademark) ZCA-601H (trade name, manufactured by Nippon Kayaku Co., Ltd.), propylene glycol monomethyl ether acetate of TrisP-PA epoxy acrylate compound (manufactured by Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) ZCR-6007H (trade name), KAYARAD (registered trademark) ZCR-6001H (trade name), KAYARAD (registered trademark) ZCR-6002H (trade name), KAYARAD (registered trademark) ZCR-6006H (trade name), and KAYARAD (registered trademark) ZXR-1889H (trade name). These compounds having an ethylenically unsaturated group may be used alone or in appropriate mixtures of two or more types.

[0060] The content of the compound having an ethylenically unsaturated group in the resin composition of the present invention containing the compound having an ethylenically unsaturated group is preferably an amount that is 0.1 to 500 equivalents relative to the ethylenically unsaturated double bond group equivalent of the terminally modified isocyanate-modified polyimide resin.

[0061] The resin composition of the present invention containing a compound having an ethylenically unsaturated group may optionally contain a curing agent (D) such as a radical initiator in order to promote the curing reaction between the terminally modified isocyanate-modified polyimide resin and the ethylenically unsaturated group. Specific examples of radical initiators 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 an ethylenically unsaturated group is 0.1 to 10% by mass based on the ethylenically unsaturated group in the entire composition.

[0062] The resin composition of the present invention can be used in combination with an organic solvent to form a varnish-like composition (hereinafter simply referred to as "varnish"). Examples of solvents that can be used 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 solids concentration excluding the organic solvent in the varnish is preferably 10 to 80% by mass, more preferably 20 to 70% by mass.

[0063] The resin composition of the present invention may be used in combination with known additives as necessary.Specific examples of the additives that can be used in combination include epoxy resin curing agents, polybutadiene or its modified products, modified acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds, silicone gel, silicone oil, and 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, colorants such as carbon black, phthalocyanine blue, and phthalocyanine green, thixotropy-imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, hydroquinone, hydroquinone monomethyl ether, phenol-based polymerization inhibitors, stabilizers, antioxidants, photopolymerization initiators, photobase generators, and photoacid generators. 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. As the additive, a silane coupling agent having an acrylic group or a methacrylic group is particularly preferred from the viewpoint of heat resistance.

[0064] The method for preparing the resin composition of the present invention is not particularly limited, and the components may be simply mixed uniformly, or may be prepolymerized. For example, the isocyanate-modified polyimide resin or terminal-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. For mixing or prepolymerization of the components, an extruder, kneader, roll, or the like may be used in the absence of a solvent, and a reaction kettle with a stirrer may be used in the presence of a solvent.

[0065] The resin composition of the present invention can be cured by heating. The curing temperature and curing time of the resin composition may be selected taking into consideration the combination of the functional group possessed by the isocyanate-modified polyimide resin or terminal-modified isocyanate-modified polyimide resin of the present invention and the reactive group possessed by the reactive compound. 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.

[0066] A prepreg can be obtained by heating and melting the resin composition of the present invention to reduce the viscosity and impregnating it into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, alumina fibers, etc. 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 a substrate (article) comprising the cured product of the present invention, such as an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material. Alternatively, a substrate having the cured product of the present invention can be obtained by coating a copper foil, drying the solvent, laminating a polyimide film or LCP (liquid crystal polymer), hot pressing, and then heat curing. In some cases, a substrate having the cured product of the present invention can be obtained by coating a polyimide film or LCP side and laminating it with copper foil. Furthermore, a substrate having the cured product of the present invention can also be obtained by coating the resin composition of the present invention on copper foil, drying the solvent, and then laminating a prepreg in which the resin is impregnated into reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, or alumina fiber, and then heat-pressing and curing the prepreg.

[0067] A substrate comprising the cured product of the resin composition of the present invention can be used for a copper clad laminate (CCL), or a printed wiring board or multilayer wiring board having a circuit pattern on the copper foil of the CCL. [Example]

[0068] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, "parts" means parts by mass, and "%" means % by mass. The GPC measurement conditions in the examples are as follows: Model: TOSOH ECOSEC Elite HLC-8420GPC Column: TSKgel Super AWM-H Eluent: NMP (N-methylpyrrolidone); 0.5 ml / min, 40°C Detector: UV (differential refractometer) Molecular weight standard: polystyrene

[0069] Example 1 (Synthesis of Isocyanate-Modified Polyimide Resin (A-1) 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 5.52 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 10.21 parts of Diamine H20 (manufactured by Okamura Oil Mills, molecular weight 325.09 g / mol), 13.96 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), 66.09 parts of anisole, 0.91 parts of triethylamine, and 14.83 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 of component (A) (component (a1) and component (a2)) to component (B) used in the synthesis of the intermediate polyimide resin (number of moles of component (B) / number of moles of component (A)) was 1.05. To the intermediate polyimide resin solution obtained above, 0.29 parts of IPDI (isophorone diisocyanate, manufactured by Degussa-Hüls, molecular weight 222.29 g / mol) and 0.66 parts of anisole were added and heated at 130° C. for 3 hours to obtain an isocyanate-modified polyimide resin (A-1) solution of the present invention. The final molar ratio of the raw material components of the isocyanate-modified polyimide resin (A-1) obtained above (number of moles of component (B) / (number of moles of component (A) + number of moles of component (C))) was 1.02.

[0070] Example 2 (Synthesis of Isocyanate-Modified Polyimide Resin (A-2) 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 5.52 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 10.21 parts of Diamine H20 (manufactured by Okamura Oil Mills, molecular weight 325.09 g / mol), 13.96 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), 66.09 parts of anisole, 0.91 parts of triethylamine, and 14.83 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 of component (A) (component (a1) and component (a2)) to component (B) used in the synthesis of the intermediate polyimide resin (number of moles of component (B) / number of moles of component (A)) was 1.05. To the intermediate polyimide resin solution obtained above, 0.22 parts of HDI (hexamethylene diisocyanate, manufactured by Asahi Kasei Corporation, molecular weight 168.20 g / mol) and 0.50 parts of anisole were added and heated at 130° C. for 3 hours to obtain an isocyanate-modified polyimide resin (A-2) solution of the present invention. The final molar ratio of the raw material components of the isocyanate-modified polyimide resin (A-2) obtained above (number of moles of component (B) / (number of moles of component (A) + number of moles of component (C))) was 1.02.

[0071] Example 3 (Synthesis of Isocyanate-Modified Polyimide Resin (A-3) of the Present Invention) A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a raw material inlet, a nitrogen inlet, and a stirrer was charged with 5.52 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 7.31 parts of Diamine H20 (manufactured by Okamura Oil Mills, Ltd., molecular weight 325.09 g / mol), 4.80 parts of PRIAMINE1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 13.96 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), 66.09 parts of anisole, 0.91 parts of triethylamine, and 14.83 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 by azeotropy with toluene. After the generation of water stopped, the remaining triethylamine and toluene were removed at 140°C, yielding an intermediate polyimide resin solution. The molar ratio of component (A) (components (a1), (a2), and (a3)) to component (B) used in the synthesis of the intermediate polyimide resin (number of moles of component (B) / number of moles of component (A)) was 1.05. To the intermediate polyimide resin solution obtained above, 0.29 parts of IPDI (isophorone diisocyanate, manufactured by Degussa Huels, molecular weight 222.29 g / mol) and 0.66 parts of anisole were added and heated at 130° C. for 3 hours to obtain an isocyanate-modified polyimide resin (A-3) solution of the present invention. The final molar ratio of the raw material components of the isocyanate-modified polyimide resin (A-3) obtained above (number of moles of component (B) / (number of moles of component (A) + number of moles of component (C))) was 1.02.

[0072] Example 4 (Synthesis of Terminally Modified Isocyanate-Modified Polyimide Resin (A-4) 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), 8.37 parts of Diamine H20 (manufactured by Okamura Oil Mills, molecular weight 325.09 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 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 of component (A) (component (a1) and component (a2)) to component (B) used in the synthesis of the intermediate polyimide resin (number of moles of component (B) / number of moles of component (A)) 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. The final molar ratio of the raw material components of the isocyanate-modified polyimide resin obtained above (number of moles of component (B) / (number of moles of component (A) + number of moles of component (C))) 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, and the mixture was reacted 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 solution of terminally modified isocyanate-modified polyimide resin (A-4) in which both terminals of the isocyanate-modified polyimide resin were modified with maleic anhydride.

[0073] Comparative Example 1 (Synthesis of Comparative Polyimide Resin (A-5)) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 9.05 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 12.41 parts of Diamine H20 (manufactured by Okamura Oil Mills, molecular weight 325.09 g / mol), 14.89 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), 80.90 parts of anisole, 0.97 parts of triethylamine, and 15.91 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 the 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 (A-5) solution. The final molar ratio of the raw material components of the comparative polyimide resin (A-5) obtained above (number of moles of component (B) / number of moles of component (A)) was 1.02.

[0074] Comparative Example 2 (Synthesis of Comparative Polyimide Resin (A-6)) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 9.05 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), 12.29 parts of PRIAMINE 1075 (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), 80.63 parts of anisole, 0.97 parts of triethylamine, and 15.89 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 the 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 (A-6) solution. The final molar ratio of the raw material components of the comparative polyimide resin (A-6) obtained above (number of moles of component (B) / number of moles of component (A)) was 1.02.

[0075] Comparative Example 3 (Synthesis of Comparative Polyimide Resin (A-7)) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer was charged with 9.05 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), 3.96 parts of 1,10-decanediamine (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 172.32 g / mol), 14.89 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), 62.10 parts of anisole, 0.97 parts of triethylamine, and 14.54 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 a comparative polyimide resin (A-7) solution. The final molar ratio of the raw material components of the comparative polyimide resin (A-7) obtained above (number of moles of component (B) / number of moles of component (A)) was 1.02.

[0076] Examples 5 to 11 and Comparative Examples 4 to 6 (Preparation of Resin Compositions of the Present Invention and Comparative Examples) The components were blended in the amounts shown in Table 1 (unit: "parts," the numbers in the table being the number of parts converted to solid content excluding solvent), and then anisole was added as a solvent in an amount to give a solid content concentration of 20 mass %, and the mixture was mixed uniformly to prepare the resin compositions of the present invention and the comparative examples.

[0077] The components in Table 1 are as follows: <Polyimide resin> (A-1) to (A-4): Polyimide resins of the present invention obtained in Examples 1 to 4 (A-5) to (A-7): Comparative polyimide resins obtained in Comparative Examples 1 to 3 <Thermosetting resin> MIR-3000-70MT: Maleimide resin, manufactured by Nippon Kayaku Co., Ltd. XD-1000: Epoxy resin, manufactured by Nippon Kayaku Co., Ltd. ZXR-1889H: Epoxy acrylate resin, manufactured by Nippon Kayaku Co., Ltd. <Curing agent> DCP: Dicumyl peroxide, manufactured by Kayaku Nouryon Co., Ltd. <Additives> KR-513: Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.

[0078] Using each of the resin compositions obtained in Examples 5 to 11 and Comparative Examples 4 to 6, the adhesive strength to copper foil, heat resistance, dielectric properties (dielectric constant and dielectric tangent), and coatability of the cured resin compositions were evaluated by the following methods.

[0079] (Evaluation of adhesive strength) The resin compositions of Examples 5 to 11 and Comparative Examples 4 to 6 were applied to the rough surface of ultra-low roughness, non-roughened electrolytic copper foil CF-T49A-DS-HD (hereafter referred to as "T49A") manufactured by Fukuda Metal Foil & Powder Co., Ltd. using an automatic applicator in an amount such that the resin composition layer would have a thickness of 30 μm after application and drying, and then heated and dried at 120°C for 10 minutes. Kapton 20EN (manufactured by DuPont-Toray Co., Ltd.) was placed on the resin composition layer on the copper foil obtained above, and the resulting laminate was vacuum-pressed at 200°C for 60 minutes under 3 MPa. The resulting test specimens were cut to a width of 10 mm, and the 90° peel strength (peel speed: 50 mm / min) between the copper foil and the cured resin composition layer was measured using an Autograph AGS-X-500N (manufactured by Shimadzu Corporation). The adhesive strength was evaluated according to the following criteria. The results are shown in Table 1. ◎...6.6N / cm or more ○ 5.0N / cm or more and less than 6.6N / cm × Less than 5.0N / cm

[0080] (Evaluation of heat resistance) 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 time until blisters appeared was measured. Heat resistance was evaluated according to the following criteria. The results are shown in Table 1. ◎ No swelling for over 1000 seconds ○ Blisters occur between 10 seconds and 1000 seconds × Blisters appear in less than 10 seconds

[0081] (Evaluation of dielectric constant and dielectric loss tangent) The same method as described above for "Evaluation of Adhesion Strength" was used to form a coating of the resin composition on the rough surface of T49A, except that the amount of resin composition applied was changed to an amount that would result in a resin composition layer thickness of 100 μm after drying. The coating was then heat-cured at 200°C for 60 minutes. The copper foil was etched away from the resulting laminate of the cured resin composition layer and copper foil using an iron(III) chloride solution with a liquid specific gravity of 45 Baume degrees. The resulting laminate was washed with ion-exchanged water and dried at 105°C for 10 minutes, yielding a cured resin composition film. The dielectric constant and dielectric loss tangent at 10 GHz of the cured film were measured using a network analyzer (Agilent Technologies) 8719ET by cavity resonance. The results are shown in Table 1.

[0082] (Evaluation of Coatability) For test pieces prepared in the same manner as in the "Evaluation of Adhesion Strength" above, voids (air bubbles) contained in the recesses of the roughened copper foil surface were confirmed using an optical microscope. Depending on the percentage of recesses where voids were observed, the coatability on the rough surface was evaluated according to the following criteria. ○ The percentage of concave portions where voids were observed was 0% or more but less than 1% △: The percentage of concave portions where voids were observed was 1% or more but less than 2% × The percentage of concave portions where voids were observed is 2% or more

[0083] [Table 1]

[0084] The results in Table 1 show that the resin compositions containing the polyimide resin of the present invention are excellent in all of adhesive strength, heat resistance, dielectric properties, and coatability, whereas the resin compositions of the comparative examples are inferior in adhesive strength, heat resistance, and coatability. [Industrial Applicability]

[0085] By using the polyimide resin of the specific structure of the present invention, it is possible to provide printed wiring boards and the like that are excellent in properties such as heat resistance, coatability, low dielectric properties, and adhesiveness.

Claims

1. The polyimide resin is a reaction product of a diamino compound (A) containing a linear aliphatic diamino compound (a1) and an aromatic diamino compound (a2), the diamino compound (A) having 17 to 24 carbon atoms in the main chain and having amino groups at both terminals and 1 to 4 methyl and / or ethyl groups in the side chain, and a tetrabasic acid dianhydride (B), and the polyimide resin is a reaction product of the amino groups and / or acid anhydride groups at both terminals and the isocyanate groups of a diisocyanate compound (C), the isocyanate-modified polyimide resin having amino groups and / or acid anhydride groups at both terminals.

2. 2. The isocyanate-modified polyimide resin according to claim 1, wherein the diisocyanate compound (C) comprises a compound selected from the group consisting of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate.

3. The tetrabasic acid dianhydride (B) is represented by the following formulas (1) to (9): 【Chemical 1】 (In formula (4), Y is C(CF ３ ) ２ , S.O. ２ , CO, an oxygen atom, a direct bond, or the following formula (10): 【Chemistry 2】 represents a divalent linking group represented by the formula:

3. The isocyanate-modified polyimide resin according to claim 1, further comprising a compound selected from the group consisting of:

4. The aromatic diamino compound (a2) is represented by the following formulas (11) to (14): 【Chemistry 3】 (In formula (13), R ２ independently represent a methyl group or a trifluoromethyl group, and in formula (14), Z is CH(CH ３ ), SO ２ , C.H. ２ , O-C ６ H ４ -O, an oxygen atom, a direct bond, or the following formula (10) 【Chemistry 4】 and a divalent linking group represented by R ３ each independently represents a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group. The isocyanate-modified polyimide resin according to any one of claims 1 to 3, comprising a compound selected from the group consisting of:

5. A terminal-modified isocyanate-modified polyimide resin, which is a reaction product of an amino group and / or an acid anhydride group at both terminals of the isocyanate-modified polyimide resin according to any one of claims 1 to 4 and a functional group of a compound (D) having one functional group reactive with an amino group or an acid anhydride group.

6. A resin composition comprising the isocyanate-modified polyimide resin according to any one of claims 1 to 4 and a compound having a functional group capable of reacting with the polyimide resin.

7. A resin composition comprising the terminally modified isocyanate-modified polyimide resin according to claim 5 and a compound having a functional group capable of reacting with the polyimide resin.

8. 8. The resin composition according to claim 6, wherein the compound capable of reacting with the polyimide resin contains a maleimide resin.

9. A cured product of the resin composition according to any one of claims 6 to 8.

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

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