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

Abstract

To provide a resin material which has a novel structure and can suitably be used for a printed-wiring board, and a resin composition which contains the resin material, and of which the cured product is excellent in adhesiveness to a metal foil with low roughness and to a base material, mechanical property, heat resistance, lamination property, and dielectric property.SOLUTION: Provided is a polyimide resin which is a reaction product of an imidization product (P) of a polyamic acid resin being a copolymer of amino compounds (A) including a 6-36C aliphatic diamino compound (a1) and an aromatic diamino compound (a2) with no phenolic hydroxy group and a tetrabasic acid dianhydride (B), and a compound (C) having a functional group capable of reacting with a terminal functional group of the imidization product (P) and an ethylenically unsaturated double bond group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyimide resin having a novel structure, a resin composition containing the same, and a cured product of the resin composition.

Background Art

[0002] Printed wiring boards are indispensable members for mobile communication devices such as smartphones and tablets, communication base station devices, and electronic devices such as computers and car navigation systems. Various resin materials having excellent properties such as adhesion to metal foil, heat resistance, and flexibility are used for printed wiring boards. In recent years, the development of printed wiring boards for next-generation high-frequency wireless with high speed and large capacity has been carried out. In addition to the above-mentioned various properties, the resin material is required to have low transmission loss, that is, low dielectric constant and low dielectric tangent.

[0003] High-frequency electrical signals are used in communication devices and electronic devices for the purpose of transmitting and processing a large amount of information at high speed. However, since high-frequency signals are very likely to attenuate, printed wiring boards are also required to have a device for suppressing transmission loss as much as possible. Transmission loss is roughly classified into conductor loss and dielectric loss. When the frequency of an electrical signal exceeds GHz, the conductor loss depends on the surface state of the copper foil used in the circuit. In order to suppress conductor loss, it is generally preferable to use copper foil with low roughness or no roughening. That is, a low-dielectric resin having high adhesiveness to these copper foils is required.

[0004] Polyimide resins having excellent properties such as heat resistance, flame retardancy, flexibility, electrical properties, and chemical resistance are widely used in electrical and electronic parts, semiconductors, communication devices and their circuit parts, peripheral devices, and the like. On the other hand, it is known that hydrocarbon-based compounds such as petroleum and natural oil exhibit high insulation and low dielectric constant. Patent Document 1 describes an example in which the skeleton of dimeric diamine, which is a long-chain alkyl, is introduced into a polyimide resin by taking advantage of the characteristics of both. However, although the polyimide resin of Patent Document 1 is excellent in terms of low dielectric tangent, it is inferior in adhesion and mechanical properties to non-roughened copper foil.

[0005] In addition, Patent Document 2 describes that the adhesion to a substrate can be improved by mixing a polyimide resin having a dimer diamine skeleton and an epoxy resin. However, the reduction of the dielectric constant and the dielectric loss tangent is insufficient, and it is necessary to further improve the adhesion to an unroughened copper foil.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a resin material having a novel structure that can be suitably used for a printed wiring board, and a resin composition containing the resin material, the cured product of which is excellent in adhesion to a metal foil and a substrate having low roughness, mechanical properties, heat resistance, laminating properties, and dielectric properties.

Means for Solving the Problems

[0008] As a result of intensive studies, the present inventors have found that a resin composition containing a novel polyimide resin having a specific structure solves the above problems, and completed the present invention. That is, the present invention is (1) A polyimide resin which is a reaction product of an imidized product (P) of a polyamic acid resin which is a copolymer of an amino compound (A) containing an aliphatic diamino compound (a1) having 6 to 36 carbon atoms and an aromatic diamino compound (a2) having no phenolic hydroxyl group and a tetracarboxylic dianhydride (B), and a compound (C) having a functional group capable of reacting with the terminal functional group of the imidized product (P) and an ethylenically unsaturated double bond group, (2) The tetracarboxylic dianhydride (B) is represented by the following formulas (1) to (5)

[0009] [Chemical formula]

[0010] (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 (6)

[0011] [Chemical formula]

[0012] )(and is selected from the group consisting of). The polyimide resin according to item [1] above, containing a compound (3) The compound (a2) is represented by the following formulas (7) to (10)

[0013] [Chemical formula]

[0014] (In formula (9), R2 independently represents a methyl group or a trifluoromethyl group. In formula (10), Z represents CH(CH3), SO2, CH2, O-C6H4-O, an oxygen atom, a direct bond, or a divalent linking group represented by the following formula (6)

[0015] [Chemical formula]

[0016] )(and R3 independently represents a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group). The polyimide resin according to item (1) above, containing a compound selected from the group consisting of (4) The functional group capable of reacting with the terminal functional group of the imidized product (P) of the compound (C) is an isocyanate group or a carboxylic acid chloride group. The polyimide resin according to item (1) above (5) A resin composition containing the polyimide resin according to any one of items (1) to (4) above and a thermosetting resin (6) The resin composition according to the preceding paragraph (5), further containing a curing agent. (7) The resin composition according to the preceding paragraph (5) or (6), further containing a silane coupling agent having an acrylic group. (8) A cured product of the resin composition according to any one of the preceding paragraphs (5) to (7), and (9) An article provided with the cured product according to the preceding paragraph (8). Relates to the above.

Effect of the Invention

[0017] The polyimide resin having a specific structure of the present invention has good adhesion to a low-roughened or non-roughened metal foil and a prepreg. Further, by using the polyimide of the present invention, 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.

[0018] The polyimide resin of the present invention is a reaction product of an imidized product (P) (hereinafter also simply referred to as "imidized product (P)") of a polyamic acid resin, which is a copolymer of an amino compound (A) (hereinafter also simply referred to as "(A) component") containing an aliphatic diamino compound (a1) having 6 to 36 carbon atoms (hereinafter also simply referred to as "(a1) component") and an aromatic diamino compound (a2) having no phenolic hydroxyl group (hereinafter also simply referred to as "(a2) component") and a tetracarboxylic dianhydride (B) (hereinafter also simply referred to as "(B) component"), and a compound (C) (hereinafter also simply referred to as "(C) component") having a functional group capable of reacting with the terminal functional group of the imidized product (P) and an ethylenically unsaturated double bond group. First, the imidized product (P), which is an intermediate raw material of the polyimide resin of the present invention, will be described.

[0019] The (a1) component used in the synthesis of the imidated product (P) is not particularly limited as long as it is an aliphatic compound having two amino groups in one molecule and having 6 to 36 carbon atoms. The aliphatic structure in the (a2) component may be linear, branched or cyclic, or may have the above structures combined, and may be either saturated aliphatic or unsaturated aliphatic. Specific examples of the (a2) component include 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 diamino polysiloxane having 6 to 36 carbon atoms, etc. These may be used alone or in combination of two or more. Also, from the viewpoint of the dielectric properties of the polyimide resin, it is preferable to use dimer diamine.

[0020] The dimer diamine described in the section of specific examples of the (a1) component is one in which two carboxyl groups of dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid, are substituted with primary amino groups (see Japanese Patent Laid-Open No. 9-12712, etc.). Specific examples of commercially available products of dimer diamine include PRIAMINE1074 and PRIAMINE1075 (both manufactured by Croda Japan Co., Ltd.), and Versamine 551 (manufactured by Cognis Japan Co., Ltd.), etc. These may be used alone or in combination of two or more. Hereinafter, a non-limiting general formula of dimer diamine is shown (in each formula, m + n = 6 to 17 is preferable, p + q = 8 to 19 is preferable, and the dashed line part means a carbon-carbon single bond or a carbon-carbon double bond).

[0021]

Chemical formula

[0022] When synthesizing the imidized product (P), the amount of the component (a1) used is preferably in the range of 10 to 50% by mass of the mass obtained by subtracting the mass of water (water generated by the dehydration condensation reaction) in an amount twice the number of moles of the component (B) from the mass of the component (A) (the mass of the produced imidized product (P)). When the amount of the component (a1) is less than the above range, the aliphatic chain derived from the component (a1) in the finally obtained polyimide resin is too small, resulting in a high dielectric tangent of the cured product of the resin composition. When the amount exceeds the above range, the aliphatic chain derived from the component (a1) in the polyimide resin is too large, resulting in a decrease in the heat resistance of the cured product of the resin composition.

[0023] The (a2) component used in the synthesis of the imidized product (P) is not particularly limited as long as it is an aromatic compound having two amino groups in one molecule and no phenolic hydroxyl group. When a diamino compound having a phenolic hydroxyl group is used, the reaction with the tetracarboxylic dianhydride (B) described below becomes slow, and problems such as insufficient high molecular weight of the imidized product (P) or deterioration of dielectric properties occur. Therefore, an aromatic diamino compound having no phenolic hydroxyl group is preferred.Specific examples of the (a2) component 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'-diaminodiphenyl sulfone sulfone, 4,4'-diaminodiphenyl sulfone 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-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, etc. These may be used alone or in combination of two or more.

[0024] The component (a2) used in the synthesis of the imidized product (P) preferably contains a compound selected from the group consisting of the following formulas (7) to (10) from the viewpoints of the heat resistance of the cured product of the resin composition and the solubility of the finally obtained polyimide resin in a solvent.

[0025] [Chemical formula]

[0026] In formula (9), R2 independently represents a methyl group or a trifluoromethyl group. In formula (10), Z represents CH(CH3), SO2, CH2, O-C6H4-O, an oxygen atom, a direct bond, or a divalent linking group represented by the following formula (6), and R3 independently represents a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group.

[0027] [Chemical formula]

[0028] The (B) component used in the synthesis of the imidized product (P) is not particularly limited as long as it has two acid anhydride groups in one molecule. Specific examples of the (B) component include pyromellitic dianhydride, ethylene glycol-bis(anhydrotrimellitate), glycerin-bis(anhydrotrimellitate) monoacetate, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methylcyclohexene-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 and bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 5,5'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), 4,4'-oxydiphthalic anhydride, etc. Among them, from the viewpoints of solvent solubility and adhesion to the substrate, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride or 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride are preferable. These may be used alone or in combination of two or more.

[0029] From the viewpoint of the solvent solubility of the polyamic acid resin, the imidized product (P) and the finally obtained polyimide resin, the (B) component used in the synthesis of the imidized product (P) preferably contains a compound selected from the group consisting of the following formulas (1) to (5).

[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 above formula (6).

[0032] When the number of moles of component (a1) in component (A) used for the synthesis of the imidized product (P) is a1M and the number of moles of component (a2) is a2M, the value of a1M / (a1M + a2M) is preferably more than 0.2 and less than 0.9, and more preferably more than 0.3 and less than 0.6. When a1M / (a1M + a2M) is 0.2 or less, the dielectric properties of the cured product of the resin composition tend to deteriorate, and the solvent solubility of the polyimide resin tends to deteriorate. When a1M / (a1M + a2M) is 0.9 or more, the heat resistance of the cured product of the resin composition tends to deteriorate.

[0033] Also, the value of a2M / (a1M + a2M) is preferably more than 0.1 and less than 0.8, and more preferably more than 0.2 and less than 0.6. When a2M / (a1M + a2M) is 0.1 or less, the solder heat resistance of the cured product of the resin composition tends to deteriorate. When a2M / (a1M + a2M) is 0.8 or more, the solvent solubility of the polyimide resin tends to deteriorate.

[0034] When the number of moles of component (A) is MA and the number of moles of component (B) is MB, and component (A) and component (B) are copolymerized in an amount that satisfies the relationship of MA / MB > 1, an imidized product (P) of a polyamic acid resin having amino groups at both ends can be obtained. At this time, the value of MA / MB is preferably in the range of more than 1.0 and less than 10.0, and more preferably in the range of more than 1.0 and less than 5.0. When the above value is 10.0 or more, in addition to the insufficient high molecular weight of the finally obtained polyimide resin, the residual rate of unreacted raw materials increases, and various properties such as the heat resistance after curing of the resin composition (described later) may decrease.

[0035] Let the number of moles of component (A) be \(M_A\) and the number of moles of component (B) be \(M_B\). When component (A) and component (B) are copolymerized in an amount satisfying the relationship \(M_B / M_A>1\), an imidized product (P) of a polyamic acid resin with carboxylic anhydride groups at both ends is obtained. At this time, the value of \(M_B / M_A\) is preferably in the range exceeding 1.0 and less than 10.0, and more preferably in the range exceeding 1.0 and less than or equal to 5.0. When the above value is 10.0 or more, in addition to insufficient high molecular weight of the finally obtained polyimide resin, the residual rate of unreacted raw materials increases, and various properties such as heat resistance after curing of the resin composition (described later) may deteriorate.

[0036] The imidized product (P) can be synthesized by a known method. For example, after dissolving component (A) and component (B) used in the synthesis in a solvent, a copolymerization reaction between diamines and tetracarboxylic dianhydrides occurs by heating and stirring at 10 to 140 °C under an inert atmosphere such as nitrogen, and a polyamic acid resin solution is obtained.

[0037] Further, a dehydrating agent and a catalyst are added to the polyamic acid resin solution obtained above as necessary, and an imidization reaction (a ring-closing reaction involving dehydration) occurs by heating and stirring at 100 to 300 °C, and an imidized product (P) is obtained. As the dehydrating agent, toluene, xylene, etc. can be used, and as the catalyst, a tertiary amine and a dehydration catalyst can be used. As the tertiary amine, a heterocyclic tertiary amine is preferable, and examples include pyridine, picoline, quinoline, and isoquinoline. Examples of the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. The reaction time during the synthesis of the polyamic acid resin and the polyimide resin is greatly affected by the reaction temperature, but it is preferable to carry out the reaction until the viscosity increase accompanying the progress of the reaction reaches equilibrium and the maximum molecular weight is obtained, and it is usually several minutes to 20 hours.

[0038] The above example is a method for synthesizing a polyimide resin via polyamic acid. However, after dissolving the components (A) and (B) used in the synthesis in a solvent, a dehydrating agent or a catalyst may be added as necessary, and the copolymerization reaction and the imidization reaction may be carried out simultaneously by heating and stirring at 100 to 300 °C to obtain an imidized product (P).

[0039] Solvents that can be used in the synthesis of the imidized product (P) 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, cyclohexene-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, isopropyl 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. However, it is not limited to these. These may be used alone or in combination of two or more.

[0040] The preferred amount of the solvent used should be appropriately adjusted according to the viscosity and use of the resulting resin, but it is preferably 60 to 10% by mass of the solid content, more preferably 50 to 20% by mass.

[0041] When synthesizing the imidized product (P), it is preferable to use a catalyst to promote the dehydration reaction. The amount of the catalyst used is preferably 1 to 30%, more preferably 5 to 15% of twice the number of moles of component (B) (the number of moles of water generated by dehydration condensation). Specific examples of the catalyst that can be used include known general basic catalysts such as triethylamine and pyridine. Among them, triethylamine is preferable because of its low boiling point and difficulty in remaining.

[0042] Next, the polyimide resin of the present invention, which is a reaction product of the imidized product (P) and component (C), will be described. Component (C) used in the reaction with the imidized product (P) is not particularly limited as long as it is a compound having a functional group capable of reacting with the terminal functional group of the imidized product (P) and an ethylenically unsaturated double bond group. The polyimide resin of the present invention, which is a reaction product of the terminal functional group of the imidized product (P) and component (C), has excellent heat resistance and adhesiveness of the cured product of the resin composition because the ethylenically unsaturated double bond groups derived from component (C) can react with each other or with the thermosetting resin described below. Further, by reacting the terminal functional group of the imidized product (P) with component (C), the pot life of the resin composition tends to be improved.

[0043] Examples of the functional group capable of reacting with the terminal functional group of the imidized product (P) that component (C) has include isocyanate group, carboxylic acid chloride group, acid anhydride group, epoxy group, silyl chloride group, alkyl halide group, ester group, sulfonyl chloride group, and carboxyl group. In particular, the isocyanate group is preferable because no residual impurities derived from the leaving group are generated from component (C). In addition, the ethylenically unsaturated double bond group that component (C) has is not particularly limited as long as it is a C=C bond. It is not limited.

[0044] Let the number of moles of component (A) be \(M_A\) and the number of moles of component (B) be \(M_B\). Since the imidized product (P) obtained by copolymerizing component (A) and component (B) in an amount satisfying the relationship \(M_A / M_B > 1\) has an amine at its terminal, a component (C) having an isocyanate group, a carboxylic acid chloride group, an acid anhydride group, an epoxy group, a silyl chloride group, an alkyl halide group, an ester group, a sulfonyl chloride group, a carboxyl group, etc. can react with the terminal functional group (amine) of the imidized product (P). On the other hand, let the number of moles of component (A) be \(M_A\) and the number of moles of component (B) be \(M_B\). Since the imidized product (P) obtained by copolymerizing component (A) and component (B) in an amount satisfying the relationship \(M_A / M_B < 1\) has an acid anhydride at its terminal, a component (C) having an isocyanate group, an epoxy group, a carboxyl group, etc. can react with the terminal functional group (acid anhydride group) of the imidized product (P).

[0045] Specific examples of component (C) include Karenz MOI (manufactured by Showa Denko K.K.), Karenz AOI, Karenz MOI - BM, Karenz MOI - BP, Karenz BEI, Karenz MOI - EG, Karenz AOI - VM, methacrylic acid chloride, acrylic acid chloride, maleimidocaproic acid chloride, allyl bromide, allyl iodide, allyl chloride, 4 - chloro - 1 - butene, 4 - bromo - 1 - butene, crotonoyl chloride, cinnamoyl chloride, and the like.

[0046] The polyimide resin of the present invention, which is a reaction product of the imidized product (P) and component (C), can be synthesized by a known method. For example, it can be synthesized by mixing a predetermined component (C) into a resin solution of the imidized product (P) and reacting it at 80°C to 150°C.

[0047] Various catalysts may be used to promote the reaction between the imidized product (P) and component (C). Known inorganic acids, organic acids, inorganic bases, organic bases, etc. can be used as the catalyst.

[0048] When the number of moles of component (C) used in the synthesis of the polyimide resin of the present invention is MC and the number of moles of the terminal functional groups of the imidized product (P) is MP, it is preferable that the value of MC / MP exceeds 0.3 and is less than 1, and more preferably exceeds 0.5 and is less than 1. When MC / MP exceeds 1, the heat resistance of the cured product of the resin composition deteriorates due to the unreacted component (C). When MC / MP is 0.3 or less, when the terminal functional group of the imidized product (P) that does not react with component (C) is an acid anhydride, the substrate adhesiveness tends to decrease. When the terminal functional group of the imidized product (P) that does not react with component (C) is an amine, the viscosity of the polyimide increases due to hydrogen bonding, the laminating property decreases, or the pot life of the composition with the thermosetting resin described later tends to decrease.

[0049] Next, the resin composition of the present invention will be described. The resin composition of the present invention contains a polyimide resin, which is a reaction product of an imidized product (P) and a component (C), a thermosetting resin (compound), and a curing agent. Specific examples of the thermosetting resin (compound) contained in the resin composition of the present invention include epoxy resins, maleimide resins, carbodiimide resins, benzoxazine compounds, and compounds having an ethylenically unsaturated group. These resins or compounds can be used alone or in appropriate mixtures of two or more depending on the physical properties and uses of the resulting cured product. In the resin composition of the present invention, by using a thermosetting resin (compound) in combination with the polyimide resin, it is possible to impart heat stability and high adhesiveness to the cured product of the resin composition.

[0050] As the thermosetting resin (compound) contained in the resin composition of the present invention, a maleimide resin or a compound having an ethylenically unsaturated group is preferable from the viewpoint of particularly excellent heat resistance and adhesiveness of the cured product of the resin composition. Regarding the polyimide resin in which, when the number of moles of component (A) used in the synthesis of the polyimide resin of the present invention is MA, the number of moles of component (B) is MB, the number of moles of component (C) is MC, and the number of moles of the terminal functional groups of the imidized product (P) is MP, it is also preferable to use an epoxy resin as the thermosetting resin when the value of MA / MB exceeds 1 and the value of MC / MP exceeds 0 and is less than 1.

[0051] Also, from the viewpoint of suppressing the increase in the viscosity of the varnish, the thermosetting resin (compound) preferably has a molecular weight of 100 to 50,000. In this specification, the molecular weight means the mass average molecular weight of polystyrene standards by gel permeation chromatography (GPC) method.

[0052] The maleimide resin as the thermosetting resin is not particularly limited as long as it has two or more maleimide groups in one molecule. However, since the cured product of the resin composition is excellent in properties such as mechanical strength and flame retardancy, a maleimide resin having an aromatic ring such as a benzene ring, a biphenyl ring, and a naphthalene ring is preferable. Specific examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.), MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.), and the like. The maleimide resin is added for the purpose of reacting with the ethylenically unsaturated double bond groups of the polyimide resin. As a result, the crosslinking density of the cured product increases, the resistance to polar solvents improves, and the adhesion to the substrate and heat resistance also improve. 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 about several minutes to several hours. The content of the maleimide resin in the resin composition of the present invention containing the maleimide resin is preferably an amount such that the maleimide group equivalent of the maleimide resin is 0.1 to 500 equivalents with respect to 1 equivalent of the ethylenically unsaturated double bond groups of the polyimide resin.

[0053] In the resin composition of the present invention containing a maleimide resin, various radical initiators can be added as curing agents as 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 addition amount of the radical initiator in the resin composition of the present invention containing a maleimide resin is 0.1 to 10% by mass based on the maleimide resin.

[0054] The epoxy resin as a thermosetting resin is not particularly limited as long as it has two or more epoxy groups in one molecule. However, since the cured product of the resin composition is excellent in properties such as mechanical strength and flame retardancy, an epoxy resin having an aromatic ring such as a benzene ring, a biphenyl ring, and a naphthalene ring is preferable. Specific examples thereof include jER828 (manufactured by Mitsubishi Chemical Corporation), NC-3000, XD-1000 (all manufactured by Nippon Kayaku Co., Ltd.). The epoxy resin is added for the purpose of reacting with the terminal amino group or acid anhydride group of the polyimide resin, whereby the crosslink density of the cured product increases, the resistance to polar solvents improves, and the adhesion to the substrate and heat resistance improve. The curing temperature of the resin composition containing an epoxy resin is preferably 150 to 250°C. The curing time depends on the curing temperature, but is generally about several minutes to several hours.

[0055] The content of the epoxy resin in the resin composition of the present invention containing an epoxy resin is preferably such that the epoxy equivalent of the epoxy resin is 0.1 to 500 equivalents with respect to the phenolic hydroxyl group of the polyimide resin and the active hydrogen and acid anhydride of the terminal amino group. In addition, since the epoxy group of the epoxy resin has reactivity with the terminal functional group of the 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 with respect to 1 equivalent of the terminal functional group of the polyimide resin as necessary.

[0056] In the resin composition of the present invention containing an epoxy resin, a curing agent can be added as needed for the purpose of accelerating 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-diazabicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octylate. The addition amount of the curing agent in the resin composition of the present invention containing an epoxy resin is 0.1 to 10% by mass based on the epoxy resin.

[0057] The compound having an ethylenically unsaturated group as a thermosetting resin is not particularly limited as long as it has an ethylenically unsaturated group in one molecule. 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, 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 neopentyl 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, triethanolamine tri(meth)acrylate, and its ethylene oxide adduct; pentaerythritol tri(meth)acrylate, and its ethylene oxide adduct; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and its ethylene oxide adduct, etc.

[0058] In addition, other examples of compounds having an ethylenically unsaturated group include urethane (meth)acrylates having both a (meth)acryloyl group and a urethane bond in the same molecule; polyester (meth)acrylates having both a (meth)acryloyl group and an ester bond in the same molecule; epoxy (meth)acrylates derived from an epoxy resin and having a (meth)acryloyl group; and reactive oligomers in which these bonds are used in combination, etc.

[0059] Urethane (meth)acrylates include reaction products of a hydroxyl group-containing (meth)acrylate, a polyisocyanate, and other alcohols used as necessary. For example, 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; sugar alcohol (meth)acrylates such as pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, and polyisocyanates such as toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexane methylene diisocyanate, and their isocyanurates and biuret reaction products, etc., are reacted to give urethane (meth)acrylates.

[0060] Polyester (meth) acrylates include, for example, 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, 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, epichlorohydrin-modified phthalic acid di (meth) acrylate; and mono-, di- or tri (meth) acrylates of triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of trimethylolpropane or glycerin.

[0061] Also included are mono-, di-, tri- or tetra (meth) acrylates of triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of pentaerythritol, dimethylolpropane, trimethylolpropane or tetramethylolpropane; mono- or poly (meth) acrylates of triols, tetraols, pentaols or hexaols and other polyhydric alcohols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of dipentaerythritol; and mono (meth) acrylate or poly (meth) acrylate thereof.

[0062] Furthermore, (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, hexanediol, etc., 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, 5-sodium sulfoisophthalic acid, etc., and anhydrides thereof; polyfunctional (poly)ester (meth)acrylates such as (meth)acrylates of cyclic lactone-modified polyester diols composed of diol components, polybasic acids and their anhydrides, and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. can be mentioned.

[0063] Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. For example, phenol novolak type epoxy (meth)acrylate, cresol novolak type epoxy (meth)acrylate, tris hydroxyphenylmethane type epoxy (meth)acrylate, dicyclopentadiene phenol type epoxy (meth)acrylate, bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, biphenol type epoxy (meth)acrylate, bisphenol A novolak type epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, etc., and acid anhydride-modified epoxy acrylates thereof can be mentioned.

[0064] For example, vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, etc.; styrenes such as styrene, methyl styrene, ethyl styrene, divinylbenzene, etc., and compounds having a vinyl group such as triallyl isocyanurate, trimethallyl isocyanurate, and bisallyl nadimide can also be mentioned as specific examples of compounds having an ethylenically unsaturated group.

[0065] As the compound having an ethylenically unsaturated group, commercially available products can be used. For example, KAYARAD (registered trademark) ZCA-601H (trade name, manufactured by Nippon Kayaku Co., Ltd.), propylene glycol monomethyl ether acetate of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H (trade name), KAYARAD (registered trademark) ZCR-6001H (trade name), KAYARAD (registered trademark) ZCR-6002H (trade name), and KAYARAD (registered trademark) ZCR-6006H (trade name) manufactured by Nippon Kayaku Co., Ltd.) can be mentioned. These compounds having an ethylenically unsaturated group can be used alone or in an appropriate mixture of two or more.

[0066] In the resin composition of the present invention containing a compound having an ethylenically unsaturated group, the content of the compound having an ethylenically unsaturated group is preferably an amount of 0.1 to 500 equivalents relative to the ethylenically unsaturated double bond group equivalent of the polyimide resin.

[0067] In the resin composition of the present invention containing a compound having an ethylenically unsaturated group, a curing agent such as a radical initiator can be added as necessary for the purpose of promoting the curing reaction between the polyimide resin and the ethylenically unsaturated group. Specific examples of the radical initiator 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 addition amount of the radical initiator in 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 whole composition.

[0068] The resin composition of the present invention can be made into a varnish-like composition (hereinafter simply referred to as varnish) by using an organic solvent in combination. Examples of the solvents that can be used include amide solvents such as γ-butyrolactones, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone; sulfones such as tetramethylene sulfone; ether 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 solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic solvents such as toluene and xylene. The organic solvent is preferably used in a range such that the solid content concentration excluding the organic solvent in the varnish is 10 to 80% by mass, more preferably 20 to 70% by mass.

[0069] In the resin composition of the present invention, known additives may be used in combination as necessary. Specific examples of the additives that can be used in combination include curing agents for epoxy resins, polybutadiene or its modified products, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesins, maleimide-based compounds, cyanate ester-based compounds, silicone gels, silicone oils, and inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, etc., surface treatment agents for fillers such as silane coupling agents, release agents, carbon black, phthalocyanine blue, phthalocyanine green and other colorants, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and defoaming agents, hydroquinone, hydroquinone monomethyl ether, phenolic polymerization inhibitors, stabilizers, antioxidants, photopolymerization initiators, photobase generators, photoacid generators, and the like. The blending amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, based on 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 preferable from the viewpoint of heat resistance.

[0070] The method for preparing the resin composition of the present invention is not particularly limited, and each component may be simply mixed or prepolymerized. For example, the polyimide resin or the terminal-modified polyimide resin and the reactive compound of the present invention can be prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. For the mixing or prepolymerization of each component, in the absence of a solvent, for example, an extruder, a kneader, a roll, etc. are used, and in the presence of a solvent, a reaction kettle equipped with a stirrer, etc. is used.

[0071] The resin composition of the present invention can be made into a cured product by heating. The curing temperature and curing time of the resin composition may be selected in consideration of the combination of the functional groups of the polyimide resin of the present invention and the reactive groups of the thermosetting resin. For example, the curing temperature of a resin composition containing a maleimide resin or an epoxy resin is preferably 120 to 250°C, and the curing time is generally about several tens of minutes to several hours.

[0072] The resin composition of the present invention can be heated and melted to reduce its viscosity, and then impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Also, the varnish can be impregnated into the reinforcing fibers and then heated and dried to obtain a prepreg. The above prepreg is cut into a desired shape, and if necessary, laminated with a copper foil or the like, and then the resin composition is heat-cured while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, etc., to obtain a base material (article) provided with a cured product of the present invention such as a laminated board for electric and electronic applications (printed wiring board) or a carbon fiber reinforced material. Also, after coating the copper foil and drying the solvent medium, a polyimide film or LCP (liquid crystal polymer) is laminated, and after hot pressing, heat curing is performed to obtain a base material provided with a cured product of the present invention. In some cases, it can also be coated on the polyimide film or LCP side and laminated with the copper foil to obtain a base material provided with a cured product of the present invention. Furthermore, after coating the resin composition of the present invention on the copper foil and drying the solvent medium, a prepreg impregnated with the resin into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers is laminated, and after hot pressing, heat curing is performed to obtain a base material provided with a cured product of the present invention.

[0073] The base material provided with the polyimide resin of the present invention described above can be used for a copper-clad laminate (CCL), or a printed wiring board or a multilayer wiring board having a circuit pattern on the copper foil of the CCL.

Examples

[0074] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. It should be noted that the present invention is not limited to these Examples. In the Examples, "parts" means parts by mass, and "%" means mass %. The measurement conditions of GPC 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

[0075] Example 1 (Synthesis of Polyimide Resin 1 of the Present Invention) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet device and a stirring device, 49.3 parts of PRIAMINE 1075 (manufactured by Clariant Japan Co., Ltd., molecular weight 534.38 g / mol), 50.7 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 170.06 parts of anisole were added and heated to 70 °C. Next, 105.00 parts of ODPA (oxydiphthalic anhydride, manufactured by MANAC Co., Ltd., molecular weight 310.22 g / mol), 2.00 parts of triethylamine and 25.77 parts of toluene were added, and the reaction was carried out at 130 °C for 8 hours while removing the water generated by the ring closure of the amic acid by azeotropy with toluene to obtain an imidized product solution (P-1) (molecular weight of the imidized product 45,000). Subsequently, 4.9 parts of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g / mol) and 0.3 part of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor were added, and after reacting at 130 °C for 4 hours, it was confirmed by IR (infrared spectroscopy) that the peak derived from the isocyanate of Karenz MOI had disappeared. Then, the remaining triethylamine and toluene were continuously removed at 130 °C to obtain a polyimide resin solution. The molar ratio (number of moles of acid anhydride component / number of moles of diamine component) of the diamine component ((a1) component, (a2) component) and the acid anhydride component ((B) component) used in Example 1 was 1.05. Also, the number of moles MC of the compound (C) component having a functional group capable of reacting with the terminal functional group of the imidized product and an ethylenically unsaturated double bond group and the number of moles MP of the terminal functional group of the imidized product in the imidized product solution (P-1) satisfied the relationship of MC / MP = 0.98.

[0076] Example 2 (Synthesis of Polyimide Resin 2 of the Present Invention) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet device and a stirring device, 49.7 parts of PRIAMINE 1075 (manufactured by Clariant Japan Co., Ltd., molecular weight 534.38 g / mol), 55.3 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 170.06 parts of anisole were added and heated to 70 °C. Next, 100.00 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g / mol), 2.00 parts of triethylamine and 25.77 parts of toluene were added, and the reaction was carried out at 130 °C for 8 hours while removing the water generated by the ring closure of the amic acid by azeotropy with toluene to obtain an imidized product solution (P-2) (molecular weight of the imidized product 42,000). Subsequently, 5.0 parts of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g / mol) and 0.3 part of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor were added, and after reacting at 130 °C for 4 hours, it was confirmed by IR (infrared spectroscopy) that the peak derived from the isocyanate of Karenz MOI had disappeared. Then, the remaining triethylamine and toluene were continuously removed at 130 °C to obtain a polyimide resin solution. The molar ratio (number of moles of diamine component / number of moles of acid anhydride component) of the diamine component ((a1) component, (a2) component) and the acid anhydride component ((B) component) used in Example 2 was 1.05. Also, the number of moles MC of the compound (C) component having a functional group capable of reacting with the terminal functional group of the imidized product and an ethylenically unsaturated double bond group and the number of moles MP of the terminal functional group of the imidized product in the imidized product resin solution (P-2) satisfied the relationship of MC / MP = 1.00.

[0077] Comparative Example 1 (Synthesis of Comparative Polyimide Resin 1) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet device and a stirring device, 49.3 parts of PRIAMINE 1075 (manufactured by Clariant Japan Co., Ltd., molecular weight 534.38 g / mol), 50.7 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 170.06 parts of anisole were added and heated to 70°C. Next, 105.00 parts of ODPA (oxydiphthalic anhydride, manufactured by MANAC Co., Ltd., molecular weight 310.22 g / mol), 2.00 parts of triethylamine and 25.77 parts of toluene were added, and the reaction was carried out at 130°C for 8 hours while removing the water generated during the ring closure of the amic acid by azeotropy with toluene to obtain a comparative polyimide resin solution (P-3) (molecular weight of the polyimide resin 45,000).

[0078] Comparative Example 2 (Synthesis of Comparative Polyimide Resin 2) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet device and a stirring device, 49.7 parts of PRIAMINE 1075 (manufactured by Clariant Japan Co., Ltd., molecular weight 534.38 g / mol), 55.3 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 170.06 parts of anisole were added and heated to 70°C. Next, 100.00 parts of ODPA (oxydiphthalic anhydride, manufactured by MANAC Co., Ltd., molecular weight 310.22 g / mol), 2.00 parts of triethylamine and 25.77 parts of toluene were added, and the reaction was carried out at 130°C for 8 hours while removing the water generated during the ring closure of the amic acid by azeotropy with toluene to obtain a comparative polyimide resin solution (P-4) (molecular weight of the polyimide resin 42,000).

[0079] Examples 3 to 8, Comparative Examples 3 and 4 (Adjustment of the Resin Compositions of the Present Invention and Comparative Purposes) After blending each component in the blending amounts shown in Table 1 (the unit is "parts", and the number of parts of the polyimide resin and the maleimide resin are the number of parts in terms of solid content excluding the solvent), anisole in an amount such that the solid content concentration becomes 20% by mass was added as a solvent and uniformly mixed, whereby the resin compositions of the present invention and for comparison were respectively adjusted.

[0080] Incidentally, each component in Table 1 is as follows. <Polyimide resin> Polyimide resins 1 and 2; the polyimide resins of the present invention obtained in Examples 1 and 2 Comparative polyimide resins 1 and 2; the comparative polyimide resins obtained in Comparative Examples 1 and 2 <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 Nurion Co., Ltd. <Additive> KR-513; silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd. TT-LX; lubricating oil additive, manufactured by Johoku Chemical Co., Ltd.

[0081] Using the resin compositions obtained in Examples 3 to 8 and Comparative Examples 3 and 4, the adhesive strength, thermal properties, storage stability, and dielectric properties (dielectric constant and dielectric tangent) of the cured products of the resin compositions with respect to copper foil were evaluated by the following methods.

[0082] (Evaluation of adhesive strength) On the rough surface of the ultra-low roughness non-roughening treated electrolytic copper foil CF-T9DA-SV (hereinafter referred to as "T9DA") manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., the resin composition was applied using an automatic applicator respectively, and heated and dried at 120 °C for 10 minutes. The thickness of the dried coating film was 30 μm. The PPE prepreg (Meteorwave4000, manufactured by AGC nelco Co., Ltd.) was overlaid on the coating film on the copper foil obtained above, and vacuum pressed at 200 °C for 60 minutes under the condition of 3 MPa. The obtained test piece was cut into a width of 10 mm, and using an autograph AGS-X-500N (manufactured by Shimadzu Corporation), the 90° peel strength between copper foils (peel rate was 50 mm / min) was measured to evaluate the adhesion strength with the PPE prepreg. The results are shown in Table 1.

[0083] (Evaluation of thermal properties) The test piece prepared by the same method as the above "Evaluation of adhesion strength" was floated in a solder bath heated to 288 °C with POT-200C (manufactured by Taiyo Electric Industry Co., Ltd.), and the thermal properties were evaluated by the time until blistering occurred. The results are shown in Table 1.

[0084] (Evaluation of storage stability) Each resin composition was put into a screw bottle, and the change in viscosity after 4 months was confirmed under the condition of 25 °C. The results are shown in Table 1. 〇··The change in viscosity over time is less than 1% for both △··The change in viscosity over time is 1% or more and less than 2% ×··The change in viscosity over time is 2% or more

[0085] (Evaluation of dielectric constant and dielectric tangent) Except for changing the coating thickness of the automatic applicator, a coating film with a thickness of 100 μm after drying was formed on the rough surface of T9DA in the same manner as the above "evaluation of adhesive strength", and heat-cured at 200 °C for 60 minutes. The copper foil was removed by etching with an iron(III) chloride solution having a liquid specific gravity of 45 Baumé, washed with ion-exchanged water, and dried at 105 °C for 10 minutes to obtain film-like cured products respectively. Regarding the film-like cured products, the breaking stress, breaking elongation, and elastic modulus were measured using an autograph AGS-X-500N (manufactured by Shimadzu Corporation), and the dielectric constant and dielectric tangent at 10 GHz were measured by the cavity resonance method using a network analyzer 8719ET (manufactured by Agilent Technologies). The results are shown in Table 1.

[0086]

Table 1

[0087] From the results in Table 1, the resin composition of the present invention is excellent in all of adhesive strength, heat resistance, storage stability of varnish, and dielectric properties, while the resin composition of the comparative example was inferior in adhesiveness, heat resistance, and storage stability of varnish.

Industrial Applicability

[0088] By using the polyimide resin having a specific structure of the present invention, it is possible to provide a printed wiring board or the like excellent in properties such as heat resistance, mechanical properties, and low dielectric properties and adhesiveness.

Claims

1. An imidized product (P) of a polyamic acid resin which is a copolymer of an amino compound (A) containing an aliphatic diamino compound (a1) having 6 to 36 carbon atoms and an aromatic diamino compound (a2) having no phenolic hydroxyl group and a tetracarboxylic dianhydride (B), and a polyimide resin which is a reaction product of the imidized product (P) and a compound (C) having a functional group capable of reacting with the terminal functional group of the imidized product (P) and an ethylenically unsaturated double bond group, The polyimide resin, wherein the functional group capable of reacting with the terminal functional group of the imidized product (P) in the compound (C) is an isocyanate group.

2. The tetracarboxylic dianhydride (B) represents a divalent linking group represented by the following formulas (1) to (5). 【Chemical 1】 (In formula (4), Y is C(CF ３ )) ２ , SO ２ , CO, an oxygen atom, a direct bond or the following formula (6) [Chemical 2] ). The polyimide resin according to Claim 1, comprising a compound selected from the group consisting of

3. The compound (a2) is represented by the following formulas (7) to (10). [Chemical 3] (In formula (9), R ２ independently represents a methyl group or a trifluoromethyl group, and in formula (10), Z is CH(CH ３ ), SO ２ , CH ２ , O-C ６ H ４ -O, an oxygen atom, a direct bond, or the following formula (6) 【Chemical Formula 4】 The divalent linking group represented by is R ３ independently represents a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group. The polyimide resin according to claim 1, comprising a compound selected from the group consisting of).

4. A resin composition containing the polyimide resin according to any one of Claims 1 to 3 and a thermosetting resin.

5. The resin composition according to Claim 4, further containing a curing agent.

6. The resin composition according to Claim 4 or 5, further containing a silane coupling agent having an acrylic group.

7. A cured product of the resin composition according to any one of Claims 4 to 6.

8. An article provided with the cured product according to Claim 7.

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