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

Abstract

To provide a resin material having a new structure suitable for use in a printed wiring board and a resin composition comprising the resin material and the cured product of which has excellent substrate adhesiveness, heat resistance and flame retardancy.SOLUTION: There is provided a polyimide resin which is a reaction product of an imidization product (P) of a polyamic acid resin which is a copolymer of an amino compound (A) containing an aminophenol compound having at least two amino groups in one molecule (a1), an aliphatic diamino compound having 6 to 36 carbons (a2) and an aromatic diamino compound having no phenolic hydroxyl group (a3) and tetrabasic acid dianhydride (B) and a compound (C) having a functional group which can react with a phenolic hydroxyl group and an ethylenically unsaturated double bond group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to polyimide resins having novel structures, resin compositions containing the polyimide resins, 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. Various resin materials with excellent properties such as adhesion to metal foil, heat resistance, and flexibility are used for printed wiring boards. Moreover, in recent years, there has been development of high-speed, large-capacity printed wiring boards for next-generation high-frequency wireless communication, and in addition to the above-mentioned characteristics, the resin material is required to have low transmission loss, i.e., low dielectric constant and low dielectric tangent.

[0003] Polyimide resins, which are excellent in 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, it is known that hydrocarbon compounds such as petroleum and natural oils exhibit high insulating properties and low dielectric constants, and Patent Document 1 describes an example in which a dimer diamine skeleton, which is a long-chain alkyl, is introduced into a polyimide resin by utilizing these two characteristics. However, although the polyimide resins of Patent Documents 1 and 2 are excellent in terms of low dielectric tangent, they are inferior in flame retardancy, adhesion to substrates, and heat resistance.

[0004] On the other hand, Patent Document 3 describes the addition of a flame retardant to a polyimide having a dimer diamine skeleton introduced therein to improve flame retardancy. However, the flame retardant causes a decrease in the heat resistance and adhesiveness of the cured product, which is a problem. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-168369 A [Patent Document 2] Patent Application No. 2020-535005 [Patent Document 3] Patent application 2019-238108 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a resin material having a novel structure that can be suitably used for printed wiring boards, and a resin composition that contains the resin material and that, when cured, has excellent substrate adhesion, heat resistance, and flame retardancy. [Means for solving the problem]

[0007] As a result of extensive investigations, the present inventors have found that a resin composition containing a novel polyimide resin having a specific structure can solve the above problems, and have 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 aminophenol compound (a1) having at least two amino groups in one molecule and an aliphatic diamino compound (a2) having 6 to 36 carbon atoms with a tetrabasic acid dianhydride (B), a compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group, and a phosphorus compound (D) having a functional group capable of reacting with an ethylenically unsaturated double bond group; (2) The polyimide resin according to the above item (1), wherein the amino compound (A) contains an aromatic diamino compound (a3) ​​having no phenolic hydroxyl group. (3) The compound (a1) is represented by the following formula (1)

[0008] [ka]

[0009] (In formula (1), R 1 represents a hydrogen atom, a methyl group, or an ethyl group, and X is C(CH 3 ) 2, C(CF 3 ) 2 , S.O. 2 , an oxygen atom, a direct bond or the following formula (3)

[0010] [ka]

[0011] (c) a divalent linking group represented by the formula (1) or (2); (4) The tetrabasic acid dianhydride (B) is represented by the following formulas (4) to (12):

[0012] [ka]

[0013] (In formula (7), Y is C(CF 3 ) 2 , S.O. 2 , CO, an oxygen atom, a direct bond or the following formula (3)

[0014] [ka]

[0015] represents a divalent linking group represented by the formula: The polyimide resin according to any one of the above items (1) to (3), which contains a compound selected from the group consisting of: (5) The compound (a3) ​​is represented by the following formulas (13) to (16):

[0016] [ka]

[0017] (In formula (15), R 2 each independently represents a methyl group or a trifluoromethyl group, and in formula (16), Z is CH(CH 3 ), SO 2 , C.H. 2 , O.C. 6H 4 -O, an oxygen atom, a direct bond, or the following formula (3):

[0018] [ka]

[0019] A divalent linking group represented by R 3 (iii) independently represent a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group; (6) The polyimide resin according to any one of the above (1) to (5), wherein the functional group capable of reacting with a phenolic hydroxyl group contained in the compound (C) is an isocyanate group or a carboxylic acid chloride group. (7) A resin composition containing the polyimide resin according to any one of (1) to (6) above and a thermosetting resin. (8) The resin composition according to the above item (7), further comprising a curing agent. (9) The resin composition according to the above item (7) or (8), further comprising a silane coupling agent having an acrylic group. (10) A cured product of the resin composition according to any one of (7) to (9) above, and (11) An article comprising the cured product according to the preceding item (10). Regarding. Effect of the Invention

[0020] 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 having excellent adhesiveness, heat resistance, and flame retardancy. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The polyimide resin of the present invention is a reaction product of an imidized product (P) (hereinafter also referred to simply as "imidized product (P)") of a polyamic acid resin which is a copolymer of an amino compound (A) (hereinafter also referred to simply as "component (A)") including an aminophenol compound (a1) (hereinafter also referred to simply as "component (a1)") having at least two amino groups in one molecule and an aliphatic diamino compound (a2) (hereinafter also referred to simply as "component (a2)") having 6 to 36 carbon atoms, and a tetrabasic acid dianhydride (B) (hereinafter also referred to simply as "component (B)"), a compound (C) (hereinafter also referred to simply as "component (C)") having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group, and a phosphorus compound (D) (hereinafter also referred to simply as "component (D)") having a functional group capable of reacting with an ethylenically unsaturated double bond group. First, the imidized product (P), which is an intermediate raw material for the polyimide resin of the present invention, will be described.

[0022] The (a1) component used in the synthesis of the imidized product (P) is not particularly limited as long as it is a compound having at least two amino groups and at least one phenolic hydroxyl group in one molecule. Specific examples of the (a1) component include 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybenzophenone, 2,2-bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, and 9,9'-bis(3-amino-4-hydroxyphenyl)fluorene. These may be used alone or in combination of two or more.

[0023] The component (a1) used in the synthesis of the imidized product (P) preferably contains a compound represented by the following formula (1).

[0024] [ka]

[0025] In formula (1), R 1 represents a hydrogen atom, a methyl group, or an ethyl group, and X is C(CH 3 ) 2 , C(CF 3 ) 2 , S.O. 2 , an oxygen atom, a direct bond, or a divalent linking group represented by the following formula (3):

[0026] [ka]

[0027] The amount of component (a1) used when synthesizing the imidized product (P) is preferably an amount such that the phenolic hydroxyl group equivalent of the imidized product (P) is in the range of 1,500 to 25,000 g / eq. If the phenolic hydroxyl group equivalent is less than 1,500 g / eq., the polarity of the final polyimide resin of the present invention becomes high, resulting in a high dielectric loss tangent of the cured product of the resin composition containing the polyimide resin, whereas if it exceeds 25,000 g / eq., the number of reaction points with component (C) described below decreases, resulting in a decrease in the number of crosslinking points of the final polyimide resin, and the heat resistance and adhesion to substrates of the cured product of the resin composition tend to decrease. In this specification, the phenolic hydroxyl group equivalent means a value measured by a method according to JIS K-0070.

[0028] The imidized product (P) is obtained by an imidization reaction of a polyamic acid resin, which is a copolymer of components (A) and (B), that is, a cyclization reaction by dehydration condensation. Therefore, the amounts (ratios) of components (A) and (B) required to synthesize an imidized product (P) having the intended hydroxyl group equivalent and aliphatic chain content can be easily calculated from the molecular weights of components (A) and (B) used in the copolymerization reaction and the number of phenolic hydroxyl groups in component (a1).

[0029] The component (a2) used in the synthesis of the imidized product (P) is not particularly limited as long as it is an aliphatic compound having two amino groups in one molecule and a carbon number of 6 to 36. The aliphatic structure in the component (a2) may be linear, branched, or cyclic, or may have a combination of the above structures, and may be either saturated 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-1,5-9-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 diaminopolysiloxane having 6 to 36 carbon atoms. These may be used alone or in combination of two or more. From the viewpoint of the dielectric properties of the polyimide resin, it is preferable to use dimer diamine.

[0030] The dimer diamine described in the section of specific examples of the component (a2) is a dimer of unsaturated fatty acid such as oleic acid, in which two carboxyl groups of the dimer acid are substituted with primary amino groups (see JP-A-9-12712, etc.). 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. Below, non-limiting general formulas of dimer diamines are shown (in each formula, m+n=6 to 17 is preferable, p+q=8 to 19 is preferable, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond).

[0031] [ka]

[0032] The amount of the (a2) component used in synthesizing the imidized product (P) is preferably an amount that is within the range of 10 to 50 mass% of the mass (mass of the generated imidized product (P)) obtained by subtracting the mass of water (water generated by the dehydration condensation reaction) twice the number of moles of the (B) component from the mass of the (A) component. If the amount of the (a2) component is below the above range, the aliphatic chains derived from the (a2) component in the finally obtained polyimide resin are too few, resulting in a high dielectric tangent of the cured product of the resin composition, whereas if the amount exceeds the above range, the aliphatic chains derived from the (a2) component in the polyimide resin are too many, resulting in a low heat resistance of the cured product of the resin composition.

[0033] For the purpose of improving the heat resistance of the polyimide resin of the present invention, an aromatic diamino compound (a3) ​​having no phenolic hydroxyl group (hereinafter, simply referred to as "component (a3)") may be used in combination with component (A). Component (a3) ​​is an aromatic diamino compound other than component (a1) described above, and is not particularly limited as long as it is an aromatic compound having two amino groups in one molecule. Specific examples of the component (a3) ​​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.

[0034] From the viewpoints of the heat resistance of the cured resin composition and the solubility in a solvent of the final polyimide resin, it is preferable that the component (a3) ​​used in the synthesis of the imidized product (P) contains a compound selected from the group consisting of the following formulas (13) to (16).

[0035] [ka]

[0036] In formula (15), R 2 Each independently represents a methyl group or a trifluoromethyl group. 3 are independently a hydrogen atom, a methyl group, or an ethyl group, and Z is CH(CH 3 ), SO 2 , C.H. 2 , O.C. 6 H 4 represents -O, an oxygen atom, a direct bond, or a divalent linking group represented by the above formula (3).

[0037] The component (B) 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 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-methylcyclopentadiene, 1,2,3,4-butanetetracarboxylic dianhydride ... 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, 5,5'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), and the like. Among these, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, or 3,3',4,4'-diphenylethertetracarboxylic dianhydride are preferred from the viewpoints of solvent solubility, adhesion to a substrate, and photosensitivity. These may be used alone or in combination of two or more.

[0038] From the viewpoint of the solvent solubility of the polyamic acid resin, the imidized product (P), and the final polyimide resin, the component (B) used in the synthesis of the imidized product (P) preferably contains a compound selected from the group consisting of the following formulas (4) to (12).

[0039] [ka]

[0040] In formula (7), Y is C(CF 3 ) 2 , S.O. 2 , CO, an oxygen atom, a direct bond, or a divalent linking group represented by the above formula (3).

[0041] In the (A) component used in the synthesis of the imidized product (P), the number of moles of the (a1) component is a1M, the number of moles of the (a2) component is a2M, and the number of moles of the (a3) ​​component is a3M. The value of a1M / (a1M+a2M+a3M) is preferably more than 0.01 and less than 0.5, and more preferably more than 0.03 and less than 0.3. When a1M / (a1M+a2M+a3M) is 0.01 or less, the reaction site with the (C) component described below is reduced, and as a result, the partial structure derived from the (D) component introduced into the polyimide resin of the present invention is reduced, so that the substrate adhesion and flame retardancy of the cured product of the resin composition tend to decrease. In addition, when a1M / (a1M+a2M+a3M) is 0.5 or more, the dielectric properties of the cured product of the resin composition tend to decrease.

[0042] Also, the value of a2M / (a1M+a2M+a3M) is preferably more than 0.2 and less than 0.9, more preferably more than 0.3 and less than 0.6. When a2M / (a1M+a2M+a3M) 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. Also, when a2M / (a1M+a2M+a3M) is 0.8 or more, the heat resistance of the cured product of the resin composition tends to deteriorate.

[0043] Furthermore, the value of a3M / (a1M+a2M+a3M) is preferably greater than 0.1 and less than 0.8, and more preferably greater than 0.2 and less than 0.6. When a3M / (a1M+a2M+a3M) is within the above preferred range, the solder heat resistance of the cured product of the resin composition is improved, and the solvent solubility of the polyimide resin tends to be improved.

[0044] When the number of moles of component (A) is MA and the number of moles of component (B) is MB, and the amount of component (A) and component (B) that satisfies the relationship MA / MB>1 is copolymerized, an imidized product (P) of a polyamic acid resin having amino groups at both ends is obtained. In this case, the value of MA / MB is preferably in the range of more than 1.0 and less than 2.0, and more preferably in the range of more than 1.0 and less than 1.5. If the value is 2.0 or more, the final polyimide resin will not be sufficiently polymerized, and the remaining rate of unreacted raw materials will be high, which may reduce various properties such as heat resistance after curing of the resin composition (described later).

[0045] When the number of moles of component (A) is MA and the number of moles of component (B) is MB, and the amount of component (A) and component (B) that satisfies the relationship MB / MA>1 is copolymerized, an imidized product (P) of a polyamic acid resin having carboxylic anhydride groups at both ends is obtained. In this case, the value of MB / MA is preferably in the range of more than 1.0 and less than 2.0, and more preferably in the range of more than 1.0 and less than 1.5. If the value is 2.0 or more, the final polyimide resin will not be sufficiently polymerized, and the remaining rate of unreacted raw materials will be high, which may reduce various properties such as heat resistance after curing of the resin composition (described later).

[0046] The imidized product (P) can be synthesized by a known method. For example, the components (A) and (B) used for the synthesis are dissolved in a solvent, and then heated and stirred at 10 to 140° C. in an inert atmosphere such as nitrogen to cause a copolymerization reaction between the diamines and the tetrabasic acid dianhydrides, thereby obtaining a polyamic acid resin solution.

[0047] In addition, a dehydrating agent or catalyst is added to the polyamic acid resin solution obtained above as necessary, and the solution is heated and stirred at 100 to 300°C to cause an imidization reaction (a ring-closing reaction accompanied by dehydration), thereby obtaining an imidized product (P). 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 thereof include pyridine, picoline, quinoline, and isoquinoline. As the dehydration catalyst, examples thereof include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. The reaction time when synthesizing 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, which is usually several minutes to 40 hours.

[0048] The above example is a method for synthesizing a polyimide resin via a polyamic acid. Alternatively, the components (A) and (B) used in the synthesis may be dissolved in a solvent, and then a dehydrating agent or catalyst may be added as necessary, followed by heating and stirring at 100 to 300° C. to carry out the copolymerization reaction and the imidization reaction in one go, thereby obtaining the imidized product (P).

[0049] Examples of the solvent that can be used in the synthesis of the imidized compound (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, 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, isopropyl acetate, and ethyl ethyl acetate. Examples of the aryl esters include, but are not limited to, propyl, 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, and dimethyl sulfoxide. These may be used alone or in combination of two or more.

[0050] The amount of the solvent used should be appropriately adjusted depending on the viscosity and use of the resulting resin, but the solid content is preferably 60 to 10% by mass, more preferably 50 to 20% by mass.

[0051] In the synthesis of the imidized product (P), it is preferable to use a catalyst to promote the dehydration reaction, and the amount of the catalyst used is preferably 1 to 30% of twice the number of moles of the component (B) (the number of moles of water generated by dehydration condensation), more preferably 5 to 15%. Specific examples of catalysts that can be used include known general basic catalysts such as triethylamine and pyridine. Among them, triethylamine is preferable because it has a low boiling point and is less likely to remain.

[0052] Next, the reaction product of the imidized compound (P) and the component (C) will be described. The 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 a phenolic hydroxyl group and an ethylenically unsaturated double bond group. The reaction product of the phenolic hydroxyl group of the imidized product (P) and the component (C) reacts with the ethylenically unsaturated double bond group derived from the component (C) and the component (D) described below, and the cured product of the resin composition has excellent flame retardancy, substrate adhesion, and heat resistance. In addition, by reacting the phenolic hydroxyl group of the imidized product (P) with the component (C), the viscosity of the polyimide resin tends to decrease and the lamination property to the substrate tends to improve.

[0053] Examples of functional groups that can react with the phenolic hydroxyl group of component (C) include isocyanate groups, carboxylic acid chloride groups, acid anhydride groups, epoxy groups, silyl chloride groups, halogenated alkyl groups, ester groups, sulfonyl chloride groups, and carboxyl groups, etc. In particular, isocyanate groups are preferred because they do not produce residual impurities derived from leaving groups from component (C). The ethylenically unsaturated double bond group contained in the component (C) is not particularly limited as long as it is a C=C bond. Furthermore, assuming that the number of moles of component (A) is MA and the number of moles of component (B) is MB, the imidized product (P) obtained by copolymerizing component (A) and component (B) in amounts that satisfy the relationship MA / MB>1 has an amine terminal, and therefore can react with the terminal amine of imidized product (P) when the functional group reactive with the phenolic hydroxyl group of component (C) is an isocyanate group, a carboxylic acid chloride group, an acid anhydride group, an epoxy group, a silyl chloride group, a halogenated alkyl group, an ester group, a sulfonyl chloride group, or a carboxyl group. On the other hand, when the number of moles of component (A) is MA and the number of moles of component (B) is MB, and the amount of component (A) and component (B) that satisfies the relationship MA / MB<1 is copolymerized to give imidized product (P), the imidized product (P) has an acid anhydride terminal, and therefore when the functional group capable of reacting with the phenolic hydroxyl group of component (C) is an isocyanate group, an epoxy group, or a carboxyl group, it can react with the terminal acid anhydride group of imidized product (P).

[0054] Specific examples of the (C) component include Karenz MOI (manufactured by Showa Denko K.K.), Karenz AOI, Karenz MOI-BM, Karenz MOI-BP, Karenz BEI, Karenz MOI-EG, 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, acrylic anhydride, methacrylic acid anhydride, glycidyl methacrylate, glycidyl acrylate, maleimidocaproic acid, and the like.

[0055] The reaction product of the imidized product (P) and the component (C) can be synthesized by a known method, for example, by mixing a resin solution of the imidized product (P) with a given component (C) and reacting at 80°C to 150°C.

[0056] Various catalysts may be used to promote the reaction between the imidized product (P) and the component (C). The catalyst may be any of known inorganic acids, organic acids, inorganic bases, and organic bases.

[0057] When the number of moles of the (C) component is MC, the number of moles of the phenolic hydroxyl group of the imidized product (P) is MAB, and the number of moles of the terminal functional group of the imidized product (P) is MP, the value of MC / (MAB+MP) is preferably more than 0.3 and less than 1, and more preferably more than 0.5 and less than 1. When MC / (MAB+MP) exceeds 1, the heat resistance of the cured product of the resin composition is deteriorated due to the unreacted (C) component. In addition, when MC / (MAB+MP) is 0.3 or less, the viscosity of the polyimide resin solution increases due to hydrogen bonds of the phenolic hydroxyl group that does not react with the (C) component, and the lamination property tends to decrease, and the substrate adhesion of the cured product of the resin composition tends to decrease.

[0058] Next, the polyimide resin of the present invention, which is a reaction product between the imidized product (P) and the component (C), and a reaction product between the component (D), will be described. The component (D) is not particularly limited as long as it is a phosphorus compound having a functional group capable of reacting with an ethylenically unsaturated double bond group. The phosphorus compound here means a compound having a phosphorus atom (P) in its structure. By reacting the component (D) with the ethylenically unsaturated bond of the reaction product of the imidized compound (P) and the component (C), flame retardancy, substrate adhesion, and heat resistance are all achieved.

[0059] Examples of functional groups that can react with the ethylenically unsaturated double bond group of component (D) include an acrylic group, a methacrylic group, a thiol group, an amino group, a phosphorous acid derivative having a PH bond, a maleimide group, a diene, etc. In particular, a phosphorous acid derivative having a PH bond is preferred because it can react with the ethylenically unsaturated bond of the reaction product of the imidized product (P) and component (C) under mild conditions without a catalyst.

[0060] Specific examples of the (D) component include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diethyl phosphite, diisopropyl phosphite, dibenzyl phosphite, bis(2-ethylhexyl) phosphite, dilauryl phosphite, di(9-octadecenyl) phosphite, diphenyl phosphite, dibutyl phosphite, phenylphosphinic acid, diethyl allylphosphonate, 3-aminopropylphosphonic acid, alendronic acid, pamidronic acid, diethyl(4-aminophenyl)phosphonate, (diphenylphosphinoyl)methyl 2-methylprop-2-enoate, FRM-1000 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0061] The polyimide resin of the present invention, which is a reaction product of the imidized product (P) and the component (C), and then the component (D), can be synthesized by a known method, for example, by mixing a resin solution of the imidized product (P) with a given component (C) and reacting at 80°C to 150°C.

[0062] Various catalysts may be used to promote the reaction between the imidized product (P) and component (C). The catalyst may be any of known inorganic acids, organic acids, inorganic bases, organic bases, radical initiators, photobase generators, and photoacid generators.

[0063] When the number of moles of the (D) component used in the synthesis of the polyimide resin of the present invention is defined as MD and the number of moles of the (C) component is defined as MC, it is preferable that the MC / MD value is less than 1, since the polyimide resin contains ethylenically unsaturated double bond groups which react with each other or with a thermosetting resin described below, resulting in a cured product of the resin composition having both excellent heat resistance and adhesiveness. In particular, the value of MC / MD is preferably more than 0.1 and less than 1, and more preferably more than 0.2 and less than 0.8. When MC / MD exceeds 1, the heat resistance of the cured product of the resin composition deteriorates due to the unreacted (D) component. Also, when MC / MD is 0.1 or less, the flame retardancy of the cured product of the resin tends to decrease.

[0064] Next, the resin composition of the present invention will be described. The resin composition of the present invention contains the polyimide resin of the present invention, which is a reaction product of the imidized product (P) with the component (C), and a reaction product of the component (D), and a thermosetting resin (compound). 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, 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 cured product to be obtained. In the resin composition of the present invention, by using a thermosetting resin (compound) in combination with a polyimide resin, it is possible to impart thermal stability and high adhesiveness to the cured product of the resin composition.

[0065] The thermosetting resin (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 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, the number of moles of phenolic hydroxyl groups in the imidized product (P) is MAB, and the number of moles of terminal functional groups in the imidized product (P) is MP, for polyimide resins in which the value of MA / MB is greater than 1 and the value of MC / (MAB+MP) is greater than 0 and less than 1, it is also preferable to use an epoxy resin as the thermosetting resin.

[0066] From the viewpoint of suppressing an 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 weight average molecular weight of a polystyrene standard measured by gel permeation chromatography (GPC).

[0067] 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, because the cured product of the resin composition has excellent properties such as mechanical strength and flame retardancy, maleimide resins having an aromatic ring such as a benzene ring, a biphenyl ring, or a naphthalene ring are preferred. Specific examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.) and MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.). When the number of moles of the component (C) used in the synthesis of the polyimide resin of the present invention is defined as MC and the number of moles of the component (D) is defined as MD, in a resin composition containing a polyimide resin and a maleimide resin, in which MD / MC is greater than 0 and less than 1, the maleimide resin reacts with the ethylenically unsaturated double bond group of the polyimide resin, thereby increasing the crosslink density of the cured product and improving the resistance to polar solvents as well as the 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 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 per equivalent of the ethylenically unsaturated double bond group of the polyimide resin.

[0068] In order to accelerate the curing reaction of the maleimide resin, various radical initiators may be added as a curing agent to the resin composition of the present invention containing the maleimide resin, as necessary. 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 amount of the radical initiator added to the resin composition of the present invention containing a maleimide resin is preferably 0.1 to 10% by mass relative to the maleimide resin.

[0069] The epoxy resin as the 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 has excellent properties such as mechanical strength and flame retardancy, epoxy resins having aromatic rings such as a benzene ring, a biphenyl ring, and a naphthalene ring are preferred. 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 phenolic hydroxyl groups, terminal amino groups, or acid anhydride groups of the polyimide resin, thereby increasing the crosslink density of the cured product, improving resistance to polar solvents, and improving adhesion to the substrate 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 about several minutes to several hours.

[0070] The content of the epoxy resin in the resin composition of the present invention containing an epoxy resin is preferably such that the epoxy group equivalent of the epoxy resin relative to 1 equivalent of the active hydrogen and acid anhydride of the phenolic hydroxyl group and terminal amino group of the polyimide resin is 0.1 to 500. Since the epoxy group of the epoxy resin has reactivity with the phenolic hydroxyl group, it is a preferred embodiment to add an epoxy resin in an amount such that the epoxy equivalent of the epoxy resin relative to 1 equivalent of the phenolic hydroxyl group of the polyimide resin is 0.1 to 500 equivalents as necessary.

[0071] In order to promote the curing reaction of the epoxy resin, a curing agent may be added to the resin composition of the present invention containing the epoxy resin, if necessary. 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 octylate. 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 based on the epoxy resin.

[0072] The compound having an ethylenically unsaturated group as the thermosetting resin is not particularly limited as long as it has an ethylenically unsaturated group in one molecule. Specific examples of compounds 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.

[0073] Other specific examples of the compound 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 epoxy resins and having both a (meth)acryloyl group; and reactive oligomers in which these bonds are used in combination.

[0074] Examples of urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylate with polyisocyanate and other alcohols used as necessary. Examples of urethane (meth)acrylates 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 polyisocyanate include urethane (meth)acrylates obtained by reacting sugar alcohol (meth)acrylates such as 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.

[0075] 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.

[0076] Further 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, δ-valerolactone, etc. 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, δ-valerolactone, etc. to 1 mole of dipentaerythritol, and mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols, or hexaols.

[0077] Further examples include polyfunctional (poly)ester (meth)acrylates such as 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 consisting of diol components, polybasic acids, their anhydrides, and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc.

[0078] Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. For example, phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, trishydroxyphenylmethane 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 novolac type epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, and the like, and the epoxy acrylates modified with acid anhydrides thereof, and the like can be mentioned.

[0079] 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.

[0080] As the compound having an ethylenically unsaturated group, commercially available products can be used, and examples thereof include KAYARAD ZCA (registered trademark)-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 can be used alone or in an appropriate mixture of two or more types.

[0081] 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 polyimide resin.

[0082] In order to promote the curing reaction between the polyimide resin and the ethylenically unsaturated group, a curing agent such as a radical initiator may be added to the resin composition of the present invention containing a compound having an ethylenically unsaturated group, as necessary. 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 amount of the radical initiator added 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 entire composition.

[0083] 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.

[0084] The resin composition of the present invention may be used in combination with known additives as necessary. Specific examples of additives that can be used in combination include epoxy resin curing agents, polybutadiene or modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ethers, polystyrene, polyethylene, polyimides, 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, 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 defoamers, hydroquinone, hydroquinone monomethyl ether, phenol-based polymerization inhibitors, stabilizers, antioxidants, photopolymerization initiators, photobase generators, and photoacid generators. The 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 preferred from the viewpoint of heat resistance.

[0085] The method for preparing the resin composition of the present invention is not particularly limited, but each component may be simply mixed uniformly, or may be prepolymerized. For example, the polyimide resin or terminal-modified polyimide resin of the present invention and the 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 each component, for example, an extruder, kneader, roll, etc. are used in the absence of a solvent, and a reaction kettle with a stirrer is used in the presence of a solvent.

[0086] The curing temperature and curing time of the resin composition of the present invention may be selected taking into consideration the combination of the functional group of the polyimide resin of the present invention and the reactive group of the thermosetting resin, and the like. 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.

[0087] 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 above prepreg is cut into a desired shape and laminated with copper foil or the like as necessary. The resin composition is then heated and cured while applying pressure to the laminate by press molding, autoclave molding, sheet winding molding 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 a copper foil. In addition, a substrate having the cured product of the present invention can be obtained by coating the resin composition of the present invention on copper foil, drying the solvent, laminating a prepreg in which the resin is impregnated into reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber, and then heat-pressing and curing the prepreg by heating. Alternatively, the resin composition of the present invention can be applied to copper foil, the solvent medium is dried, and the two are laminated together so that the resin surfaces overlap, and then the resulting laminate is heat-pressed and heat-cured to obtain a substrate having the cured product of the present invention. Further, the resin composition of the present invention may be cured by active energy rays to form a hard coat agent or a resist material such as a solder resist for the purpose of coating a surface, and may further include a so-called dry film in which the resin composition is temporarily applied to a peelable substrate to form a film, which is then laminated to the intended substrate to form a coating.

[0088] The substrate comprising the polyimide resin of the present invention can be used for copper clad laminates (CCL), or for printed wiring boards and multilayer wiring boards having a circuit pattern on the copper foil of the CCL. EXAMPLES

[0089] 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 standards: polystyrene

[0090] Example 1 (Synthesis of polyimide resin 1 of the present invention) A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet, and a stirrer was charged with 5.84 parts of DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 10.29 parts of PRIAMINE1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 2.16 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 69.4 parts of anisole, and heated to 70°C. Next, 12.409 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g / mol), 0.81 parts of triethylamine and 19.13 parts of toluene were added, and the water generated by the ring closure of the amic acid was removed by azeotropy with toluene while reacting for 8 hours at 130 ° C. to obtain an imide compound (P-1) (phenolic OH equivalent, 1,440 g / eq., molecular weight 71,400) solution. Subsequently, the remaining triethylamine and toluene were removed at 130 ° C., and then 6.19 parts of Karenz AOI (manufactured by Showa Denko Co., Ltd., molecular weight 141.12 g / mol) were added and reacted for 3 hours at 80 ° C., and then 9.47 parts of HCA (manufactured by Sanko Co., Ltd., molecular weight 216.17 g / mol) were added and reacted for 3 hours at 80 ° C. to obtain a polyimide resin (A-1) solution. The molar ratio (moles of diamine component / moles of acid anhydride component) of the diamine components (components (a1), (a2), and (a3)) and the acid anhydride component (component (B)) used in Example 1 was 1.01.

[0091] Example 2 (Synthesis of polyimide resin 2 of the present invention) After removing residual triethylamine and toluene at 130°C from the imidized product (P-1) solution obtained in the same manner as in Example 1, 2.12 parts of Karenz AOI (manufactured by Showa Denko K.K., molecular weight 141.12 g / mol), 6.81 parts of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 151.15 g / mol), and 0.5 parts of BHT (2,6-di-tert-butyl-p-cresol) were added and reacted at 80°C for 3 hours, and then 9.47 parts of HCA (manufactured by Sanko Co., Ltd., molecular weight 216.17 g / mol) was added and reacted at 80°C for 3 hours to obtain a polyimide resin (A-2) solution. The molar ratio (moles of diamine component / moles of acid anhydride component) of the diamine components (components (a1), (a2), and (a3)) and the acid anhydride component (component (B)) used in Example 2 was 1.01.

[0092] Comparative Example 1 (Synthesis of Comparative Polyimide Resin 1) A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet, and a stirrer was charged with 5.40 parts of DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 54.2 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 41.4 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 1 part of anisole. 70.06 parts were added and heated to 70 ° C. Then, 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 mixture was reacted at 130 ° C. for 8 hours while removing water generated by ring closure of amic acid by azeotropic distillation with toluene to obtain a solution of polyimide resin (A-3) for comparison (phenolic OH equivalent, 6,780 g / eq., molecular weight 54,200). The molar ratio (moles of diamine component / moles of acid anhydride component) of the diamine component ((a1) component, (a2) component and (a3) ​​component) and the acid anhydride component ((B) component) used in Comparative Example 1 was 1.01.

[0093] Comparative Example 2 (Synthesis of Comparative Polyimide Resin 2) A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen introducing apparatus, and a stirrer was charged with 55.1 parts of PRIAMINE 1075 (manufactured by Croda Japan Ltd., molecular weight 534.38 g / mol), 45.9 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, and heated to 70°C. Next, 100.00 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), 2.00 parts of triethylamine, and 25.77 parts of toluene were added, and the mixture was reacted at 130° C. for 8 hours while removing water generated by ring closure of the amic acid by azeotropic distillation with toluene, and then the remaining triethylamine and toluene were removed at 130° C. to obtain a solution of polyimide resin (A-4) (molecular weight 69,400) for comparison. The molar ratio (moles of diamine component / moles of acid anhydride component) of the diamine component (component (a2) and component (a3)) and the acid anhydride component (component (B)) used in Comparative Example 2 was 1.01.

[0094] Comparative Example 3 (Synthesis of Comparative Polyimide Resin 3) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet, and a stirrer, 9.20 parts of DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., The mixture was heated to 70° C. after adding 91.8 parts of oxydiphthalic anhydride (manufactured by Manac Corporation, molecular weight 310.22 g / mol), 2.00 parts of triethylamine, and 25.77 parts of toluene. The mixture was reacted at 130° C. for 8 hours while removing water generated by the ring closure of the amic acid by azeotropy with toluene to obtain an imidized product (P-5) (phenolic OH equivalent, A solution of 4,374 g / eq. and molecular weight 70,000 was obtained. Subsequently, 7.4 parts of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g / mol) and 0.3 parts of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor were added and reacted at 130°C for 4 hours, and the remaining triethylamine and toluene were subsequently removed at 130°C to obtain a solution of polyimide resin (A-5) for comparison. The molar ratio of the diamine components (components (a1) and (a2)) to the acid anhydride component (component (B)) (number of moles of diamine component / number of moles of acid anhydride component) was 1.01. Furthermore, assuming that the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group is MC, the number of moles of the phenolic hydroxyl group in the imidized product (P-5) is MAB, and the number of moles of the terminal functional group in the imidized product (P-5) is MP, then MC / (MAB+MP) = 0.55.

[0095] Examples 3 to 6 and Comparative Examples 4 to 6 (Preparation of Resin Compositions of the Present Invention and Comparative Examples) The components were mixed in the amounts shown in Table 1 (the unit is "parts", and the parts of the polyimide resin and the maleimide resin are parts converted into solid content excluding the solvent), and then anisole was added as a solvent in an amount such that the solid content concentration became 20 mass %, and the mixture was mixed uniformly to prepare the resin compositions of the present invention and the comparative examples.

[0096] The components in Table 1 are as follows: <Polyimide resin> (A-1): Polyimide resin (A-1) obtained in Example 1 (A-2): Polyimide resin (A-2) obtained in Example 2 (A-3): Comparative polyimide resin (A-3) obtained in Comparative Example 1 (A-4): Comparative polyimide resin (A-4) obtained in Comparative Example 2 (A-5): Comparative polyimide resin (A-5) obtained in Comparative Example 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. <Hardening agent> DCP: Dicumyl peroxide, manufactured by Nouryon Chemical Co., Ltd.

[0097] Using each of the resin compositions obtained in Examples 3 to 6 and Comparative Examples 4 to 6, the adhesive strength to copper foil and heat resistance of the cured products of the resin compositions were evaluated by the following methods.

[0098] (Adhesion test) The resin composition was applied to the rough surface of ultra-low roughness non-roughened electrolytic copper foil CF-T9DA-SV (hereinafter referred to as "T9DA") manufactured by Fukuda Metal Foil and Powder Co., Ltd. using an automatic applicator, and then heated and dried at 120°C for 10 minutes. The thickness of the coating film after drying was 30 μm. A PPE prepreg (Meteorwave4000, manufactured by AGC Nelco Co., Ltd.) was superimposed 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 the 90° peel strength between the copper foils (peel speed was 50 mm / min) was measured using an autograph AGS-X-500N (manufactured by Shimadzu Corporation), and the adhesion to the PPE prepreg was evaluated according to the following evaluation criteria. The results are shown in Table 1. 〇...5.0N / cm or more △ 2.5N / cm or more, less than 5.0N / cm × Less than 2.5N / cm

[0099] (Heat resistance test) Test pieces prepared in the same manner as in the "Adhesion Test" above were floated in a solder bath heated to 288°C using a POT-200C (manufactured by Taiyo Electric Industry Co., Ltd.), the time until blisters appeared was measured, and the heat resistance was evaluated according to the following evaluation criteria. The results are shown in Table 1. ○ No swelling for more than 600 seconds △: 100 seconds or more, less than 600 seconds: no swelling × Blisters appear in less than 100 seconds

[0100] (Flame Retardancy Test) A coating film of the resin composition was formed on the rough surface of T9DA in the same manner as in the above "Adhesion Test" except that the coating amount of the resin composition was changed to an amount that would result in a film thickness of the resin composition layer after drying of 100 μm, and the coating film was cured at 200 ° C for 60 minutes. From the laminate of the cured layer of the resin composition and the copper foil obtained above, the copper foil was etched off with an iron (III) chloride solution having a liquid specific gravity of 45 Baume degrees, washed with ion-exchanged water, and dried at 105 ° C for 10 minutes to obtain a film-like cured product of the resin composition. The burning time of this test piece was measured according to the UL94 flammability test, and the flame retardancy was evaluated according to the following evaluation criteria. The results are shown in Table 1. ◎: UL V-0 equivalent (The total burning time of five test pieces, each ignited twice, is less than 50 seconds.) ○: UL V-1 equivalent (The total burning time of five test pieces, each ignited twice, exceeds 50 seconds and reaches 250 seconds.) ×: No self-extinguishing properties

[0101] [Table 1]

[0102] From the results in Table 1, it is clear that the resin composition of the present invention is superior in adhesive strength, heat resistance and flame retardancy to the resin compositions of the comparative examples. [Industrial Applicability]

[0103] 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 having excellent adhesiveness, heat resistance, and flame retardancy.

Claims

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 aminophenol compound (a1) having at least two amino groups in one molecule and an aliphatic diamino compound (a2) having 6 to 36 carbon atoms with a tetrabasic acid dianhydride (B), a compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group, and a phosphorus compound (D) having a functional group capable of reacting with an ethylenically unsaturated double bond group.

2. 2. The polyimide resin according to claim 1, wherein the amino compound (A) comprises an aromatic diamino compound (a3) ​​having no phenolic hydroxyl group.

3. The compound (a1) is represented by the following formula (1): 【Chemistry 1】 (In formula (1), R １ represents a hydrogen atom, a methyl group, or an ethyl group, and X is C(CH ３ ) ２ , C(CF ３ ) ２ , S.O. ２ , an oxygen atom, a direct bond, or the following formula (3) 【Chemistry 2】 represents a divalent linking group represented by the formula: The polyimide resin according to claim 1 or 2, which contains a compound represented by the formula:

4. The tetrabasic acid dianhydride (B) is represented by the following formulas (4) to (12): 【Chemistry 3】 (In formula (7), Y is C(CF ３ ) ２ , S.O. ２ , CO, an oxygen atom, a direct bond, or the following formula (3): 【Chemical Formula 4】 represents a divalent linking group represented by the formula: The polyimide resin according to claim 1 , further comprising a compound selected from the group consisting of:

5. The compound (a3) ​​is represented by the following formulas (13) to (16): 【Chemistry 5】 (In formula (15), R ２ each independently represents a methyl group or a trifluoromethyl group, and in formula (16), Z is CH(CH ３ ), S.O. ２ , C.H. ２ , O-C ６ H ４ -O, an oxygen atom, a direct bond, or the following formula (3): 【Chemistry 6】 The divalent linking group represented by R ３ each independently represents a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group. The polyimide resin according to claim 1 , further comprising a compound selected from the group consisting of:

6. 6. The polyimide resin according to claim 1, wherein the functional group capable of reacting with a phenolic hydroxyl group contained in the compound (C) is an isocyanate group or a carboxylic acid chloride group.

7. A resin composition comprising the polyimide resin according to claim 1 and a thermosetting resin.

8. The resin composition according to claim 7, further comprising a curing agent.

9. The resin composition according to claim 7 or 8, further comprising a silane coupling agent having an acrylic group.

10. A cured product of the resin composition according to any one of claims 7 to 9.

11. An article comprising the cured product according to claim 10.

Images