JP2023108082A - Polyimide resin, resin composition comprising the polyimide resin and cured product thereof - Google Patents

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

BACKGROUND ART Printed wiring boards are indispensable members for electronic devices such as mobile communication devices such as smartphones and tablets, communication base station devices, computers and car navigation systems. 2. Description of the Related Art 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, high-speed, large-capacity printed wiring boards for next-generation high-frequency radio have been developed. It is required to be tangent.

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 parts, semiconductors, communication equipment and its circuit parts, peripheral equipment, and the like. On the other hand, it is known that hydrocarbon compounds such as petroleum and natural oils exhibit high insulating properties and low dielectric constants. An example in which a skeleton of dimer diamine is introduced is described. However, although the polyimide resins of Patent Documents 1 and 2 are excellent in terms of low dielectric loss tangent, they are inferior in flame retardancy, substrate adhesion and heat resistance.

On the other hand, Patent Document 3 describes that a flame retardant is added to a polyimide having a dimer diamine skeleton to improve flame retardancy, but the flame retardant reduces the heat resistance and adhesiveness of the cured product. was a problem.

JP 2018-168369 A Japanese Patent Application No. 2020-535005 Patent application 2019-238108

An object of the present invention is to provide a resin material having a novel structure that can be suitably used for printed wiring boards, and a resin composition containing the resin material, the cured product of which is excellent in substrate adhesion, heat resistance and flame retardancy. to do.

As a result of intensive studies, the present inventors have found that a resin composition containing a novel polyimide resin having a specific structure can solve the above problems, and completed the present invention.
That is, the present invention
(1) 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 and a tetrabasic dianhydride ( A reaction product of an imidized polyamic acid resin (P) that is a copolymer of B) and a compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group, A polyimide resin that is a reaction product with a phosphorus compound (D) having a functional group capable of reacting with an ethylenically unsaturated double bond group,
(2) The polyimide resin according to (1) above, wherein the amino compound (A) contains an aromatic diamino compound (a3) having no phenolic hydroxyl group,
(3) Compound (a1) is represented by the following formula (1)

(In formula (1), R ₁ represents a hydrogen atom, a methyl group or an ethyl group, X is C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , SO ₂ , an oxygen atom, a direct bond or the following formula (3) )

Represents a divalent linking group represented by ) The polyimide resin according to the preceding item (1) or (2) containing a compound represented by
(4) Tetrabasic dianhydride (B) is represented by the following formulas (4) to (12)

(In formula (7), Y is C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or the following formula (3)

Represents a divalent linking group represented by )
The polyimide resin according to any one of the preceding items (1) to (3) containing a compound selected from the group consisting of
(5) Compound (a3) is represented by the following formulas (13) to (16)

(In formula (15), R ₂ independently represents a methyl group or a trifluoromethyl group; in formula (16), 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 (3)

_R3 independently represents a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group. ) The polyimide resin according to any one of the preceding items (1) to (4) containing a compound selected from the group consisting of
(6) The polyimide resin according to any one of (1) to (5) above, wherein the functional group capable of reacting with the phenolic hydroxyl group of the compound (C) is an isocyanate group or a carboxylic acid chloride group,
(7) A resin composition containing the polyimide resin and the thermosetting resin according to any one of (1) to (6) above,
(8) The resin composition according to the preceding item (7), which further contains a curing agent;
(9) The resin composition according to (7) or (8) above, which further contains 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 (10) above,
Regarding.

By using the polyimide resin having the specific structure of the present invention, it is possible to provide a printed wiring board or the like excellent in adhesiveness, heat resistance and flame retardancy.

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

The component (a1) used for synthesizing the imidized compound (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 component (a1) 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 and the like. These may be used alone or in combination of two or more.

The component (a1) used for synthesizing the imidized compound (P) preferably contains a compound represented by the following formula (1).

In formula (1), R ₁ represents a hydrogen atom, a methyl group or an ethyl group, X is C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , SO ₂ , an oxygen atom, a direct bond or the following formula (3) Represents a divalent linking group represented by

The amount of component (a1) used when synthesizing the imidized product (P) is such that the phenolic hydroxyl equivalent of the imidized product (P) is 1,500 to 25,000 g/eq. is preferred. A phenolic hydroxyl equivalent of 1,500 g/eq. is lower than 25,000 g/eq. If it exceeds, the number of cross-linking points of the polyimide resin finally obtained by reducing the reaction points with the component (C) described later is reduced, and the heat resistance of the cured product of the resin composition and the adhesiveness to the substrate. tends to decline.
Incidentally, the phenolic hydroxyl group equivalent in the present specification means a value measured by a method according to JIS K-0070.

The imidized product (P) is obtained by an imidization reaction of a polyamic acid resin which is a copolymer of the components (A) and (B), ie, a cyclization reaction by dehydration condensation. Therefore, the amounts (ratios) of the components (A) and (B) necessary for synthesizing the imidized product (P) having the intended hydroxyl group equivalent and aliphatic chain content are and (B) components and the number of phenolic hydroxyl groups in component (a1).

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 6 to 36 carbon atoms and having two amino groups in one molecule. The aliphatic structure in the component (a2) may be linear, branched or cyclic, or may have the above structures, and may be saturated or unsaturated. may Specific examples of component (a2) include hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,3-bisaminomethylcyclohexane, norbornanediamine, isophoronediamine, dimerdiamine, 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, diaminopolysiloxane having 6 to 36 carbon atoms, and the like. These may be used alone or in combination of two or more. Moreover, it is preferable to use a dimer diamine from a viewpoint of the dielectric property of a polyimide resin.

The dimer diamine described in the specific examples of component (a2) is obtained by substituting primary amino groups for the two carboxyl groups of dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid. See Japanese Laid-Open Patent Publication No. 9-12712, etc.). Specific examples of commercially available dimer diamines include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.) and Versamin 551 (manufactured by Cognis Japan Co., Ltd.). These may be used alone or in combination of two or more. Hereinafter, 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 broken line indicates a carbon-carbon single bond or a carbon-carbon double bond. means).

The amount of component (a2) used when synthesizing the imidized product (P) is determined by dividing the mass of component (A) by the number of moles of water (water generated by the dehydration condensation reaction) that is twice the number of moles of component (B). ) (the mass of the imidized product (P) produced) is preferably in the range of 10 to 50% by mass. If the amount of component (a2) is below the above range, the number of aliphatic chains derived from component (a2) in the finally obtained polyimide resin is too small, resulting in a high dielectric loss tangent of the cured product of the resin composition. On the other hand, if the above range is exceeded, the number of aliphatic chains derived from component (a2) in the polyimide resin is too large, and the heat resistance of the cured product of the resin composition is lowered.

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)") is used in combination with component (A). good too. Component (a3) is not particularly limited as long as it is an aromatic diamino compound other than component (a1) and is an aromatic compound having two amino groups in one molecule.
Specific examples of 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'-diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenylthioether, 3, 3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, 3,3′-dimethoxy-4,4′-diaminodiphenylthioether, 2,2′-bis(3-aminophenyl)propane, 2,2′-bis(4-aminophenyl)propane, 4, 4'-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 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-propyl phenyl)methane and bis(4-amino-3,5-dipropylphenyl)methane, and the like. These may be used alone or in combination of two or more.

The (a3) component used for the synthesis of the imidized product (P) has the following formulas (13) to ( It preferably contains a compound selected from the group consisting of 16).

In formula (15), _R2 independently represents a methyl group or a trifluoromethyl group. In formula (16), R ₃ is independently a hydrogen atom, a methyl group or an ethyl group; Z is CH(CH ₃ ), SO ₂ , CH ₂ , O—C ₆ H ₄ —O, an oxygen atom, or a direct bond; Or represents a divalent linking group represented by the above formula (3).

The component (B) used for synthesis of the imidized compound (P) is not particularly limited as long as it has two acid anhydride groups in one molecule. Specific examples of component (B) include pyromellitic anhydride, ethylene glycol-bis(anhydrotrimellitate), glycerin-bis(anhydrotrimellitate) monoacetate, 1,2,3,4,-butane Tetracarboxylic 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-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) and the like. Among them, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride and 3,3′,4,4′-benzophenone are preferred in terms of solvent solubility, adhesion to substrates, and photosensitivity. Tetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride or 3,3′,4,4′-diphenylethertetracarboxylic dianhydride is preferred. These may be used alone or in combination of two or more.

The (B) component used for the synthesis of the imidized product (P) is represented by the following formulas (4) to (12) from the viewpoint of the solvent solubility of the polyamic acid resin, the imidized product (P), and the polyimide resin finally obtained. It is preferable to contain a compound selected from the group consisting of

In formula (7), Y represents C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or a divalent linking group represented by formula (3) above.

When the number of moles of component (a1) in component (A) used for synthesis of imidized compound (P) is a1M, the number of moles of component (a2) is a2M, and the number of moles of component (a3) is a3M, a1M The value of /(a1M+a2M+a3M) is preferably greater than 0.01 and less than 0.5, more preferably greater than 0.03 and less than 0.3. When a1M/(a1M+a2M+a3M) is 0.01 or less, the number of reaction sites with component (C), which will be described later, is reduced, and as a result, the partial structure derived from component (D) introduced into the polyimide resin of the present invention is reduced. Therefore, the substrate adhesiveness and flame retardancy of the cured product of the resin composition tend to decrease. Further, when a1M/(a1M+a2M+a3M) is 0.5 or more, the dielectric properties of the cured product of the resin composition tend to deteriorate.

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. If a2M/(a1M+a2M+a3M) is less than 0.2, 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 a2M/(a1M+a2M+a3M) is 0.8 or more, the heat resistance of the cured product of the resin composition tends to deteriorate.

Also, the value of a3M/(a1M+a2M+a3M) is preferably more than 0.1 and less than 0.8, more preferably more than 0.2 and less than 0.6. When a3M/(a1M+a2M+a3M) is within the above preferable range, the soldering heat resistance of the cured product of the resin composition tends to improve, and the solvent solubility of the polyimide resin tends to improve.

The number of moles of component (A) is MA, and the number of moles of component (B) is MB. An imidized product (P) of the polyamic acid resin of the group is obtained. At this time, the value of MA/MB is preferably over 1.0 and less than 2.0, more preferably over 1.0 and less than 1.5. If the above value is 2.0 or more, in addition to insufficient increase in the molecular weight of the finally obtained polyimide resin, the residual rate of unreacted raw materials increases, resulting in a resin composition (described later). Various properties such as heat resistance after curing may deteriorate.

The number of moles of component (A) is MA, and the number of moles of component (B) is MB. An imidized product (P) of a polyamic acid resin having an acid anhydride group is obtained. At this time, the value of MB/MA is preferably more than 1.0 and less than 2.0, more preferably more than 1.0 and less than 1.5. If the above value is 2.0 or more, in addition to insufficient increase in the molecular weight of the finally obtained polyimide resin, the residual rate of unreacted raw materials increases, resulting in a resin composition (described later). Various properties such as heat resistance after curing may deteriorate.

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

In addition, if necessary, a dehydrating agent or a catalyst is added to the polyamic acid resin solution obtained above, and the mixture is heated and stirred at 100 to 300° C. to cause an imidization reaction (ring-closure reaction accompanied by dehydration) to form the imidized product (P). can get. Toluene, xylene and the like can be used as dehydrating agents, and tertiary amines and dehydrating catalysts can be used as catalysts. Preferred tertiary amines are heterocyclic tertiary amines such as pyridine, picoline, quinoline, and isoquinoline. Dehydration catalysts include, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. The reaction time for 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 increase in viscosity accompanying the progress of the reaction reaches equilibrium and the maximum molecular weight is obtained. , usually from a few minutes to 40 hours.

The above example is a method of synthesizing a polyimide resin via polyamic acid. The copolymerization reaction and the imidization reaction may be performed together by heating and stirring at 300° C. to 300° C. to obtain the imidized product (P).

Solvents that can be used in synthesizing 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, and 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, aceto Methyl acetate, 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, isovaleric acid Ethyl, isoamyl isovalerate, diethyl oxalate, dibutyl oxalate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Examples include, but are not limited to, sulfoxides. These may be used alone or in combination of two or more.

The preferred amount of the solvent to be used should be appropriately adjusted depending on the viscosity of the resin to be obtained and the intended use.

When synthesizing the imidized product (P), it is preferable to use a catalyst to promote the dehydration reaction. ), preferably 1 to 30%, more preferably 5 to 15%. Specific examples of usable catalysts include known basic catalysts such as triethylamine and pyridine. Among them, triethylamine is preferable because it has a low boiling point and does not easily remain.

Next, the reaction product of imidized product (P) and component (C) will be described.
The (C) component used for 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 to cure the resin composition. Excellent flame retardancy, adhesion to substrates, and heat resistance are compatible. 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 be lowered and the laminating property to the substrate tends to be improved.

Examples of functional groups capable of reacting with phenolic hydroxyl groups of component (C) include isocyanate groups, carboxylic acid chloride groups, acid anhydride groups, epoxy groups, silyl chloride groups, halogenated alkyl groups, ester groups, and sulfonyl chlorides. groups, carboxyl groups, and the like. In particular, an isocyanate group is preferred because residual impurities derived from leaving groups are not generated from the component (C).
In addition, the ethylenically unsaturated double bond group of the component (C) is not particularly limited as long as it is a C═C bond.
Further, the imide obtained by copolymerizing the amount of component (A) and component (B) satisfying the relationship MA/MB>1, where MA is the number of moles of component (A) and MB is the number of moles of component (B). Since the compound (P) has an amine terminal, the functional groups capable of reacting with the phenolic hydroxyl group of component (C) are isocyanate group, carboxylic acid chloride group, acid anhydride group, epoxy group, silyl chloride group, halogen In the case of an alkyl group, an ester group, a sulfonyl chloride group and a carboxyl group, they can react with the terminal amine of the imidized compound (P).
On the other hand, the number of moles of component (A) is MA and the number of moles of component (B) is MB. Since the terminal of the compound (P) is an acid anhydride, when the functional group capable of reacting with the phenolic hydroxyl group of the component (C) is an isocyanate group, an epoxy group, or a carboxyl group, the terminal of the imidized compound (P) It can react with anhydride groups.

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

A reaction product of 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) with a resin solution of the imidized compound (P) and reacting it at 80°C to 150°C.

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

Where MC is the number of moles of the component (C), MAB is the number of moles of the phenolic hydroxyl group of the imidized product (P), and MP is the number of moles of the terminal functional group of the imidized product (P), the value of MC/(MAB+MP) is preferably greater than 0.3 and less than 1, more preferably greater than 0.5 and less than 1. When MC/(MAB+MP) exceeds 1, the unreacted component (C) deteriorates the heat resistance of the cured product of the resin composition. Further, when MC/(MAB+MP) is 0.3 or less, the viscosity of the polyimide resin solution increases due to the hydrogen bonding of the phenolic hydroxyl groups that do not react with the component (C), and the lamination property tends to decrease. The substrate adhesion of the cured product tends to decrease.

Next, the polyimide resin of the present invention, which is the reaction product of imidized product (P) and component (C) and the reaction product of component (D), will be described.
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 referred to here means a compound having a phosphorus atom (P) in its structure. By reacting the (D) component with the ethylenically unsaturated bond of the reaction product of the imidized product (P) and the (C) component, flame retardancy, substrate adhesion and heat resistance are all achieved.

Examples of functional groups capable of reacting with the ethylenically unsaturated double bond groups of component (D) include acrylic groups, methacrylic groups, thiol groups, amino groups, phosphorous acid derivatives having a PH bond, and maleimide groups. , diene, and the like. In particular, a phosphorous acid derivative having a PH bond is preferred because it can react with the ethylenically unsaturated bond of the reactant of the imidized product (P) and the component (C) under mild conditions without a catalyst. .

Specific examples of component (D) include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diethyl phosphite, diisopropyl phosphite, dibenzyl phosphite, bis( 2-ethylhexyl), 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.

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

Various catalysts may be used to promote the reaction between the imidized product (P) and the component (C). As the catalyst, known inorganic acids, organic acids, inorganic bases, organic bases, radical initiators, photobase generators, photoacid generators and the like can be used.

When the number of moles of component (D) used in the synthesis of the polyimide resin of the present invention is MD and the number of moles of component (C) is MC, when the value of MC/MD is less than 1, the polyimide resin is ethylene It is preferable because it contains a polyunsaturated double bond group, which reacts with each other or with a thermosetting resin described later, and the cured product of the resin composition has both excellent heat resistance and adhesiveness.
In particular, the value of MC/MD is preferably more than 0.1 and less than 1, more preferably more than 0.2 and less than 0.8. When MC/MD exceeds 1, the unreacted component (D) deteriorates the heat resistance of the cured product of the resin composition. Moreover, when MC/MD is 0.1 or less, the flame retardancy of the cured resin tends to be lowered.

Next, the resin composition of the present invention will be explained.
The resin composition of the present invention contains the polyimide resin and the thermosetting resin (compound) of the present invention, which are the reaction product of the imidized product (P) and component (C) and the reaction product of component (D).
Specific examples of thermosetting resins (compounds) contained in the resin composition of the present invention include epoxy resins, maleimide resins, carbodiimide resins, benzoxazine compounds and compounds having ethylenically unsaturated groups. These resins or compounds can be used singly or in admixture of two or more depending on the physical properties and applications of the resulting cured product.
In the resin composition of the present invention, heat stability and high adhesiveness can be imparted to the cured product of the resin composition by using a thermosetting resin (compound) together with the polyimide resin.

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 because the cured product of the resin composition has particularly excellent heat resistance and adhesiveness. .
Incidentally, the number of moles of the component (A) used in the synthesis of the polyimide resin of the present invention is MA, the number of moles of the component (B) is MB, the number of moles of the component (C) is MC, and the phenolic property of the imide (P) When the number of moles of hydroxyl groups is MAB and the number of moles of terminal functional groups of the imide (P) is MP, the value of MA/MB exceeds 1 and the value of MC/(MAB+MP) exceeds 0 and 1 It is also preferable to use an epoxy resin as a thermosetting resin with respect to the polyimide resin which is less than.

Moreover, the thermosetting resin (compound) preferably has a molecular weight of 100 to 50,000 from the viewpoint of suppressing an increase in the viscosity of the varnish. In addition, the molecular weight in the present specification means the weight average molecular weight of polystyrene standard by gel permeation chromatography (GPC) method.

The maleimide resin as a thermosetting resin is not particularly limited as long as it has two or more maleimide groups in one molecule. , A maleimide resin having an aromatic ring such as a benzene ring, a biphenyl ring and a naphthalene ring is preferable, and specific examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.) and MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.). etc.
When the number of moles of the component (C) used for the synthesis of the polyimide resin of the present invention is MC and the number of moles of the component (D) is MD, the polyimide resin and the maleimide resin in which MD/MC exceeds 0 and is less than 1 In the resin composition containing, the maleimide resin reacts with the ethylenically unsaturated double bond group of the polyimide resin, thereby increasing the crosslink density of the cured product, improving the resistance to polar solvents, and the substrate Adhesion to and heat resistance are improved.
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 several minutes to several hours.
The content of the maleimide resin in the resin composition of the present invention containing a maleimide resin is such that the maleimide group equivalent of the maleimide resin is 0.1 to 500 equivalents per equivalent of the ethylenically unsaturated double bond groups of the polyimide resin. preferable.

The resin composition of the present invention containing a maleimide resin may optionally contain various radical initiators as a curing agent for the purpose of promoting the curing reaction of the maleimide resin. Radical initiators include peroxides such as dicumyl peroxide and dibutyl peroxide, 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile), and the like. azo compounds, and the like.
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 based on the maleimide resin.

The epoxy resin as a thermosetting resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Epoxy resins having an aromatic ring such as a benzene ring, a biphenyl ring and a naphthalene ring are preferred, and specific examples thereof include jER828 (Mitsubishi Chemical Co., Ltd.), NC-3000, and XD-1000 (both Nippon Kayaku Co., Ltd. made) and the like.
The epoxy resin is added for the purpose of reacting with the phenolic hydroxyl group or terminal amino group or acid anhydride group of the polyimide resin, thereby increasing the crosslink density of the cured product and improving the resistance to polar solvents. Adhesion to substrates and heat resistance are improved.
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 several minutes to several hours.

The content of the epoxy resin in the resin composition of the present invention containing an epoxy resin is such that the epoxy group equivalent of the epoxy resin is 0.1 to 0.1 to 1 equivalent of the active hydrogen and acid anhydride of the phenolic hydroxyl group and terminal amino group of the polyimide resin. An amount that gives 500 equivalents is preferred. In addition, since the epoxy group of the epoxy resin has reactivity with the phenolic hydroxyl group, it is necessary to use the epoxy resin in such an amount that the epoxy equivalent of the epoxy resin per equivalent of the phenolic hydroxyl group of the polyimide resin is 0.1 to 500 equivalents. It is a preferable aspect to add according to necessity.

If necessary, a curing agent can be added to the resin composition of the present invention containing an epoxy resin for the purpose of accelerating the curing reaction of the epoxy resin. Curing agents include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. imidazoles, tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, octylic acid Metal compounds such as tin and the like are included.
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.

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 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 ) 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, adipate 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 ) acrylate, triethylolpropane 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 ethylene oxide adducts thereof.

In addition to these, 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 Epoxy (meth) acrylates derived from resins and having (meth) acryloyl groups; reactive oligomers in which these bonds are used in combination are also specific examples of compounds having ethylenically unsaturated groups.

Urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylates, polyisocyanates, and other alcohols used as necessary. For example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; ) acrylates; sugar alcohol (meth)acrylates such as pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and toluene diisocyanate , hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and their isocyanurates, burette reaction products, etc., reacted with polyisocyanates, etc., urethane ( meth)acrylates.

Polyester (meth)acrylates include, for example, 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 tetrahydro Monofunctional (poly)ester (meth)acrylates such as furfuryl (meth)acrylate; hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, epichlorohydrin-modified Di (poly) ester (meth) acrylates such as phthalic acid di (meth) acrylate; 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone per 1 mol of trimethylolpropane or glycerin Mono-, di- or tri(meth)acrylates of adducted triols may be mentioned.

Also, a triol obtained by adding 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mol of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane. mono-, di-, tri-, or tetra-(meth)acrylates; mono-triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone to 1 mol of dipentaerythritol, or Examples include mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols or hexaols of poly(meth)acrylates.

Furthermore, diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, hexanediol, maleic acid, fumaric Polybasic acids such as acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, and anhydrides thereof (meth)acrylate of polyester polyol which is the reaction product of; (meth)acrylate of cyclic lactone-modified polyester diol composed of diol component, polybasic acid and their anhydrides and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. and polyfunctional (poly)ester (meth)acrylates such as

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, 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)acrylates, and acid anhydride-modified epoxy acrylates thereof.

For example, 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; A compound having a vinyl group such as lunadiimide is also included as a specific example of the compound having an ethylenically unsaturated group.

As the compound having an ethylenically unsaturated group, commercially available products can be used. Glycol monomethyl ether acetate (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), and KAYARAD (registered trademark) ZCR-6006H (trade name), KAYARAD (registered trademark) ZXR-1889H (trade name) These compounds having an ethylenically unsaturated group can be used alone or in combination of two or more. It is also possible to mix them appropriately and use them.

The content of the compound having an ethylenically unsaturated group in the resin composition of the present invention containing a compound having an ethylenically unsaturated group is 0.1 to 0.1 with respect to the ethylenically unsaturated double bond group equivalent of the polyimide resin. An amount that gives 500 equivalents is preferred.

In the resin composition of the present invention containing a compound having an ethylenically unsaturated group, a curing agent such as a radical initiator is optionally added for the purpose of promoting the curing reaction between the polyimide resin and the ethylenically unsaturated group. can do Specific examples of radical initiators include peroxides such as dicumyl peroxide and dibutyl peroxide, 2,2′-azobis(isobutyronitrile) and 2,2′-azobis(2,4-dimethylvalero nitrile) and other azo compounds.
The amount of the radical initiator added to the resin composition of the present invention containing a compound having an ethylenically unsaturated group is 0.1 to 10% by mass based on the ethylenically unsaturated groups in the entire composition.

An organic solvent can be used together with the resin composition of the present invention to form a varnish-like composition (hereinafter simply referred to as varnish). Solvents that can be used include, for example, γ-butyrolactones, amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and N,N-dimethylimidazolidinone, and tetramethylenesulfone. Ether solvents such as sulfones, 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 Solvents include aromatic solvents such as toluene and xylene.
The organic solvent is used in such a range that the solid concentration of the varnish excluding the organic solvent is preferably 10 to 80% by mass, more preferably 20 to 70% by mass.

If necessary, known additives may be used in combination with the resin composition of the present invention. Specific examples of additives that can be used in combination include curing agents for epoxy resins, polybutadiene or modified products thereof, modified acrylonitrile copolymers, polyphenylene ethers, polystyrene, polyethylene, polyimide, fluororesins, maleimide compounds, cyanate esters. compound, silicone gel, silicone oil, silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, inorganic fillers such as glass powder, silane Surface treatment agents for fillers such as coupling agents, release agents, coloring agents such as carbon black, phthalocyanine blue, and phthalocyanine green, thixotropic agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, Hydroquinone, hydroquinone monomethyl ether, phenol-based polymerization inhibitors, stabilizers, antioxidants, photopolymerization initiators, photobase generators, photoacid generators, and the like. The amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, per 100 parts by mass of the resin composition. As the additive, a silane coupling agent having an acrylic group or a methacrylic group is particularly preferable from the viewpoint of heat resistance.

The method for preparing the resin composition of the present invention is not particularly limited, but each component may be mixed uniformly or may be prepolymerized. For example, the polyimide resin or terminal-modified polyimide resin and 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 mixing or prepolymerizing each component, for example, an extruder, kneader, rolls, etc. are used in the absence of a solvent, and a reactor equipped with a stirrer is used in the presence of a solvent.

The curing temperature and curing time of the resin composition of the present invention may be selected in consideration of the combination of the functional group of the polyimide resin of the present invention and the reactive group of the thermosetting resin. The curing temperature of the resin composition containing or the epoxy resin is preferably 120 to 250° C., and the curing time is generally several tens of minutes to several hours.

A prepreg can be obtained by heating and melting the resin composition of the present invention, reducing the viscosity, and impregnating reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers with the resin composition. A prepreg can also be obtained by impregnating reinforcing fibers with the varnish and heating and drying the varnish.
After cutting the above prepreg into a desired shape and laminating it with copper foil or the like if necessary, the resin composition is heated and cured while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like. Base materials (articles) comprising the cured product of the present invention, such as electronic laminates (printed wiring boards) and carbon fiber reinforcing materials, can be obtained.
In addition, after coating on a 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 the cured product of the present invention. can also In some cases, a base material provided with the cured product of the present invention can also be obtained by coating on the polyimide film or LCP side and laminating it with a copper foil.
In addition, after coating the resin composition of the present invention on a copper foil and drying the solvent medium, a prepreg in which reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber are impregnated with the resin is laminated. It is also possible to obtain a substrate provided with the cured product of the present invention by heat-curing after heat-pressing.
Further, after coating the resin composition of the present invention on a copper foil and drying the solvent medium, they are laminated so that the resin surfaces overlap each other, and after hot pressing, the cured product of the present invention is provided by heat curing. A substrate can also be obtained.
In addition, the resin composition of the present invention is cured by an active energy ray, and a resist material such as a hard coating agent and a solder resist for the purpose of coating the surface, and a resin composition is temporarily applied to a peelable substrate. A so-called dry film is also included, in which a film is formed by laminating it on a base material originally intended to form a film.

The substrate comprising the polyimide resin of the present invention can be used for copper clad laminates (CCL), printed wiring boards and multilayer wiring boards having circuit patterns on the copper foil of CCL.

EXAMPLES 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. "Parts" in the examples means parts by mass, and "%" means % by 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

Example 1 (synthesis of polyimide resin 1 of the present invention)
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 5.84 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol) 10.29 parts, BAFL (9,9-bis 2.16 parts of (4-aminophenyl)fluorene, manufactured by JFE Chemical Co., Ltd., molecular weight 348.16 g/mol) and 69.4 parts of anisole were added 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 due to ring closure of amic acid was removed. A solution of imidized compound (P-1) (phenolic OH equivalent, 1,440 g/eq., molecular weight: 71,400) was obtained by reacting at 130° C. for 8 hours while azeotropically removing with toluene. Subsequently, after removing residual triethylamine and toluene at 130° C., 6.19 parts of Karenz AOI (manufactured by Showa Denko KK, molecular weight: 141.12 g/mol) was added and reacted at 80° C. for 3 hours, followed by HCA. (manufactured by Sanko Co., Ltd., molecular weight 216.17 g/mol) 9.47 parts were added and reacted at 80° C. for 3 hours to obtain a polyimide resin (A-1) solution.
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Example 1 (the number of moles of the diamine component/the number of the acid anhydride component number of moles) was 1.01.

Example 2 (synthesis of polyimide resin 2 of the present invention)
After removing residual triethylamine and toluene from the imidized product (P-1) solution obtained in the same manner as in Example 1 at 130° C., Karenz AOI (manufactured by Showa Denko K.K., molecular weight 141.12 g/mol) 2.12. 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 the mixture was stirred at 80°C for 3 hours. 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 of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Example 2 (the number of moles of the diamine component/the number of the acid anhydride component number of moles) was 1.01.

Comparative Example 1 (Synthesis of Comparative Polyimide Resin 1)
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4′-(hexafluoroisopropylidene)bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 5.40 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534 .38 g / mol) 54.2 parts, BAFL (9,9-bis (4-aminophenyl) fluorene, JFE Chemical Co., Ltd., molecular weight 348.16 g / mol) 41.4 parts, and anisole 170.06 parts and heated to 70° C. Then, 100.00 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., molecular weight: 310.22 g/mol), 2.00 parts of triethylamine and 25.77 parts of toluene were added, and the amic acid was added. The reaction was carried out at 130 ° C. for 8 hours while removing the water generated due to the ring closure by azeotrope with toluene. 200) solution was obtained.The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Comparative Example 1 (molar number/moles of acid anhydride component) was 1.01.

Comparative Example 2 (Synthesis of Comparative Polyimide Resin 2)
55.1 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol) was added to a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen introduction device and a stirring device. , 45.9 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, JFE Chemical Co., Ltd., 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 water generated due to the ring closure of the amic acid was removed. After reacting at 130° C. for 8 hours with azeotropic removal with toluene, residual triethylamine and toluene were subsequently removed at 130° C. to prepare a solution of comparative polyimide resin (A-4) (molecular weight 69,400). got The molar ratio of the diamine component (components (a2) and (a3)) and the acid anhydride component (component (B)) used in Comparative Example 2 (moles of diamine component/moles of acid anhydride component) was 1. 0.01.

Comparative Example 3 (Synthesis of Comparative Polyimide Resin 3)
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4′-(hexafluoroisopropylidene)bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 9.20 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534) .38 g/mol) and 170.06 parts of anisole were added and heated to 70° C. Then, 100.00 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., 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 due to the ring closure of the amic acid by azeotroping with toluene, and imidized product (P-5) (phenol OH equivalent, 4,374 g/eq., molecular weight: 70,000) solution, followed by 7.4 parts of Karenz MOI (manufactured by Showa Denko K.K., molecular weight: 155.15 g/mol) and BHT as a polymerization inhibitor. 0.3 part of (2,6-di-tert-butyl-p-cresol) was added and reacted at 130° C. for 4 hours. A resin (A-5) solution was obtained.The molar ratio of the diamine component ((a1) component and (a2) component) and the acid anhydride component ((B) component) used in Comparative Example 3 (the number of moles of the diamine component / the number of moles of the acid anhydride component) is 1.01, and 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 imide ( MC/(MAB+MP)=0.55, where MAB is the number of moles of phenolic hydroxyl groups in P-5) and MP is the number of moles of terminal functional groups of imidized product (P-5).

Examples 3 to 6, Comparative Examples 4 to 6 (Preparation of the present invention and comparative resin compositions)
After blending each component in the blending amount shown in Table 1 (the unit is "part", the number of parts of polyimide resin and maleimide resin is the number of parts in terms of solid content not including solvent), the solid content concentration is 20% by mass. The resin composition of the present invention and the comparative resin composition were each prepared by adding anisole as a solvent and mixing uniformly.

In addition, each component in Table 1 is 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, Nippon Kayaku Co., Ltd. XD-1000; Epoxy resin, Nippon Kayaku Co., Ltd. ZXR-1889H; Epoxy acrylate resin, Nippon Kayaku Co., Ltd. <Hardener>
DCP; dicumyl peroxide, manufactured by Kayaku Nourion Co., Ltd.

Using the resin compositions obtained in Examples 3 to 6 and Comparative Examples 4 to 6, the adhesion strength and heat resistance of the cured resin compositions to copper foil were evaluated by the following methods.

(Adhesion test)
A resin composition is 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 & Powder Co., Ltd. using an automatic applicator. Each was applied and dried by heating at 120° C. for 10 minutes. The thickness of the coating film after drying was 30 μm. A PPE prepreg (Meteorwave 4000, 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 at 3 MPa. The obtained test piece was cut into a width of 10 mm, and the 90° peeling strength (peeling speed: 50 mm/min) between copper foils was measured using Autograph AGS-X-500N (manufactured by Shimadzu Corporation). Then, the adhesiveness to the PPE prepreg was evaluated according to the following evaluation criteria. Table 1 shows the results.
○: 5.0 N/cm or more △: 2.5 N/cm or more and less than 5.0 N/cm ×: less than 2.5 N/cm

(Heat resistance test)
A test piece prepared by the same method as the above "adhesion test" is floated in a solder bath heated to 288 ° C. with POT-200C (manufactured by Taiyo Denki Sangyo Co., Ltd.), and the time until blisters appear is measured. Heat resistance was evaluated according to the following evaluation criteria. Table 1 shows the results.
◯: No swelling for 600 seconds or more △: No swelling for 100 seconds or more and less than 600 seconds ×: Blistering occurred in less than 100 seconds

(Flame retardant test)
A coating of the resin composition was applied to 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 so that the film thickness of the resin composition layer after drying was 100 μm. were formed and cured by heating at 200° C. for 60 minutes. From the laminate of the cured product layer of the resin composition and the copper foil obtained above, the copper foil is etched away with an iron (III) chloride solution having a liquid specific gravity of 45 Baume degrees, washed with ion-exchanged water, and then heated at 105 ° C. By drying for 10 minutes, a film-like cured product of the resin composition was obtained. 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. Table 1 shows the results.
◎: Equivalent to UL V-0
(The total burning time when each of the five test pieces is ignited twice is 50 seconds or less.)
○: Equivalent to UL V-1 (Total burning time when 5 test pieces are ignited twice each exceeds 50 seconds and is 250 seconds)
×: No self-extinguishing property

From the results in Table 1, it is clear that the resin compositions of the present invention are superior to the resin compositions of Comparative Examples in adhesive strength, heat resistance and flame retardancy.

By using the polyimide resin having the specific structure of the present invention, it is possible to provide a printed wiring board or the like excellent in adhesiveness, heat resistance and flame retardancy.

Claims (11)

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, and a tetrabasic dianhydride (B) A reaction product of a polyamic acid resin imidized product (P) which is a copolymer of and a compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group, and an ethylenically unsaturated A polyimide resin which is a reactant with a phosphorus compound (D) having a functional group capable of reacting with a saturated double bond group. 2. The polyimide resin according to claim 1, wherein the amino compound (A) contains an aromatic diamino compound (a3) having no phenolic hydroxyl group. Compound (a1) is represented by the following formula (1)

(In formula (1), R ₁ represents a hydrogen atom, a methyl group or an ethyl group, X is C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , SO ₂ , an oxygen atom, a direct bond or the following formula (3) )

Represents a divalent linking group represented by )
Polyimide resin according to claim 1 or 2 containing a compound represented by. Tetrabasic dianhydride (B) is represented by the following formulas (4) to (12)

(In formula (7), Y is C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or the following formula (3)

Represents a divalent linking group represented by )
4. The polyimide resin according to any one of claims 1 to 3, comprising a compound selected from the group consisting of Compound (a3) is represented by the following formulas (13) to (16)

(In formula (15), R ₂ independently represents a methyl group or a trifluoromethyl group; in formula (16), 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 (3)

_R3 independently represents a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group. )
5. The polyimide resin according to any one of claims 1 to 4, comprising a compound selected from the group consisting of 6. The polyimide resin according to any one of claims 1 to 5, wherein the functional group capable of reacting with the phenolic hydroxyl group of the compound (C) is an isocyanate group or a carboxylic acid chloride group. A resin composition comprising the polyimide resin according to any one of claims 1 to 6 and a thermosetting resin. The resin composition according to claim 7, further comprising a curing agent. The resin composition according to claim 7 or 8, further comprising a silane coupling agent having an acrylic group. A cured product of the resin composition according to any one of claims 7 to 9. An article comprising the cured product according to claim 10.