WO2023112849A1 - Isocyanate-modified polyimide resin, and resin composition containing said isocyanate-modified polyimide resin and cured product of same - Google Patents

Abstract

The purpose of the present invention is to provide: a resin material that has a novel structure and can be suitably used in a printed wiring board; and a resin composition that contains the resin material, has excellent coatability onto a base material, and can be cured into a cured article having excellent adhesiveness to a metal foil and a base material each having low roughness and also having excellent heat resistance and dielectric properties. The present disclosure discloses an isocyanate-modified polyimide resin which is a reaction product of an amino group and/or an acid anhydride group located at each end of a polyimide resin with an isocyanate group in a diisocyanate compound (C) and has an amino group and/or an acid anhydride group at each end thereof, in which the polyimide resin is a reaction product of (A) a diamino compound comprising (a1) a linear aliphatic diamino compound having an amino group at each end, having 1 to 4 methyl groups and/or ethyl groups in a side chain thereof and having 17 to 24 carbon atoms in a main chain thereof and (a2) an aromatic diamino compound with (B) a tetrabasic acid dianhydride (B).

Description

Isocyanate-modified polyimide resin, resin composition containing said isocyanate-modified polyimide resin, and cured product thereof

The present invention relates to an isocyanate-modified polyimide resin with a novel structure, a resin composition containing the isocyanate-modified polyimide resin, 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 resin, which has excellent properties such as heat resistance, flame retardancy, flexibility, electrical properties, and chemical resistance, is widely used in electric and electronic parts, semiconductors, communication equipment and its circuit parts, peripheral equipment, 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. Patent Documents 1 and 2 describe examples in which a long alkyl chain is introduced into a polyimide resin, and Patent Document 3 describes an example in which a dimer diamine skeleton, which is an alkyl having a longer carbon chain, is introduced into a polyimide resin. there is However, although these polyimide resins are excellent in terms of low dielectric loss tangent, they have high melt viscosities and low filling properties (filling properties means that the resin is properly filled) into the unevenness of the base material, so air bubbles are mixed in. In addition, the heat resistance is insufficient in addition to the cases where the adhesiveness to the base material is lowered.

JP 2008-308551 A WO2021/049503A1 JP 2017-119361 A

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, a metal foil containing the resin material, excellent in coatability to a substrate, and having a cured product with low roughness, and An object of the present invention is to provide a resin composition which is excellent in adhesiveness to substrates, heat resistance and dielectric properties.

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

(In formula (4), Y is C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or the following formula (10)

Represents a divalent linking group represented by )
The isocyanate-modified polyimide resin according to the preceding item (1) or (2) containing a compound represented by at least one selected from the group consisting of
(4) the aromatic diamino compound (a2) is represented by the following formulas (11) to (14)

(In formula (13), R ₂ independently represents a methyl group or a trifluoromethyl group; in formula (14), Z is C(CF ₃ ) ₂ , CH(CH ₃ ), SO ₂ , CH ₂ , O—C ₆ H ₄ —O, oxygen atom, direct bond or formula (10) below

_R3 independently represents a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group. )
The isocyanate-modified polyimide resin according to any one of claims 1 to 3, comprising a compound represented by at least one selected from the group consisting of
(5) The isocyanate-modified polyimide resin according to any one of the preceding items (1) to (4) has amino groups and/or acid anhydride groups at both ends, and reacts with the amino groups or the acid anhydride groups. A terminal-modified isocyanate-modified polyimide resin which is a reaction product of the compound (D) having one functional group capable of
(6) The isocyanate-modified polyimide resin according to any one of (1) to (4) above, and a resin composition containing a compound having a functional group capable of reacting with the isocyanate-modified polyimide resin,
(7) A resin composition containing a terminal-modified isocyanate-modified polyimide resin according to (5) above and a compound having a functional group capable of reacting with the terminal-modified isocyanate-modified polyimide resin,
(8) The resin composition according to the preceding item (6) or (7), wherein the compound capable of reacting with the isocyanate-modified polyimide resin or the compound capable of reacting with the terminal-modified isocyanate-modified polyimide resin comprises a maleimide resin,
(9) a cured product of the resin composition according to any one of the preceding items (6) to (8), and (10) a substrate having the cured product according to the preceding item (9),
Regarding.

The isocyanate-modified polyimide resin having the specific structure of the present invention has a low melt viscosity, good embedding properties in the irregularities of the base material, and high adhesiveness. Moreover, by using the polyimide resin of the present invention, it is possible to provide printed wiring boards and the like which are excellent in heat resistance, low dielectric properties, and the like.

The isocyanate-modified polyimide resin of the present invention has amino groups at both ends, has 1 to 4 methyl groups and/or ethyl groups in side chains, and has a main chain of 17 to 24 carbon atoms. A diamino compound (A) containing a family diamino compound (a1) (hereinafter simply referred to as "(a1) component") and an aromatic diamino compound (a2) (hereinafter simply referred to as "(a2) component") ( hereinafter simply referred to as "(A) component") and tetrabasic dianhydride (B) (hereinafter simply referred to as "(B) component") reaction product (polymerization and dehydration cyclization reaction product substance) polyimide resin (hereinafter simply referred to as "intermediate polyimide resin") has amino groups and / or acid anhydride groups at both ends and a diisocyanate compound (C) (hereinafter simply "(C) component ”) is a reaction product with an isocyanate group, and is an isocyanate-modified polyimide resin having amino groups and/or acid anhydride groups at both ends.

[Intermediate polyimide resin]
First, the intermediate polyimide resin will be described.
The (A) component used for synthesizing the intermediate polyimide resin contains the (a1) component and the (a2) component as essential components.
Component (a1) is a linear aliphatic hydrocarbon compound having a main chain of 17 to 24 carbon atoms, having amino groups at both ends of the main chain, and methyl and/or ethyl groups in side chains. is not particularly limited as long as it is a compound having 1 to 4. The linear aliphatic hydrocarbon having 17 to 24 carbon atoms and serving as the main chain of the component (a1) may be either a saturated aliphatic hydrocarbon or an unsaturated aliphatic hydrocarbon.
Specific examples of component (a1) include 7,12-dimethyloctadecanediamine, 8,13-dimethyloctadecanediamine, 8-methylnonadecanediamine, 9-methylnonadecanediamine, 7,12-dimethyloctadecanediamine-7, 11-ene and 8,13-dimethyloctadecanediamine-8,12-ene and the like. These may be used alone or in combination of two or more. As a commercial product, Diamine H20 (manufactured by Okamura Oil Co., Ltd.) can be suitably used.
The main chain of component (a1) is preferably a saturated aliphatic hydrocarbon, that is, alkylene, and preferably has 17 to 22 carbon atoms, more preferably 17 to 20 carbon atoms. The number of methyl groups and/or ethyl groups in the side chain is preferably 1 to 3, more preferably 1 or 2.

The amount of component (a1) used for the synthesis of the intermediate polyimide resin is not particularly limited, but from the total mass of the components (A), (B) and (C) used for synthesis, the intermediate polyimide resin synthesis The amount is preferably in the range of 10 to 50% by mass of the mass obtained by subtracting the mass of water generated in the dehydration cyclization reaction step (substantially the same mass as the finally obtained isocyanate-modified polyimide resin). If the amount of component (a1) is less than the above range, the number of aliphatic chains derived from component (a1) in the intermediate polyimide resin is too small, and the dielectric constant and dielectric loss tangent of the cured product of the resin composition become high. If the above range is exceeded, the number of aliphatic chains derived from component (a1) in the polyimide resin is too large, and the heat resistance of the cured product may be lowered.

The component (a2) used for synthesizing the intermediate polyimide resin is not particularly limited as long as it is an aromatic compound having two amino groups in one molecule. In addition, it is preferable that the amino group of the component (a2) is directly bonded to the aromatic ring.
Specific examples of component (a2) include m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 4,4'-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-aminophenoxy phenyl)propane, 1,3-bis(4-aminophenoxyphenyl)benzene, 1,3′-bis(3-aminophenoxyphenyl)propane, bis(4-amino-3-methylphenyl)methane, bis(4- amino-3,5-dimethylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-propylphenyl) methane and bis(4-amino-3,5-dipropylphenyl)methane, and the like. These may be used alone or in combination of two or more.

The component (a2) used to synthesize the intermediate polyimide resin preferably contains at least one compound selected from the group consisting of the following formulas (11) to (14).

In formula (13), _R2 independently represents a methyl group or a trifluoromethyl group, and in formula (14), Z is C( _CF3 ) ₂ , CH( _CH3 ), _SO2 , _CH2 , O —C ₆ H ₄ —O, an oxygen atom, a direct bond or a divalent linking group represented by the above formula (10), R ₃ independently represents a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group; show.

The amount of component (a2) used for the synthesis of the intermediate polyimide resin is not particularly limited, but from the total mass of the components (A), (B) and (C) used for synthesis, the intermediate polyimide resin synthesis The amount is preferably in the range of 10 to 50% by mass of the mass obtained by subtracting the mass of water generated in the dehydration cyclization reaction step (substantially the same mass as the finally obtained isocyanate-modified polyimide resin). If the amount of component (a2) is below the above range, the heat resistance of the cured product may be lowered, and if below the above range, the dielectric properties of the cured product may be reduced.

The (A) component used for synthesizing the intermediate polyimide resin includes the (a1) component and the (a2) component, but the diamino compound (a3) other than the (a1) component and the (a2) component (hereinafter simply “(a3 ) component)).
Component (a3) is not particularly limited as long as it is a compound other than components (a1) and (a2) and has two amino groups in one molecule, but an aliphatic diamino compound other than component (a1) is Aliphatic diamino compounds having 6 to 36 carbon atoms other than the component (a1) are preferred, and dimer diamine is more preferred, since a polyimide resin having a low dielectric constant and low dielectric loss tangent can be obtained. Specific examples of the component (a3) include hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,3-bisaminomethylcyclohexane, norbornanediamine, isophoronediamine, and dimerdiamine, in addition to the dimerdiamine described above. , 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12- diaminododecane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebiscyclohexylamine, diaminopolysiloxane having 6 to 36 carbon atoms, and the like. As the component (a3), these may be used alone or in combination of two or more.

The dimer diamine described in the specific examples of component (a3) 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 (a3) used in the synthesis of the intermediate polyimide resin is not particularly limited as long as it does not impair the effect of the invention, but it is usually 50% by mass or less, preferably 10 to 30% by mass of the mass of component (A). be.

The component (B) used for synthesizing the intermediate polyimide resin is not particularly limited as long as it has two acid anhydride groups in one molecule.
Specific examples of component (B) include pyromellitic anhydride, ethylene glycol-bis(anhydrotrimellitate), glycerin-bis(anhydrotrimellitate) monoacetate, 1,2,3,4-cyclobutanetetra carboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4, 4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methylcyclohexene- 1,2-dicarboxylic anhydride, 3a,4,5,9b-tetrahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione , 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bicyclo[2 .2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 5,5′-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis (isobenzofuran-1,3-dione) 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 component (B) used for synthesizing the intermediate polyimide resin preferably contains a compound selected from the group consisting of the following formulas (1) to (9).

In formula (4), Y represents C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or a divalent linking group represented by formula (10) below.

The reaction between component (A) and component (B) comprises a step of copolymerizing amino groups in component (A) and acid anhydride groups in component (B) to obtain a polyamic acid, and dehydration of the polyamic acid. It includes a step of obtaining an intermediate polyimide resin by a cyclization reaction (imidization reaction). The above two steps may be performed separately, but it is efficient to perform them continuously in batch.
When the number of moles MA of component (A) and the number of moles MB of component (B) used in the copolymerization reaction satisfy the relationship MA>MB, both ends of the intermediate polyimide resin obtained are amino groups, and MA<MB When the relationship is satisfied, both ends of the obtained intermediate polyimide resin are acid anhydride groups. Further, when the relationship MA=MB is satisfied, the theoretically obtained intermediate polyimide resin has an infinite molecular weight and has one amino group and one acid anhydride group at each end.

The intermediate polyimide resin can be synthesized by a known method.
For example, a solvent, a dehydrating agent, and a catalyst are added to the components (A) and (B) used in the synthesis, and the mixture is heated and stirred at 100 to 300°C in an atmosphere of an inert gas such as nitrogen to form an imidization reaction via a polyamic acid. (A ring closure reaction (cyclization reaction) accompanied by dehydration) occurs to obtain an intermediate polyimide resin solution. At this time, the water generated by imidization is distilled out of the system, and after the reaction is completed, the dehydrating agent and catalyst are also distilled out of the system to obtain an intermediate polyimide resin of high purity without washing. be able to. Examples of dehydrating agents include toluene and xylene, and examples of catalysts include pyridine and triethylamine.

Solvents that can be used in synthesizing the intermediate polyimide resin include methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclopentanone, Cyclohexanone, methylcyclohexanone, acetylacetone, γ-butyrolactone, diacetone alcohol, cyclohexen-1-one, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, ethyl isoamyl ether, ethyl-t-butyl ether, ethyl benzyl ether, cresyl methyl ether, anisole, phenetole, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, acetoacetic acid Methyl, ethyl acetoacetate, methyl propionate, ethyl propionate, butyl propionate, benzyl propionate, methyl butyrate, ethyl butyrate, isopropyl butyrate, butyl butyrate, isoamyl butyrate, methyl lactate, ethyl lactate, butyl lactate, ethyl isovalerate , isoamyl isovalerate, diethyl oxalate, dibutyl oxalate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide etc., but not limited to these. These may be used alone or in combination of two or more.

[Isocyanate-modified polyimide resin]
Next, the isocyanate-modified polyimide resin of the present invention will be described.
The reaction between the intermediate polyimide resin and the component (C) is a copolymerization reaction between the amino group or acid anhydride group at the end of the intermediate polyimide resin and the isocyanate group of the component (C), and the amino group and the isocyanate Reaction with groups forms urea bonds, and reaction of acid anhydrides with isocyanate groups forms imide bonds.

Component (C) used for synthesizing the isocyanate-modified polyimide resin can be used as long as it has two isocyanate groups in the molecule, and can react with a plurality of diisocyanate compounds at the same time.
Component (C) includes phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, allylene sulfone ether diisocyanate, and allyl cyan diisocyanate. , N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane or norbornane-diisocyanatomethyl are preferred. Among them, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, or isophorone diisocyanate is more preferable because of its excellent balance of flexibility, adhesiveness, and the like.

The amount of the component (C) used in the copolymerization reaction between the intermediate polyimide resin and the component (C) is such that the isocyanate group of the component (C) is less than 1 equivalent with respect to 1 equivalent of the terminal functional group of the intermediate polyimide resin. Although it is not particularly limited as long as the amount is By setting the amount of component (C) used relative to the intermediate polyimide in the above range, the molecular weight of the isocyanate-modified polyimide resin is sufficiently large, and the residual rate of unreacted raw materials is reduced, resulting in isocyanate-modified polyimide resin, etc. Various properties such as heat resistance and flexibility of the resin composition to be contained after curing are improved.
The terminal functional group equivalent of the intermediate polyimide resin referred to herein means a value calculated from the amount of each raw material used when synthesizing the intermediate polyimide resin.

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

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

[Terminal-modified isocyanate-modified polyimide resin]
Since the isocyanate-modified polyimide resin of the present invention has amino groups and/or acid anhydride groups at both ends, it has one functional group that can react with these functional groups (i.e., amino groups or acid anhydride groups). The terminal can be modified by reacting with the compound (D) (hereinafter simply referred to as "(D) component") to obtain the terminal-modified isocyanate-modified polyimide resin of the present invention.
Examples of component (D) include compounds having an acid anhydride group such as maleic anhydride, compounds having an alcoholic hydroxyl group such as hydroxyethyl acrylate, compounds having a phenolic hydroxyl group such as phenol, and 2-methacryloyloxyethyl isocyanate. compounds having an isocyanate group such as and compounds having an epoxy group such as glycidyl methacrylate.
By modifying the terminals, both terminals of the isocyanate-modified polyimide resin of the present invention can be changed to functional groups other than amino groups and acid anhydride groups (for example, when terminal modification is performed using hydroxyethyl acrylate, Terminals of the isocyanate-modified polyimide resin can be changed to acryloyl groups), and a composition can be prepared by combining with a compound capable of reacting with a functional group other than an amino group or an acid anhydride group.

[Resin composition]
The resin composition of the present invention contains the isocyanate-modified polyimide resin of the present invention and a compound capable of reacting with the isocyanate-modified polyimide resin. In addition, the resin composition of the present invention in a mode different from the above contains the terminal-modified isocyanate-modified polyimide resin of the present invention and a compound capable of reacting with the terminal-modified isocyanate-modified polyimide resin. Hereinafter, a compound capable of reacting with an isocyanate-modified polyimide resin and a compound capable of reacting with a terminal-modified isocyanate-modified polyimide resin are simply referred to as "reactive compounds". As the reactive compound, one or more kinds of compounds can be used, and as the reactive compound, not only low-molecular-weight compounds but also high-molecular-weight compounds such as resins can be used.

The reactive compound is a compound (resin) having a reactive group capable of reacting with an amino group, an acid anhydride group or a functional group (e.g., the acryloyl group described above) at the end of the terminal-modified isocyanate-modified polyimide resin. Not limited.
Specific examples of reactive compounds 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 resistance and high adhesiveness can be imparted to the cured product of the resin composition by using a reactive compound in combination with the isocyanate-modified polyimide resin.

As the reactive 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 heat resistance and adhesiveness of the cured product of the resin composition are particularly excellent.
In addition, when the number of moles of component (A) used for synthesizing the isocyanate-modified polyimide resin of the present invention is MA, the number of moles of component (B) is MB, and the number of moles of component (C) is MC, (MA + MC )/MB exceeds 1, it is also preferable to use a thermosetting resin such as an epoxy resin as the reactive compound.

In addition, the reactive compound preferably has a molecular weight of 100 to 50,000 from the viewpoint of suppressing an increase in the viscosity of the varnish (a varnish-like composition obtained by combining a resin composition with an organic solvent). 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 (maleimide compound) as the reactive compound is not particularly limited as long as it has a maleimide group, but preferably has two or more maleimide groups in one molecule. In addition, maleimide resins having aromatic rings such as benzene, biphenyl and naphthalene rings are preferred because the cured product of the resin composition has excellent properties such as mechanical strength and flame retardancy. -3000 (manufactured by Nippon Kayaku Co., Ltd.), MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
The maleimide resin is a terminal amino group of an isocyanate-modified polyimide resin or a terminal ethylenically unsaturated double bond group of a terminally modified isocyanate-modified polyimide resin (the ethylenically unsaturated double bond group is sometimes simply referred to as an ethylenically unsaturated group. ), which increases the crosslink density of the cured product, improves resistance to polar solvents, and improves 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 several minutes to several hours.
The content of the maleimide resin in the resin composition of the present invention containing a maleimide resin is 1 equivalent of the terminal amino group of the isocyanate-modified polyimide resin or 1 equivalent of the terminal ethylenically unsaturated double bond group of the terminal-modified isocyanate-modified polyimide resin. The amount is preferably such that the maleimide group equivalent of the resin is 0.1 to 500 equivalents.

For the purpose of promoting the curing reaction of the maleimide resin, various radical initiators can be added as curing agents to the resin composition of the present invention containing the maleimide resin, if necessary. 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 0.1 to 10% by mass based on the maleimide resin.

Epoxy resins (epoxy compounds) as reactive compounds are not particularly limited as long as they have epoxy groups, but those having two or more epoxy groups in one molecule are preferred. In addition, epoxy resins having aromatic rings such as benzene rings, biphenyl rings and naphthalene rings are preferable because the cured product of the resin composition has excellent properties such as mechanical strength and flame retardancy. (manufactured by Mitsubishi Chemical Corporation), NC-3000, XD-1000 (both of which are manufactured by Nippon Kayaku Co., Ltd.), and the like.
The epoxy resin is added for the purpose of reacting with the terminal amino group or acid anhydride group of the isocyanate-modified polyimide resin, thereby increasing the crosslink density of the cured product, improving the resistance to polar solvents, and Adhesion to 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 per equivalent of the phenolic hydroxyl group and the active hydrogen of the terminal amino group of the isocyanate-modified polyimide resin and the acid anhydride is 0.00. An amount of 1 to 500 equivalents is preferred. In addition, since the epoxy group of the epoxy resin has reactivity with the terminal functional group of the isocyanate-modified polyimide resin, the epoxy equivalent of the epoxy resin with respect to 1 equivalent of the terminal functional group of the isocyanate-modified polyimide resin is 0.1 to 500 equivalents. It is a preferred embodiment to add additional amounts of epoxy resin as needed.

If necessary, a curing agent can be added to the resin composition of the present invention containing an epoxy resin for the purpose of promoting 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 reactive compound is not particularly limited as long as it has an ethylenically unsaturated group.
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, urethane (meth)acrylates having multiple (meth)acryloyl groups and urethane bonds in the same molecule; polyester (meth)acrylates having multiple (meth)acryloyl groups and ester bonds in the same molecule Acrylates; Epoxy (meth)acrylates derived from epoxy resins and having multiple (meth)acryloyl groups; Reactive oligomers having multiple (meth)acryloyl groups in which these bonds are used in combination Specific examples of compounds having an ethylenically unsaturated group include:

Urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylates, polyisocyanates, and other alcohols used as needed. 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 polyisocyanates such as their isocyanurates and burette reaction products, etc., reacted with urethane (Meth)acrylates are mentioned.

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) of cyclic lactone-modified polyester diol consisting of diol component, polybasic acid and their anhydrides and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. Examples include polyfunctional (poly)ester (meth)acrylates such as acrylates.

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. Propylene 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 use them by appropriately mixing 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 based on 1 equivalent of the ethylenically unsaturated double bond group of the terminal-modified isocyanate-modified polyimide resin. The amount is preferably such that the amount of double bond groups in the compound having an ethylenically unsaturated group is 0.1 to 500 equivalents.

The resin composition of the present invention containing a compound having an ethylenically unsaturated group, for the purpose of promoting the curing reaction of the terminal-modified isocyanate-modified polyimide resin and the compound having an ethylenically unsaturated group, radical initiation if necessary Curing agents such as curing agents can be added. 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 in the resin composition of the present invention containing a compound having an ethylenically unsaturated group is 0.1 to 10% by mass relative to the compound having an ethylenically unsaturated group in the entire composition. be.

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.

A known additive may be used in combination with the resin composition of the present invention, if necessary. 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 to be blended 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 of 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 isocyanate-modified polyimide resin or terminal-modified isocyanate-modified polyimide resin and the reactive compound of the present invention can be prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. . For mixing or prepolymerizing each component, for example, an extruder, kneader, roll, 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 resin composition of the present invention can be cured by heating.
The curing temperature and curing time of the resin composition may be selected in consideration of the combination of the functional group possessed by the isocyanate-modified polyimide resin or terminal-modified isocyanate-modified polyimide resin of the present invention and the reactive group possessed by the reactive compound. For example, a resin composition containing a maleimide resin or a resin composition containing an epoxy resin preferably has a curing temperature of 120 to 250° C. and a curing time of approximately 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.
Alternatively, after the resin composition is applied to a copper foil and the solvent is dried, a polyimide film or LCP (liquid crystal polymer) is laminated and heat-cured by a hot press to obtain a substrate provided with the cured product of the present invention. can also In some cases, it is also possible to obtain a substrate provided with the cured product of the present invention by coating it on the polyimide film or LCP side, laminating it with a copper foil, and heat-curing it with a hot press.
Furthermore, after applying the resin composition of the present invention to a copper foil and drying the solvent, 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, A substrate provided with the cured product of the present invention can also be obtained by heat curing with a hot press.

The substrate provided with the cured product of the resin composition of the present invention can be used for a copper clad laminate (CCL), or a printed wiring board or multilayer wiring board having a circuit pattern on the copper foil of the CCL.

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 GPC measurement conditions in the examples are as follows.
Model: TOSOH ECOSEC Elite HLC-8420GPC
Column: TSKgel Super AWM-H
Eluent: NMP (N-methylpyrrolidone); 0.5 ml/min, 40°C
Detector: UV (differential refractometer)
Molecular weight standard: Polystyrene

Example 1 (Synthesis of isocyanate-modified polyimide resin (A-1) of the present invention)
A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a raw material inlet, a nitrogen introduction device and a stirring device was charged with BAFL (9,9-bis (4-aminophenyl) fluorene, manufactured by JFE Chemical Co., Ltd. , molecular weight 348.45 g / mol) 5.52 parts, Diamine H20 (manufactured by Okamura Oil Co., Ltd., molecular weight 325.09 g / mol) 10.21 parts, ODPA (oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22 g /mol) 13.96 parts of anisole, 66.09 parts of anisole, 0.91 parts of triethylamine and 14.83 parts of toluene were added and heated to 120°C to dissolve the raw materials. The reaction was carried out at 135° C. for 4 hours while removing water produced by ring closure of the amic acid by azeotropic distillation with toluene. After the generation of water stopped, residual triethylamine and toluene were subsequently removed at 140° C. to obtain an intermediate polyimide resin solution. The molar ratio of the (A) component ((a1) component and (a2) component) and the (B) component used in the synthesis of the intermediate polyimide resin (the number of moles of the component (B)/the number of moles of the component (A)) is was 1.05.
To the intermediate polyimide resin solution obtained above, IPDI (isophorone diisocyanate, manufactured by Degusahüls, molecular weight 222.29 g / mol) 0.29 parts and anisole 0.66 parts were added and heated at 130 ° C. for 3 hours. An isocyanate-modified polyimide resin (A-1) solution of the invention was obtained. Molar ratio of the final raw material components of the isocyanate-modified polyimide resin (A-1) obtained above (moles of component (B) / (moles of component (A) + moles of component (C))) was 1.02.

Example 2 (Synthesis of isocyanate-modified polyimide resin (A-2) of the present invention)
A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a raw material inlet, a nitrogen introduction device and a stirring device was charged with BAFL (9,9-bis (4-aminophenyl) fluorene, manufactured by JFE Chemical Co., Ltd. , molecular weight 348.45 g / mol) 5.52 parts, Diamine H20 (manufactured by Okamura Oil Co., Ltd., molecular weight 325.09 g / mol) 10.21 parts, ODPA (oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22 g /mol) 13.96 parts of anisole, 66.09 parts of anisole, 0.91 parts of triethylamine and 14.83 parts of toluene were added and heated to 120°C to dissolve the raw materials. The reaction was carried out at 135° C. for 4 hours while removing water produced by ring closure of the amic acid by azeotropic distillation with toluene. After the generation of water stopped, residual triethylamine and toluene were subsequently removed at 140° C. to obtain an intermediate polyimide resin solution. The molar ratio of the (A) component ((a1) component and (a2) component) and the (B) component used in the synthesis of the intermediate polyimide resin (the number of moles of the component (B)/the number of moles of the component (A)) is was 1.05.
To the intermediate polyimide resin solution obtained above, HDI (hexamethylene diisocyanate, manufactured by Asahi Kasei Corporation, molecular weight 168.20 g / mol) 0.22 parts and anisole 0.50 parts are added and heated at 130 ° C. for 3 hours. Thus, an isocyanate-modified polyimide resin (A-2) solution of the present invention was obtained. Molar ratio of the final raw material components of the isocyanate-modified polyimide resin (A-2) obtained above (moles of component (B) / (moles of component (A) + moles of component (C))) was 1.02.

Example 3 (Synthesis of isocyanate-modified polyimide resin (A-3) of the present invention)
A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a raw material inlet, a nitrogen introduction device and a stirring device was charged with BAFL (9,9-bis (4-aminophenyl) fluorene, manufactured by JFE Chemical Co., Ltd. , molecular weight 348.45 g / mol) 5.52 parts, Diamine H20 (manufactured by Okamura Oil Co., Ltd., molecular weight 325.09 g / mol) 7.31 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol) 4 .80 parts, 13.96 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g/mol), 66.09 parts of anisole, 0.91 parts of triethylamine and 14.83 parts of toluene were added to obtain 120 parts. ℃ to dissolve the raw materials. The reaction was carried out at 135° C. for 4 hours while removing water produced by ring closure of the amic acid by azeotropic distillation with toluene. After the generation of water stopped, residual triethylamine and toluene were subsequently removed at 140° C. to obtain an intermediate polyimide resin solution. The molar ratio of the (A) component ((a1) component, (a2) component and (a3) component) and (B) component used in the synthesis of the intermediate polyimide resin (moles of component (B) / component (A) number of moles) was 1.05.
To the intermediate polyimide resin solution obtained above, IPDI (isophorone diisocyanate, manufactured by Degusahüls, molecular weight 222.29 g / mol) 0.29 parts and anisole 0.66 parts were added and heated at 130 ° C. for 3 hours. An isocyanate-modified polyimide resin (A-3) solution of the invention was obtained. The molar ratio of the final raw material components of the isocyanate-modified polyimide resin (A-3) obtained above (moles of component (B) / (moles of component (A) + moles of component (C))) was 1.02.

Example 4 (Synthesis of terminal-modified isocyanate-modified polyimide resin (A-4) of the present invention)
BAPP(2,2-bis[4-(4-aminophenoxy)phenyl]propane, Wakayama Seika Kogyo Co., Ltd., molecular weight 410.52 g / mol) 9.13 parts, Diamine H20 (manufactured by Okamura Oil Co., Ltd., molecular weight 325.09 g / mol) 8.37 parts, BPDA (biphenyltetracarboxylic dianhydride , manufactured by Mitsubishi Chemical Corporation, molecular weight 294.22 g / mol) 11.77 parts, 77.15 parts of anisole, 0.81 parts of triethylamine and 20.14 parts of toluene were added and heated to 120 ° C. to dissolve the raw materials. . The reaction was carried out at 135° C. for 4 hours while removing water produced by ring closure of the amic acid by azeotropic distillation with toluene. After the generation of water stopped, residual triethylamine and toluene were subsequently removed at 140° C. to obtain an intermediate polyimide resin solution. The molar ratio of the (A) component ((a1) component and (a2) component) and the (B) component used in the synthesis of the intermediate polyimide resin (the number of moles of the component (B)/the number of moles of the component (A)) is was 1.20.
Next, 1.19 parts of HDI (hexamethylene diisocyanate, manufactured by Asahi Kasei Corporation, molecular weight 168.20 g / mol) and 2.64 parts of anisole are added to the intermediate polyimide resin solution obtained above, and the mixture is heated at 130 ° C. for 3 hours. An isocyanate-modified polyimide resin solution was obtained by heating. The molar ratio of the final raw material components of the isocyanate-modified polyimide resin obtained above (the number of moles of component (B)/(the number of moles of component (A) + the number of moles of component (C))) is 1.02. there were.
Next, 0.08 parts of maleic anhydride (molecular weight: 98.06 g/mol), 0.3 parts of triethylamine and 5.2 parts of toluene were further added to the isocyanate-modified polyimide resin solution and reacted at 135° C. for 4 hours. After water generation stopped, residual triethylamine and toluene were removed at 140° C. to obtain a terminal-modified isocyanate-modified polyimide resin (A-4) solution in which both ends of the isocyanate-modified polyimide resin were modified with maleic anhydride. rice field.

Comparative Example 1 (Synthesis of comparative polyimide resin (A-5))
A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a raw material inlet, a nitrogen introduction device and a stirring device was charged with BAFL (9,9-bis (4-aminophenyl) fluorene, manufactured by JFE Chemical Co., Ltd. , molecular weight 348.45 g / mol) 9.05 parts, Diamine H20 (manufactured by Okamura Oil Co., Ltd., molecular weight 325.09 g / mol) 12.41 parts, ODPA (oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22 g /mol) 14.89 parts of anisole, 80.90 parts of anisole, 0.97 parts of triethylamine and 15.91 parts of toluene were added and heated to 120°C to dissolve the raw materials. The reaction was carried out at 135° C. for 4 hours while removing water produced by ring closure of the amic acid by azeotropic distillation with toluene. After the generation of water stopped, residual triethylamine and toluene were continuously removed at 140° C. to obtain a polyimide resin (A-5) solution for comparison. The final molar ratio of the raw material components (the number of moles of component (B)/the number of moles of component (A)) in the comparative polyimide resin (A-5) obtained above was 1.02.

Comparative Example 2 (Synthesis of comparative polyimide resin (A-6))
A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a raw material inlet, a nitrogen introduction device and a stirring device was charged with BAFL (9,9-bis (4-aminophenyl) fluorene, manufactured by JFE Chemical Co., Ltd. , molecular weight 348.45 g / mol) 9.05 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol) 12.29 parts, ODPA (oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22 g / mol), 80.63 parts of anisole, 0.97 parts of triethylamine and 15.89 parts of toluene were added and heated to 120° C. to dissolve the raw materials. The reaction was carried out at 135° C. for 4 hours while removing water produced by ring closure of the amic acid by azeotropic distillation with toluene. After the generation of water stopped, residual triethylamine and toluene were continuously removed at 140° C. to obtain a polyimide resin (A-6) solution for comparison. The final molar ratio of the raw material components (the number of moles of component (B)/the number of moles of component (A)) in the comparative polyimide resin (A-6) obtained above was 1.02.

Comparative Example 3 (Synthesis of comparative polyimide resin (A-7))
A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a raw material inlet, a nitrogen introduction device and a stirring device was charged with BAFL (9,9-bis (4-aminophenyl) fluorene, manufactured by JFE Chemical Co., Ltd. , molecular weight 348.45 g / mol) 9.05 parts, 1,10-decanediamine (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 172.32 g / mol) 3.96 parts, ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd. , molecular weight 310.22 g/mol), 62.10 parts of anisole, 0.97 parts of triethylamine and 14.54 parts of toluene were added and heated to 120°C to dissolve the raw materials. The reaction was carried out at 135° C. for 4 hours while removing water produced by ring closure of the amic acid by azeotropic distillation with toluene. After the generation of water stopped, residual triethylamine and toluene were continuously removed at 140° C. to obtain a polyimide resin (A-7) solution for comparison. The final molar ratio of the raw material components (the number of moles of component (B)/the number of moles of component (A)) in the comparative polyimide resin (A-7) obtained above was 1.02.

Examples 5 to 11, 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 (unit is "part", the number of parts in the table is the number of parts in terms of solid content without solvent), the solid content concentration is 20% by mass. anisole was added as a solvent and uniformly mixed to prepare resin compositions of the present invention and comparison.

In addition, each component in Table 1 is as follows.
<Polyimide resin>
(A-1): The isocyanate-modified polyimide resin of the present invention obtained in Example 1 (A-2): The isocyanate-modified polyimide resin of the present invention obtained in Example 2 (A-3): In Example 3 Obtained isocyanate-modified polyimide resin of the present invention (A-4): Terminal-modified isocyanate-modified polyimide resin of the present invention obtained in Example 4 (A-5): Comparative polyimide resin obtained in Comparative Example 1 (A-6): Comparative polyimide resin obtained in Comparative Example 2 (A-7): Comparative polyimide resin obtained in Comparative Example 3 <reactive compound (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. <Additive>
KR-513; silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.

Using the resin compositions obtained in Examples 5 to 11 and Comparative Examples 4 to 6, the adhesiveness (adhesive strength) to copper foil, heat resistance, dielectric properties ( dielectric constant and dielectric loss tangent) and coatability were evaluated.

(Evaluation of adhesiveness (adhesive strength))
Apply using an automatic applicator to the rough surface of ultra-low roughness non-roughening treated electrolytic copper foil CF-T49A-DS-HD (hereinafter referred to as "T49A") manufactured by Fukuda Metal Foil & Powder Co., Ltd. Then, the resin compositions of Examples 5 to 11 and Comparative Examples 4 to 6 were applied in an amount such that the film thickness of the resin composition layer after drying was 30 μm, and dried by heating at 120° C. for 10 minutes. Kapton 20EN (manufactured by DuPont-Toray Co., Ltd.) was overlaid on the resin composition layer 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 using Autograph AGS-X-500N (manufactured by Shimadzu Corporation), the 90° peeling strength (pull The peeling speed was 50 mm/min), and the adhesiveness (adhesive strength) was evaluated according to the following evaluation criteria. Table 1 shows the results.
◎ (excellent) ... 6.6 N / cm or more ○ (good) ... 5.0 N / cm or more and less than 6.6 N / cm × (improper) ... less than 5.0 N / cm

(Evaluation of heat resistance)
A test piece prepared by the same method as the above "Evaluation of adhesiveness (adhesive strength)" is floated in a solder bath heated to 288 ° C. with POT-200C (manufactured by Taiyo Denki Sangyo Co., Ltd.) until blisters appear. The time was measured, and the heat resistance was evaluated according to the following evaluation criteria. Table 1 shows the results.
◎ (excellent): no swelling for 1000 seconds or longer ○ (good): swelling occurs for 10 seconds or more and less than 1000 seconds × (improper): swelling occurs for less than 10 seconds

(Evaluation of dielectric constant and dielectric loss tangent)
Resin was applied onto the rough surface of T49A in the same manner as in the above “Evaluation of Adhesion (Adhesion Strength)” 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. A coating film of each composition was 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. For the film-like cured product, the dielectric constant and dielectric loss tangent at 10 GHz were measured by the cavity resonance method using a network analyzer 8719ET (manufactured by Agilent Technologies). Table 1 shows the results.

(Evaluation of coatability)
Voids (bubbles) contained in concave portions of the rough surface of the copper foil were confirmed using an optical microscope for the test piece prepared by the same method as in the above "Evaluation of Adhesiveness (Adhesive Strength)". The ratio of depressions in which voids were observed was used to evaluate the coatability on the uneven surface according to the following criteria.
○ (Good): The ratio of concave portions where voids are observed is 0% or more and less than 1% △ (Fair): The ratio of concave portions where voids are observed is 1% or more and less than 2% × (Unacceptable) …・The percentage of recesses where voids are observed is 2% or more

From the results of Table 1, the resin composition containing the isocyanate-modified polyimide resin of the present invention is excellent in all of adhesiveness (adhesive strength), heat resistance, dielectric properties and coatability, whereas comparative examples The resin composition was poor in adhesiveness, heat resistance and coatability.

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

Claims (10)

1. A linear aliphatic diamino compound (a1) having amino groups at both ends, having 1 to 4 methyl groups and/or ethyl groups in side chains, and having a main chain of 17 to 24 carbon atoms and an aromatic A diamino compound (A) containing a diamino compound (a2) and a polyimide resin that is a reaction product of a tetrabasic dianhydride (B) having amino groups and/or acid anhydride groups at both ends, and a diisocyanate compound An isocyanate-modified polyimide resin which is a reaction product with an isocyanate group of (C) and has amino groups and/or acid anhydride groups at both ends.
2. The isocyanate-modified polyimide resin according to claim 1, wherein the diisocyanate compound (C) contains at least one compound selected from the group consisting of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and isophorone diisocyanate.
3. The tetrabasic dianhydride (B) is represented by the following formulas (1) to (9)
   

   

   (In formula (4), Y is C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or the following formula (10)
   

   

   Represents a divalent linking group represented by )
   The isocyanate-modified polyimide resin according to claim 1 or 2, comprising a compound represented by at least one selected from the group consisting of.
4. The aromatic diamino compound (a2) is represented by the following formulas (11) to (14)
   

   

   (In formula (13), R ₂ independently represents a methyl group or a trifluoromethyl group; in formula (14), Z is C(CF ₃ ) ₂ , CH(CH ₃ ), SO ₂ , CH ₂ , O—C ₆ H ₄ —O, oxygen atom, direct bond or formula (10) below
   

   

   _R3 independently represents a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group. )
   The isocyanate-modified polyimide resin according to any one of claims 1 to 3, comprising a compound represented by at least one selected from the group consisting of.
5. 5. The isocyanate-modified polyimide resin according to any one of claims 1 to 4 has amino groups and / or acid anhydride groups at both ends, and a functional group capable of reacting with the amino group or the acid anhydride group. A terminal-modified isocyanate-modified polyimide resin which is a reaction product of the compound (D) having the above-mentioned functional groups.
6. A resin composition containing the isocyanate-modified polyimide resin according to any one of claims 1 to 4 and a compound having a functional group capable of reacting with the isocyanate-modified polyimide resin.
7. A resin composition containing the terminal-modified isocyanate-modified polyimide resin according to claim 5 and a compound having a functional group capable of reacting with the terminal-modified isocyanate-modified polyimide resin.
8. The resin composition according to claim 6 or 7, wherein the compound capable of reacting with the isocyanate-modified polyimide resin or the compound capable of reacting with the terminal-modified isocyanate-modified polyimide resin contains a maleimide resin.
9. A cured product of the resin composition according to any one of claims 6 to 8.
10. A substrate having the cured product according to claim 9 .