KR20170042278A - Resin composition and the laminate using same - Google Patents

Abstract

An object of the present invention is to provide a resin composition which is excellent in both adhesion to a conductor layer and an organic insulating substrate and which can form an adhesive layer having high heat resistance and excellent solder resistance after moisture absorption. The present invention relates to a resin composition containing an epoxy resin (A), a polyarylate resin (B) and a curing agent (C) having at least two epoxy groups in a molecule, wherein the glass transition temperature (A) / (B) of the epoxy resin (A) with respect to the polyarylate resin (B) is from 30/70 to 90/10 (mass ratio).

Description

RESIN COMPOSITION AND THE LAMINATE USING SAME [0002]

The present invention relates to a resin composition capable of forming an adhesive layer having high heat resistance and excellent in solder resistance after moisture absorption.

BACKGROUND ART In recent years, advances in the field of electronics have been remarkable, and in particular, electronic devices have become smaller, lighter, and denser, and their performance has been strongly demanded. In order to cope with such a demand, thinning of electronic materials, multilayering, and high definition are actively studied. The printed wiring board often uses a flexible printed wiring board, and in many cases, it is highly integrated and multilayered.

As a method of multilayering such a printed wiring board, a technique of manufacturing a build-up type multilayered printed circuit board in which a conductor layer (mainly copper or silver is used) and an organic insulating layer are alternately laminated is attracting attention. A common method of alternately stacking the conductor layer and the organic insulating layer is to laminate the laminate composed of the conductor layer and the organic insulating substrate (mainly polyimide) with an insulating adhesive layer. It is essential that this insulating adhesive layer is firmly adhered to both the conductor layer forming the circuit and the organic insulating substrate, and furthermore, the conductor layer in the circuit pattern must be buried in the gap.

In order to meet such a demand, various studies have been conducted, and a flexible wiring board adhesive containing polyarylate and an epoxy resin as essential components (Patent Documents 1 and 2), a polyester / polyurethane resin having a specific acid value and an epoxy resin (See, for example, Patent Document 3), an adhesive composition containing a urethane-modified carboxyl group-containing polyester resin, an epoxy resin and a curing agent (for example, see Patent Document 4) .

On the other hand, there is disclosed a thermosetting elastomer (Patent Document 5) having excellent heat resistance and flexibility, obtained by thermally curing a resin composition containing an epoxy resin, a polyarylate resin and an amine curing agent in a specific ratio.

Japanese Patent Application Laid-Open No. 5-263058 Japanese Patent Laid-Open No. 5-271637 Japanese Patent Application Laid-Open No. 11-116930 Japanese Patent Application Laid-Open No. 2007-51212 Japanese Patent Application Laid-Open No. 2013-189544

The present inventors have found the following.

According to the techniques described in Patent Documents 1 to 5, excellent adhesiveness can not be obtained for both or one of the conductor layer and the organic insulating substrate. Even though excellent adhesiveness was obtained for both the conductor layer and the organic insulating substrate, the heat resistance was lowered. In detail, flexible printed wiring boards have been used in a wide range of fields in recent years, in addition to their thinness and flexibility, capable of producing fine circuits. In the field of electronic appliances, the use temperature is 100 캜 or less, And heat resistance that can withstand a use temperature of 150 ° C or higher is required in a vehicle application. However, the flexible printed wiring boards using the compositions of the above Patent Documents 1 to 5 as an adhesive layer were not able to withstand use in lighting and vehicle applications.

In addition, the moisture absorption of the adhesive layer may lower solder resistance. Specifically, when the adhesive layer is absorbed under high temperature and high humidity and heated by melting of the solder, bubbles are generated by the evaporated water, which causes a problem that the adhesive layer is inflated and peeled off from the conductive layer or the organic insulating substrate.

In addition, when the adhesive layer is hot-pressed to cure, there is a problem that the resin composition has too much fluidity, resulting in a large amount of voids.

An object of the present invention is to provide a resin composition which is excellent in both adhesion to a conductor layer and an organic insulating substrate and which can form an adhesive layer having high heat resistance and excellent solder resistance after moisture absorption.

The present invention is also characterized in that it has excellent adhesiveness to both the conductor layer and the organic insulating substrate, has high heat resistance, is excellent in solder resistance after moisture absorption, and has a characteristic of being resistant to release during a hot press for curing It is an object of the present invention to provide a resin composition capable of forming a good adhesive layer.

The inventors of the present invention have made intensive studies in order to solve the above problems, and as a result, they have reached the present invention.

That is, the gist of the present invention is as follows.

(1) A resin composition comprising an epoxy resin (A) having at least two epoxy groups in one molecule, a polyarylate resin (B) and a curing agent (C)

Wherein the polyarylate resin (B) has a glass transition temperature of 200 DEG C or higher,

Wherein a content ratio (A) / (B) of the epoxy resin (A) to the polyarylate resin (B) is 30/70 to 90/10 (mass ratio).

(2) The resin composition according to (1), wherein the epoxy equivalent of the epoxy resin (A) is 90 to 500 g / eq.

(3) the polyarylate resin (B) comprises at least one divalent phenol residue selected from the group consisting of aromatic dicarboxylic acid residues and divalent phenol residues represented by the following formulas (i) to (iv) The resin composition according to (1) or (2)

In formula (i), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, ≪ / RTI > to about 20 aromatic hydrocarbon groups;

In formula (ii), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, And R ¹⁵ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

In formula (iii), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, is selected from the group consisting of an aromatic hydrocarbon of ~20, R ²⁵ are each independently an aliphatic hydrocarbon group of 1 to 20 carbon atoms, having a carbon number of 3-20 alicyclic hydrocarbon group, aromatic hydrocarbon group of 6 to 20 carbon atoms, having 1 to 20 carbon atoms And k is an integer of 2 to 12, and m is an integer of 0 or more and 2k or less; And

R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, And R ³⁵ is selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms And R ³⁶ is selected from the group consisting of an aromatic hydrocarbon group having 6 to 20 carbon atoms.

(4) The resin composition according to any one of (1) to (3), wherein the polyarylate resin (B) further comprises a divalent phenol moiety represented by the following formula (v)

R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a carbon number of 6 ≪ / RTI > to about 20 aromatic hydrocarbon groups.

(5) The resin composition according to any one of (1) to (4), wherein the resin composition is a resin composition for an adhesive sheet.

(6) A resin varnish obtained by dissolving the resin composition according to any one of (1) to (5) in an organic solvent.

(7) A coating film formed by drying the resin varnish described in (5).

(8) A laminate obtained by forming the film described in (7) on a substrate.

(9) A wiring board using the laminate according to (8).

According to the present invention, a resin composition capable of forming an adhesive layer having high heat resistance and excellent in solder resistance after moisture absorption can be obtained.

The laminate using such a resin composition can be suitably used particularly in a wiring board or the like, and even when the wiring board is heated by melting the solder, occurrence of peeling or peeling of the adhesive insulating layer can be suppressed.

The resin composition of the present invention can form an adhesive layer having excellent adhesion to both the conductor layer and the organic insulating substrate.

The resin composition of the present invention is also capable of forming an adhesive layer having excellent anti-creeping property at the time of hot pressing for curing.

The resin composition of the present invention can also form an adhesive layer having excellent dielectric properties.

Hereinafter, the present invention will be described in detail.

The number of epoxy groups contained in the epoxy resin (A) used in the present invention is not particularly limited as long as it is two or more in one molecule. As the epoxy resin (A), a known epoxy resin can be used, and an epoxy resin having 2 to 5 epoxy groups per molecule is preferably used. When the number of epoxy groups contained in one molecule is more than 5, viscosity increase sometimes becomes remarkable when a resin varnish is produced from the resin composition to be obtained. On the other hand, the epoxy group number means the average number of epoxy groups per molecule since the epoxy resin has a molecular weight distribution.

The epoxy equivalent of the epoxy resin (A) having two or more epoxy groups in a molecule is preferably 90 to 500 g / eq, more preferably 90 to 300 g / eq, and even more preferably 90 to 250 g / eq. If the epoxy equivalent is less than 90 g / eq, the epoxy group is excessively dense, the reactivity with the curing agent is lowered, and the crosslinking density is too high, so that the viscosity of the resin varnish dissolved in an organic solvent may become excessively high. If the epoxy equivalent is more than 500 g / eq, the crosslinking density of the epoxy resin after the curing reaction is lowered, so that the glass transition temperature of the obtained resin composition is not high and the heat resistance can not be improved.

Examples of the epoxy resin (A) having two or more epoxy groups in a molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, Novolac epoxy resin, cresol novolak epoxy resin, glycidylamine epoxy resin, isocyanurate epoxy resin, Haidanto dolphin epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, acrylic acid modified epoxy resin , Polyfunctional epoxy resins, brominated epoxy resins and phosphorus modified epoxy resins. Among them, bisphenol A type epoxy resin and phenol novolak type epoxy resin, especially bisphenol A type epoxy resin, can be suitably used. Such an epoxy resin is commercially available. Specific examples of the commercially available product include a product name: GAN (manufactured by Nippon Kayaku K.K.), a product name: jER630 (manufactured by Mitsubishi Chemical), a product name: HP4032 (manufactured by DIC) (Product name: jER807 manufactured by Mitsubishi Chemical), product name: MY-0500 (produced by Mitsubishi Chemical Co., Ltd.), product name: jER807 (manufactured by Mitsubishi Chemical), product name: Epiclon EXA-1514 EXA-4580-1000 (manufactured by DIC), product name: SR-HHPA (manufactured by Sakamoto Pharmaceutical Industries Co., Ltd.), trade name: MY-0600 (manufactured by Huntsman), product name: TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., And Araldite AER4152 (manufactured by Asahi Chemical Industry Co., Ltd.), and the like, but are not limited thereto. The above-mentioned epoxy resins may be used alone or in combination of two or more. The epoxy resin (A) may have a functional group other than the above, provided that it has two or more epoxy groups in one molecule.

Among the above epoxy resins, bisphenol A type epoxy resins (e.g., commercial products such as jER828), phenol novolak type epoxy resins (such as commercial products such as jER152), bisphenol F type epoxy resins (such as commercial products such as jER807) (For example, commercially available products such as jER604) are preferred, and bisphenol A type epoxy resins and phenol novolak type epoxy resins are preferable because of the high effect of improving the adhesiveness of copper foils and polyimide films of the obtained coating films. Particularly preferred.

Depending on the number of repeating units of the bisphenol skeleton, the above-mentioned bisphenol A type epoxy resin exists as a liquid at normal temperature and a solid at room temperature. The bisphenol A type epoxy resin having 1 to 3 repeating units of the main chain bisphenol skeleton is a liquid at room temperature and the bisphenol A type epoxy resin having 2 to 10 repeating units of the main chain bisphenol skeleton is a solid at room temperature. Therefore, in the step of forming a film on a substrate to obtain a laminate, the film is firmly adhered to the adherend by heating and solidified, whereby the film and the adherend are firmly adhered to each other. Such a relatively low molecular weight bisphenol A type epoxy resin has a feature of high mechanical strength, good chemical resistance, high curability, and small hygroscopicity (because the free volume becomes small) because the cross-linking density of the relatively low molecular weight bisphenol A type epoxy resin is high.

In the present invention, as the bisphenol A type epoxy resin, it is preferable to use a bisphenol A type epoxy resin which is solid at room temperature as described above and a bisphenol A type epoxy resin which is liquid at room temperature. By using the solid and liquid at room temperature together, flexibility can be obtained while maintaining the mechanical strength, so that flexibility can be obtained while maintaining the inherent mechanical strength of the resin composition. As a result, bonding strength between adherends can be improved. As the bisphenol A type epoxy resin which is solid at room temperature, it is preferable that the glass transition temperature is in the range of 50 to 150 캜 from the viewpoints of mechanical strength and heat resistance. Specifically, as the bisphenol A type epoxy resin having 1 to 3 repeating units of the main chain bisphenol skeleton, which is a liquid at room temperature, jER 828 (manufactured by Mitsubishi Chemical) is used as the repeating unit of the main chain bisphenol skeleton As the bisphenol A type epoxy resin having a number of 2 to 10, jER1001 (manufactured by Mitsubishi Chemical) can be exemplified.

The viscosity of the epoxy resin (A) having two or more epoxy groups in one molecule is preferably 5 to 30 Pa · s at 25 ° C, more preferably 8 to 25 Pa · s, More preferably 20 Pa · s. The epoxy resin (A) may have a viscosity at 52 캜 within a predetermined range, instead of the viscosity at 25 캜 being within the above range. For example, the viscosity at 52 ° C is preferably 0.5 to 10 Pa · s, more preferably 0.8 to 8 Pa · s, and even more preferably 1 to 3 Pa · s.

The polyarylate resin (B) used in the present invention is an aromatic polyester polymer composed of an aromatic dicarboxylic acid and / or a derivative thereof and a divalent phenol and / or a derivative thereof and is produced by a method such as solution polymerization, melt polymerization, Lt; / RTI >

The polyarylate raw material for introducing an aromatic dicarboxylic acid residue is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6- Dicarboxylic acids such as dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methylterephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'- 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylsulfon dicarboxylic acid, 4,4'-diphenylisopropylidene dicarboxylic acid, 1,2-bis (4-carboxyphenoxy ) Ethane, and 5-sodium sulfoisophthalic acid. Among them, terephthalic acid and isophthalic acid are preferable, and from the viewpoint of solubility in solvents, it is particularly preferable to use them in combination. In this case, the mixing ratio (terephthalic acid / isophthalic acid) is arbitrarily selected from the range of 100/0 to 0/100 (molar%), but preferably 80/20 to 10/90 (molar%), Is in the range of 25 to 25/75 (mol%), the solubility of the obtained polyarylate resin (B) is excellent.

Aliphatic dicarboxylic acids may be used together with the above-mentioned aromatic dicarboxylic acids insofar as the characteristics and effects of the present invention are not impaired. The aliphatic dicarboxylic acids are not particularly limited and include dicarboxymethylcyclohexane, cyclohexane dicarboxylic acid, adipic acid, sebacic acid, glutaric acid, and dodecane diacid.

The polyarylate raw material for introducing the divalent phenol residue is not particularly limited, but from the viewpoints of improving the heat resistance of the resulting resin composition and improving the solubility in an organic solvent, the polyarylate raw materials represented by the following formulas (i) to (iv) (Hereinafter sometimes referred to as a bisphenol I residue) selected from the group consisting of divalent phenol residues to be introduced into the reaction system.

In formula (i), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, 20 aromatic hydrocarbon groups. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferred halogen atoms are a fluorine atom, a chlorine atom, and a bromine atom. Examples of the aliphatic hydrocarbon group include an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, have. The preferable aliphatic hydrocarbon group is an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5, particularly 1 to 3 carbon atoms. Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group and cyclodecyl group. Preferred alicyclic hydrocarbon groups are cycloalkyl groups having 3 to 10 carbon atoms, especially 3 to 6 carbon atoms. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, and an anthranyl group. Preferred aromatic hydrocarbon groups are aryl groups of 6 to 14 carbon atoms, especially 6 to 10 carbon atoms.

In the preferred divalent phenol moiety of formula (i), R ¹ and R ³ are each independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms, Especially an aryl group of 6 to 10; R ² and R ⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms.

More preferably, in the divalent phenol residue of the formula (i), R ¹ and R ³ are each independently preferably an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms; R ² and R ⁴ are simultaneously hydrogen atoms.

Examples of the compound for introducing the divalent phenol residue of the above formula (i) include 9,9-bis (4-hydroxyphenyl) fluorene (BPF), 9,9-bis (4- 3-methylphenyl) fluorene (BCF), 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9- .

In formula (ii), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, 20 aromatic hydrocarbon groups. The halogen atom is the same as the halogen atom in the formula (i), and preferred halogen atoms are a fluorine atom, a chlorine atom and a bromine atom. The aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group in the formula (i), and the preferable aliphatic hydrocarbon group is an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5, particularly 1 to 3. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the formula (i), and the preferable alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, especially 3 to 6 carbon atoms. The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in the formula (i), and the preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.

R ¹⁵ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Preferred alkyl groups are alkyl groups of 1 to 5, especially 1 to 3 carbon atoms. As the alkenyl group, there can be mentioned a vinyl group and an allyl group. A preferred alkenyl group is an alkenyl group having 2 to 3 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group and an anthranyl group. Preferred aryl groups are aryl groups of 6 to 14 carbon atoms, especially 6 to 10 carbon atoms.

In a preferable divalent phenol residue of the formula (ii), R ¹¹ and R ¹³ are each independently preferably a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ¹² and R ¹⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ¹⁵ is an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms, or an aryl group having 6 to 20 carbon atoms, especially 6 to 10 carbon atoms.

More preferably, in the divalent phenol moiety of the formula (ii), R ¹¹ to R ¹⁴ are simultaneously hydrogen or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ¹⁵ is an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms, or an aryl group having 6 to 20 carbon atoms, especially 6 to 10 carbon atoms.

Examples of the compound for introducing the divalent phenol residue of the above formula (ii) include N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine (PPPBP) 3-bis (4-hydroxyphenyl) phthalimidine, and the like.

In formula (iii), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, 20 aromatic hydrocarbon groups. The halogen atom is the same as the halogen atom in the formula (i), and preferred halogen atoms are a fluorine atom, a chlorine atom and a bromine atom. The aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group in the formula (i), and the preferable aliphatic hydrocarbon group is an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5, particularly 1 to 3 carbon atoms. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the formula (i), and the preferable alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, especially 3 to 6 carbon atoms. The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in the formula (i), and the preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.

R ²⁵ is selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a halogenated alkyl group having 1 to 20 carbon atoms. The aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group in the formula (i), and the preferable aliphatic hydrocarbon group is an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5, particularly 1 to 3. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the formula (i), and the preferable alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, especially 3 to 6 carbon atoms. The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in the formula (i), and the preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms. The halogenated alkyl group preferably has 1 to 2 hydrogen atoms in the alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5, particularly 1 to 3 carbon atoms, a halogen atom (e.g., a fluorine atom, a chlorine atom, Atoms). Preferable halogenated alkyl groups include a monofluoromethyl group, a difluoromethyl group, a monochloromethyl group, and a dichloromethyl group. When m is an integer of 2 or more, the two or more R ^{25 s} may be independently selected from the above group.

k is an integer of 2 to 12, preferably 4 to 11, more preferably 4 to 6. In the carbon ring in which the number of the constituent carbon atoms varies according to the value of k, the hydrogen atom of each carbon atom is omitted. When m is 1 or more, the one or more R < ²⁵ > s are substituted with hydrogen atoms contained in the carbon atoms constituting the carbon ring.

m is an integer of 0 or more and 2k or less, preferably 0 to 4, and more preferably 1 to 4.

In the preferred divalent phenol moiety of the formula (iii), R ²¹ and R ²³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ²² and R ²⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ²⁵ is an alkyl group of 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; In particular, when m is an integer of 2 or more, the two or more R ^{25 s} may be each independently an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms at the same time; k is an integer from 4 to 11, in particular from 4 to 6; m is an integer of 0 to 4, particularly 1 to 4;

More preferably, in the divalent phenol residue of the formula (iii), R ²¹ to R ²⁴ are simultaneously hydrogen or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ²⁵ is an alkyl group of 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; Particularly when m is an integer of 2 or more, the two or more R < ²⁵ > s are simultaneously alkyl groups having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; k is an integer from 4 to 6; m is an integer of 2 to 4;

Examples of the compound for introducing the divalent phenol moiety of the above formula (iii) include 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 1,1- (4-hydroxyphenyl) cyclohexane (DMBPC), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- Bis (4-hydroxy-3-methylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclopentane, (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane (BPTMC), 1,1- 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4-hydroxy-3,5-dimethylphenyl) cyclododecane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclododecane Can.

In formula (iv), R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, 20 aromatic hydrocarbon groups. The halogen atom is the same as the halogen atom in the formula (i), and preferred halogen atoms are a fluorine atom, a chlorine atom and a bromine atom. The aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group in the formula (i), and the preferable aliphatic hydrocarbon group is an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5, particularly 1 to 3. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the formula (i), and the preferable alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, especially 3 to 6 carbon atoms. The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in the formula (i), and the preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.

R ³⁵ is selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. The halogen atom is the same as the halogen atom in the formula (i), and preferred halogen atoms are a fluorine atom, a chlorine atom and a bromine atom. The aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group in the formula (i), and the preferable aliphatic hydrocarbon group is an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5, particularly 1 to 3. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the formula (i), and the preferable alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, especially 3 to 6 carbon atoms. The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in the formula (i), and the preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.

And R ³⁶ is selected from the group consisting of an aromatic hydrocarbon group having 6 to 20 carbon atoms. The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in the formula (i), and the preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms. When R ³⁶ is a hydrogen atom or an alkyl group, the heat resistance is lowered, and in particular, the solder resistance is lowered after moisture absorption of the adhesive layer.

In the divalent phenol residue of the preferable formula (iv), R ³¹ and R ³³ each independently preferably represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms, An aryl group of 6 to 20, in particular 6 to 10; R ³² and R ³⁴ are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ³⁵ is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ³⁶ is an aryl group having 6 to 20 carbon atoms, especially 6 to 10 carbon atoms.

More preferably, in the divalent phenol moiety of the formula (iv), R ³¹ to R ³⁴ simultaneously represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ³⁵ is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ³⁶ is an aryl group having 6 to 20 carbon atoms, especially 6 to 10 carbon atoms.

Examples of the compound for introducing the divalent phenol moiety of the above formula (iv) include bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) (BPAP), 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1- , 1-bis (4-hydroxy-3,5-dibromophenyl) -1-phenylethane and 1,1-bis (4-hydroxy-3-phenylphenyl) .

Of the compounds for introducing the bisphenol I residue, 9,9-bis (4-hydroxyphenyl) fluorene (BPF), 9,9-bis (4-hydroxy- (3-hydroxyphenyl) phthalimide (PPPBP), 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ) (DMBPC), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC) , And 1,1-bis (4-hydroxyphenyl) -1-phenylethane (BPAP). These compounds may be used alone or in combination of two or more.

A divalent phenol moiety represented by the following formula (v) (hereinafter sometimes referred to as a bisphenol moiety moiety) may be further introduced in addition to one or more divalent phenol moieties represented by the above formulas (i) to (iv) The solubility in an organic solvent increases, and the adhesiveness of an obtained coating film to an adherend can be enhanced.

Formula (v) of, R ^5, R ^6, R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, having 3 to 20 carbon atoms in the alicyclic hydrocarbon group of 1 to 20 carbon atoms, having a carbon number of 6 to 20 aromatic hydrocarbon groups. The halogen atom is the same as the halogen atom in the formula (i), and preferred halogen atoms are a fluorine atom, a chlorine atom and a bromine atom. The aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group in the formula (i), and the preferable aliphatic hydrocarbon group is an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5, particularly 1 to 3. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the formula (i), and the preferable alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, especially 3 to 6 carbon atoms. The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in the formula (i), and the preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.

In a preferable divalent phenol residue of the formula (v), R ⁵ and R ⁷ are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R ⁶ and R ⁸ are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms.

Examples of the compound for introducing the divalent phenol residue of the above formula (v) include 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2- (3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane (BPC), 2,2- Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, and the like. These compounds may be used alone or in combination of two or more.

Of the compounds for introducing the divalent phenol moiety of the above formula (v), 2-bis (4-hydroxyphenyl) propane (BPA), 2,2- 3-methylphenyl) propane (BPC) and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane (TMBPA) can be preferably used and a balance between heat resistance and economy In particular, 2-bis (4-hydroxyphenyl) propane (BPA) is particularly preferred. (I) to (iv), in addition to the compound for introducing the divalent phenol residue of the above-mentioned formulas (i) to (iv), from the viewpoints of heat resistance and economical efficiency of the obtained polyarylate resin (B) As a compound for introducing the divalent phenol residue of v), it is preferable to use two or less, especially BPA, alone, including BPA.

(Bisphenol I residue) / (bisphenol I residue + bisphenol II residue) is introduced into the polyarylate resin (B) by introducing a divalent phenol residue selected from a bisphenol I residue and optionally introducing a bisphenol II residue It is preferably 10/100 to 100/100 (molar ratio), more preferably 30/100 to 100/100 (molar ratio). If the bisphenol I residue is less than 10 mol% based on the total amount of the dihydric phenol components, the heat resistance of the polyarylate resin (B) may be poor. (Bisphenol I residue) / (bisphenol I residue + bisphenol II residue) is preferably 10/100 to 80/100 (molar ratio), more preferably 20/100 to 80/100 (molar ratio), from the viewpoint of further improving the economical efficiency. Is more preferable.

To the polyarylate resin (B), a bisphenol residue other than the bisphenol I residue or the bisphenol II residue may be introduced as long as the properties and effects of the present invention are not impaired. Examples of such bisphenols include 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy diphenylmethane, 4,4'-dihydroxy diphenylmethane, 4,4'- Dihydroxydiphenyl sulfone, 4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy diphenyl ether, 4,4'-dihydroxy diphenyl sulfide, 4,4'-dihydroxy diphenyl ketone, 1,1 Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane and 4-methyl-2,2-bis (4-hydroxyphenyl) pentane.

Furthermore, aliphatic glycols and dihydroxybenzenes may be used in the polyarylate resin (B) as long as the properties and effects of the present invention are not impaired. The aliphatic glycols are not particularly limited and include aliphatic glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, nonene diol, decanediol, cyclohexanedimethanol, bisphenol A Ethylene oxide adducts, copper propylene oxide adducts, and ethylene oxide adducts of bisphenol S, and dihydroxybenzenes may include hydroquinone, resorcinol, and catechol.

The polyalylate resin (B) preferably has an intrinsic viscosity of 0.30 to 1.00 dL / g, more preferably 0.35 to 0.80 dL / g. If the inherent viscosity is less than 0.30 dL / g, the flexibility of the resulting resin composition becomes poor, and the resin composition may fall out from the end face of the layered product in the form of powder when punching or router processing. When the inherent viscosity is more than 1.00 dL / g, the viscosity when mixed with an epoxy resin or an organic solvent increases, and the dispersibility and the coating property are deteriorated, which is not preferable. On the other hand, the inherent viscosity is an index of the molecular weight, and the resin solution was dissolved in a mixed liquid of phenol / 1,1,2,2-tetrachloroethane 60/40 (mass ratio) so as to have a concentration of 1 g / .

In order to adjust the intrinsic viscosity, that is, the molecular weight, of the polyarylate resin (B) to a predetermined range, there are a method of adjusting the molecular weight by controlling the reaction rate by controlling the polymerization time, a method of adjusting the molecular weight of the aromatic dicarboxylic acid component or the dihydric phenol component A method in which the molecular weight is adjusted by blending any one of the components in an excess amount; a method in which aliphatic monohydric alcohols, phenols or monocarboxylic acids having only one reactive functional group in the molecule are added together with a monomer as a terminal blocking agent, And the like. Among them, a method of adding an end block agent is preferable because it is easy to control the molecular weight.

Examples of the terminal blocking agent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, Aliphatic monohydric alcohols; Phenols such as phenol, cresol, 2,6-xylenol, 2,4-xylenol, p-tert-butylphenol (PTBP), p-tert-octylphenol and cumylphenol; And monocarboxylic acids such as benzoic acid, methylbenzoic acid, naphthoic acid, acetic acid, propionic acid, butyric acid, oleic acid and stearic acid, and derivatives thereof.

The glass transition temperature of the polyarylate resin (B) used in the present invention is 200 ° C or higher, preferably 200 ° C or higher and lower than 320 ° C, more preferably 210 ° C or higher and lower than 310 ° C, And most preferably 230 deg. C or more and less than 290 deg. By setting the glass transition temperature to a predetermined range, the resulting resin composition has high heat resistance. If the glass transition temperature is less than 200 占 폚, the heat resistance of the resin composition becomes poor. If the glass transition temperature is 320 占 폚 or higher, the glass transition temperature of the resin composition becomes excessively high, and the curing reaction does not progress sufficiently.

The carboxyl value of the polyarylate resin (B) is preferably 10 mol / ton or more, more preferably 20 mol / ton or more, still more preferably 30 mol / ton or more. The carboxyl group of the polyarylate resin (B) represents the content of the terminal carboxyl group in the polyarylate resin (B), but the carboxyl group reacts with the epoxy group of the epoxy resin (A) ) And the polyarylate resin (B) can be easily commercialized. The method of introducing a terminal carboxyl group into the polyarylate resin (B) includes a method of stopping the polymerization reaction before the completion of the reaction and a method of hydrolyzing the ester bond by an alkali or the like.

In the resin composition of the present invention, the content ratio of the epoxy resin (A) and the polyarylate resin (B) is 30/70 to 90/10 (mass ratio) (Mass ratio), more preferably 40/60 to 80/20 (mass ratio), and still more preferably 40/60 to 70/30 (mass ratio). If the content of the epoxy resin (A) is less than 30 mass%, the adhesion of the resin composition to the adherend becomes insufficient. When the content of the epoxy resin (A) exceeds 90 mass%, the heat resistance after the heat treatment is not sufficient.

The curing agent (C) used in the present invention is not particularly limited as long as it is cured by reaction with the epoxy resin (A), and examples thereof include aliphatic Alicyclic polyamine compounds such as polyamine compounds, menendaiamines, isophorone diamines, bis (4-amino-3-methylcyclohexyl) methane and bis (4-aminocyclohexyl) Aromatic polyamine compounds such as diaminodiphenylmethane, diaminodiphenylsulfone and metaphenylene diamine, polyamine compounds such as dicyandiamide, adipic acid dihydrazide and polyamidopolyamine, or anhydrides such as phthalic anhydride, tetra Hydrohalophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophosphate Examples thereof include monofunctional acid anhydrides such as acetic anhydride, methylnadic acid, dodecylsuccinic anhydride and chlorogenic anhydride, anhydrous pyromellitic acid, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimate), methylcyclohexane Bifunctional acid anhydrides such as tetracarboxylic acid anhydride, and free acid anhydride carboxylic acids such as trimellitic anhydride and polyazelaic acid anhydride. These curing agents may be used alone or in combination of two or more.

The content of the curing agent (C) is not particularly limited, but is generally in a range such that the ratio of the stoichiometric amount of the epoxy group of the epoxy resin (A) to the stoichiometric amount of the functional group of the curing agent (epoxy / curing agent) is 0.5 to 1.5 . Since the reaction mechanism differs from the stoichiometric amount depending on the type of the curing agent, the curing agent content can be determined by the ratio of the equivalent weight of the active hydrogen and the epoxy equivalent of the curing agent. For example, when the curing agent is an amine compound, the compounding amount of the amine compound can be calculated by the ratio of the equivalent amount of active hydrogen bonded to the amino group to the epoxy equivalent. Here, the epoxy equivalent is a value obtained by dividing the average molecular weight of the epoxy resin by the number of epoxy groups per one molecule. When the curing agent is an amine compound, the equivalent of active hydrogen is a value obtained by dividing the average molecular weight of the amine compound by the number of hydrogen atoms bonding to the amino group per molecule.

In the resin composition of the present invention, a curing accelerator may be used instead of or in combination with the curing agent. The curing accelerator is not particularly limited and includes, for example, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, benzyldimethylamine, 2 Tertiary amines such as - (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol can be used. The blending amount of the curing accelerator can be appropriately set.

In the resin composition of the present invention, resins other than the polyarylate resin (B) may be added within the range of the performance required in the present invention in order to give a desired performance. Examples of other resins include polycarbonate, polystyrene, polyester, acrylic resin, polyphenylene ether, polysulfone, polyethersulfone, and polyetherimide. Further, various additives such as an antioxidant, a flame retardant, an ultraviolet absorber, a flowability modifier, and a particulate inorganic filler may be mixed and used.

A method for producing the resin composition of the present invention will be described.

The resin composition of the present invention can be prepared by dissolving and mixing at least an epoxy resin (A), a polyarylate resin (B) and a curing agent (C) in an organic solvent to a predetermined ratio.

Examples of the dissolution method include a method in which an epoxy resin (A), a polyarylate resin (B) and a curing agent (C) are collectively added to an organic solvent and mixed while dissolving the epoxy resin (A), the polyarylate resin (B) (A) and a polyarylate resin (B) are mixed, and then the curing agent (C) is added to the organic solvent while being added to the organic solvent to dissolve and dissolve the epoxy resin And the like. (A), the polyarylate resin (B) and the curing agent (C) are collectively added to an organic solvent in order to improve the workability at the time of dissolution and mixing and to increase the uniformity of the obtained resin composition It is particularly preferable to use a method of mixing while mixing. On the other hand, a method of melting and mixing the epoxy resin (A), the polyarylate resin (B) and the curing agent (C) is also considered, but since the viscosity of the resulting resin composition becomes too high, , It should not be employed in the present invention unless it is necessary.

As for the organic solvent to be used, it is necessary to pay attention to the following points. That is, the epoxy resin (A) and the polyarylate resin (B) are different from each other in the kinds of organic solvents which are easily dissolved. If an organic solvent in which either one is difficult to dissolve is used, it becomes difficult to make the obtained resin composition uniform.

In a preferred embodiment, the epoxy resin (A) and the polyarylate resin (B) used in the present invention may be dissolved in a common organic solvent and mixed in a resin solution to prepare a resin varnish. When resin varnishes are prepared, it is preferable that a resin varnish having high compatibility is obtained without separating the two components of the epoxy resin (A) and the polyarylate resin (B) from each other. When a film is formed using such a resin varnish, the epoxy resin (A) and the polyarylate resin (B) are not separated from each other in the resin composition and a uniform resin composition is obtained. Therefore, . In other words, the polyarylate resin (B) must be dissolved in the same organic solvent as the organic solvent dissolving the epoxy resin (A), but the polyarylate resin (B) used in the present invention is particularly preferably soluble in a dissolvable solvent The selection of a solvent is wide. Therefore, various organic solvents can be selected according to the purpose, and various coating films can be formed.

As the organic solvent to be used, it is preferable that the polyarylate resin (B) alone can be dissolved in a solid content concentration of 20 mass% or more, more preferably 30 mass% or more.

As the organic solvent, it is necessary to choose an appropriate one depending on the kind of the epoxy resin (A) to be used in combination with other resins to be used if necessary, and 1,4-dioxane, dimethylacetamide, dimethylformamide, N-methyl Pyrrolidone, dimethylsulfoxide, methyl ethyl ketone, cyclohexanone, toluene, xylene, etc. These may be used alone or in admixture of two or more kinds. Of these, 1,4-dioxane, dimethylformamide, N-methylpyrrolidone, toluene, and mixtures of at least one of them with methyl ethyl ketone are preferable.

The resin composition after curing tends to be excellent in mechanical properties and heat resistance when the curing agent (C) is dissolved in a solvent. However, the organic solvent soluble in the curing agent (C) together with the epoxy resin (A) and the polyarylate resin . In such a case, it is preferable that the curing agent (C) is crushed as finely as possible and uniformly dispersed in a solution in which the epoxy resin (A) and the polyarylate resin (B) are dissolved.

When the resin varnish is dissolved in the organic solvent to obtain the resin varnish, the solid content concentration is preferably 10 to 70 mass%, more preferably 15 to 60 mass%, and most preferably 20 to 50 mass% Is more preferable. When the solid concentration is less than 10 mass%, it is difficult to obtain a thickness necessary for forming the film. When the solid concentration exceeds 70 mass%, the film is hardly formed and the thickness precision of the obtained film is lowered. not.

As a method of forming a coating film using the above-described resin varnish, a coating film can be formed by applying and drying on various substrates using a known coating method such as Mayer bar coating, gravure coating, kiss coating, and spin coating have. Concretely, a film made of a resin composition can be formed by coating on a film substrate made of a polyethylene terephthalate (PET) resin or the like subjected to release treatment and then drying.

The film may be pulled off from the film substrate to be used as a single layer of the resin composition film, or may be used as a laminate having a film formed on the substrate.

The selection of the drying temperature at the time of formation of the coating film made of the resin composition is very important because it greatly affects the adhesion characteristics in the case of being used as a coating or laminate in the present invention.

In the present invention, the heating temperature at the time of drying is a temperature at which evaporation of the organic solvent from the resin varnish is promoted, and also the temperature at which the epoxy resin (A) in the resin composition reacts with the curing agent (C). The reaction temperature differs depending on the combination of the epoxy resin (A) and the curing agent (C), and can not be uniformly determined. However, the reaction temperature is preferably in the range of 80 to 160 캜. Therefore, it is preferable to select an organic solvent which can be dried in this temperature range in addition to the above-mentioned solubility. Further, the heating time is required not only to remove the organic solvent but also to set the resin composition to reach a desired reaction rate, but the reaction rate can not be uniformly determined because it depends on the heating temperature. As an example, if the heating temperature is 80 to 160 占 폚, the heating time is 5 to 50 minutes. The reaction rate of the resin composition after heating is preferably set so that the epoxy resin reaches the semi-cured B-stage. In this way, a film made of the resin composition can be formed. The drying is preferably carried out in a multistage manner in which the reaction temperature (drying temperature) is different. In this case, drying may be performed in multiple stages so that the temperature gradually increases within the above range, and the drying time of each step may be set so that the total time is within the above range.

When the resin composition of the present invention is dissolved in an organic solvent for mixing, a defoaming agent, a leveling agent, an ionic repairing agent, and the like may be added to the extent that the object of the present invention is not impaired.

The laminate having a coating film formed on the coating film or the substrate of the present invention can be used in various applications. Particularly, it can be suitably used for electric and electronic parts applications. As a specific example of use, a bonding sheet will be described as an example. The bonding sheet is a so-called adhesive layer for adhering a circuit, a component or another substrate on a substrate, and usually an adhesive layer is formed on a film substrate. In the case of manufacturing a multilayer printed wiring board, for example, a laminate is firstly formed on a patterned circuit board as a bonding sheet, the film substrate is peeled from the adhesive layer, and an organic insulating layer, a conductor, Laminated. Thereafter, final curing is performed to complete the multilayer printed wiring board. Here, at the time of final curing, it is preferable that the curing is promoted by heating at a low temperature in order to prevent oxidation of the wiring and the like and to prevent the adhesion of the wiring and the substrate from being lowered. Therefore, in the present invention, the heat curing temperature is preferably 100 占 폚 to 250 占 폚, more preferably 120 占 폚 to 200 占 폚, further preferably 130 占 폚 to 190 占 폚. If the final heating temperature exceeds 250 DEG C, oxidation deterioration of the wiring may progress. The heat curing time is not particularly limited as long as sufficient curing can be achieved. For example, in the case of the above-mentioned heat curing temperature, the heat curing time is 30 to 120 minutes, particularly 60 to 100 minutes.

The film or laminate formed from the resin composition of the present invention is excellent in heat resistance, chemical resistance, flexibility and smoothness, and is suitable for a build-up type multilayer printed wiring, particularly a lamination adhesive sheet for a multilayer flexible printed wiring board. By using the film or laminate of the present invention, the flexible printed wiring board can suppress the occurrence of peeling or peeling of the adhesive insulating layer even when heated to melt the solder.

Specifically, in the production of a multilayer flexible printed wiring board, first, an inner layer circuit is formed by pattern-etching each of the copper foils attached to both surfaces of a flexible substrate material made of polyimide resin, For example, a coverlay made of a polyimide resin is pressed to cover the entire surface of the built-in circuit on both sides to obtain a flexible printed wiring board. Further, on the both surfaces thereof, for example, an outer flexible substrate bonded to only the opposite surface of a flexible printed wiring board made of a polyimide resin as a separate substrate is bonded by an adhesive and pressed by pressure processing to form a multilayer Layer flexible printed wiring board is obtained. The flex-rigid printed wiring board is a multilayer wiring board obtained by laminating a rigid substrate material obtained by laminating a prepreg obtained by impregnating a substrate with a resin on a flexible printed wiring board similar to the above, with an adhesive. An adhesive sheet formed from the resin composition of the present invention is used as an adhesive in such a multilayer flexible printed wiring board and a flex-rigid printed wiring board.

Example

EXAMPLES The present invention will now be described in detail based on examples, but the present invention is not limited to these examples.

1. Evaluation Method

(1) Intrinsic viscosity of polyarylate resin

The polyarylate resin was dissolved in 1,1,2,2-tetrachloroethane to prepare a sample solution having a concentration of 1 g / dL. Subsequently, the dropping time T of the sample solution and the falling time T ₀ of the solvent were measured at a temperature of 25 ° C using a Ubbelohde type viscometer, and the intrinsic viscosity? Was obtained using the following equation.

Intrinsic viscosity η = Ln (η _rel ) / c

However, η _rel is the relative viscosity and is calculated by the following formula. C = 1 g / dL.

η _rel = T / T ₀

(2) Glass transition temperature

The temperature was raised from 40 DEG C to 340 DEG C at a heating rate of 20 DEG C / min using a differential scanning calorimeter (DSC7, manufactured by Perkin Elmer), and the start temperature of the discontinuous change derived from the glass transition temperature in the obtained temperature rising curve was set to the glass transition temperature did.

(3) Adhesion to copper foil

The resin varnish obtained in the following Examples or Comparative Examples was applied to a PET film base (pavement PET37SG-1) flexibly with an applicator to a final dry thickness of 15 m.

After drying at 80 占 폚 for 30 minutes and then heating at 120 占 폚 or 150 占 폚 for 10 minutes, the film of the resin composition to be formed was made into a semi-cured B-stage state (hereinafter referred to as laminate A). On the other hand, the heating temperature for the B stage state is 150 占 폚 for the use of the curing agent (c1) and 120 占 폚 for the case of using the curing agent (c2). The film-formed surface of the laminate was superimposed on the copper foil side of a copper clad laminate (hereinafter referred to as one-side CCL, manufactured by Sumitomo Metal Mining Co., Ltd., copper foil / polyimide film = 8/25 占 퐉), laminated using a vacuum laminator, The PET film base material was released from the laminate to obtain a laminate [B] in which the film was laminated on the copper foil surface of the copper clad laminate. Further, a film-forming surface of the laminate [B] was laminated on the copper foil side of another one-side CCL in the same manner as described above to obtain a laminate [C] having a configuration in which a film was sandwiched between two copper clusters of CCL. The laminate [C] was hot-pressed at a heating temperature of 190 占 폚 and a pressing pressure of 3 MPa for 90 minutes to completely cure the film to obtain a sample for evaluation of adhesion. The sample was cut into a short sheet having a width of 10 mm, and the peel strength at an angle of 90 was measured under a test condition of a tensile speed of 100 mm / min. , The cases where the peel strength was more than 2.0 N / cm were evaluated as "? &Quot;, the cases where the peel strength exceeded 1.5 N / cm were evaluated as & / cm " is " x ".

In the present invention, it is practically preferable that the evaluation result is "O" or more, particularly "⊚".

(4) Adhesion to polyimide film

Two polyimide films were coated with the coating film (C) in the same manner as in the production of the laminate [C] in the above (3) except that a polyimide film (Kapton, To obtain a layered product [D] having the constitution. The laminate [D] was hot-pressed at a heating temperature of 190 占 폚 and a pressing pressure of 3 MPa for 90 minutes to completely cure the coating, thereby obtaining a sample for evaluation of adhesion. The sample was cut into a short-cut shape with a width of 10 mm and subjected to a peel strength test at an angle of 90 degrees under the test conditions of a tensile speed of 100 mm / min to evaluate the failure mode. The failure mode is an order of "material breakdown" in which the polyimide film is broken, "cohesive failure" in which the adhesive layer is broken (practically no problem), and "interface peeling" in which the adhesive layer is peeled off from the polyimide film.

In the present invention, it is practically preferable that the evaluation result is " material breakdown ".

(5) Solder bath test

The layered product [C] produced in the step (3) was hot-pressed at a heating temperature of 190 占 폚 and a pressing pressure of 3 MPa for 90 minutes, and then cut into a size of 50 mm 占 50 mm. The sample was stored in a desiccator containing a desiccant for 24 hours (hereinafter referred to as a full sample) and a sample stored for 16 hours in a constant temperature and humidity bath at 40 占 폚 and 90% RH (hereinafter referred to as a moisture absorption sample) We prepared two kinds. The moisture content of the moisture absorption sample was 0.3%. Each of the tight sample and the moisture absorption sample was floated in a solder bath at 260 ° C for 1 minute, and the appearance change before and after the stand was evaluated. The case where the appearance change was not observed after the solder bath was judged to be "? &Quot;, the case where a small bump was observed was judged to be " DELTA " (no problem in practice), and the case where severe bump or peeling was observed.

In the present invention, it is preferable for practical use to be "? &Quot;.

The heat resistance can be evaluated by the result of the evaluation by a full-size sample.

The solder resistance after moisture absorption can be evaluated by the evaluation result of the moisture absorption sample.

(6) Dielectric properties

A layered product was produced in the same manner as in the case of using the glass base material as the substrate and the "(3) Adhesion to copper foil" layered product [C]. The laminate was hot-pressed at a heating temperature of 190 占 폚 and a press pressure of 3 MPa for 90 minutes, and then the film was peeled from the glass substrate. Cut into a size of 50 mm x 50 mm and used as a sample. The obtained coating film was set on the following measurement jig, and the dielectric constant and dielectric loss tangent were measured at room temperature by the following apparatus.

<Device> Agilent Technologies Inc. (current key site, technology company) Impedance / material analyzer E4991A

<Measurement jig> The company 16453A

2. Raw materials

(1) Epoxy resin

(a1) an epoxy equivalent of 184 to 194 g / eq, a viscosity of 120 to 150 P (= 12 to 15 Pa · s) (25 캜), the number of epoxy groups present in one molecule = 2 dog

(a2) an epoxy equivalent of 176 to 178 g / eq, a viscosity of 14 to 18 P (= 1.4 to 1.8 Pa · s) (52 ° C), a number of epoxy groups present in one molecule = 3 or more

(2) Polyarylate resin

Polyarylate resins (b1) to (b9) having the following characteristics were obtained by the method described in Production Examples to be described later.

(3) Curing agent

(c1) Dicyandiamide (manufactured by Nippon Carbide Industries, Ltd.)

(c2) diaminodiphenylsulfone (a special grade reagent manufactured by Kanto Chemical Co., Ltd.)

Production Example 1

1.2 L of water was added to a reaction vessel equipped with a stirrer, and then 0.79 mol of sodium hydroxide, 0.194 mol of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (BCF) as a dihydric phenol, -tert-butylphenol (PTBP) was dissolved, 0.0013 mol of a polymerization catalyst (tributylbenzylammonium chloride) was added, and the mixture was stirred vigorously (aqueous alkali solution). In a separate vessel, 0.100 mol of terephthalic acid chloride (TPC) and 0.100 mol of isophthalic acid chloride (IPC) were weighed and dissolved in 0.7 L of methylene chloride.

The methylene chloride solution was mixed with the previously prepared alkali aqueous solution while stirring to initiate polymerization. The polymerization reaction temperature was about 20 캜. The polymerization was carried out for 2 hours under stirring. Thereafter, stirring was stopped, and the reaction solution was allowed to stand to separate the aqueous phase from the organic phase. Only the aqueous phase was withdrawn from the reaction vessel and 2 g of acetic acid was added to the remaining organic phase. Then, 1.5 L of water was added and the mixture was stirred for 30 minutes. This washing operation was repeated until the pH of the aqueous phase after washing became about 7. The obtained organic phase was gradually added to a warm water bath equipped with a homomixer at 50 DEG C while methylene chloride was evaporated to precipitate a polymer in powder form, which was taken out and dehydrated and dried to obtain a polyarylate resin (b1). The inherent viscosity of the polyarylate resin (b1) was 0.49 dL / g. As a result of DSC measurement, no crystal melting peak was observed and the glass transition temperature was 285 ° C. The results are shown in Table 1.

Production Example 2

A polyarylate resin (b2) was obtained in the same manner as in Production Example 1 except that the dihydric phenol was replaced by N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine (PPPBP). The polyarylate resin (b2) had an intrinsic viscosity of 0.49 dL / g. As a result of DSC measurement, no crystal melting peak was observed and the glass transition temperature was 300 ° C. The results are shown in Table 1.

Production Example 3

A polyarylate resin (b3) was obtained in the same manner as in Production Example 1 except that the dihydric phenol was changed to 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC) . The polyarylate resin (b3) had an intrinsic viscosity of 0.49 dL / g. As a result of DSC measurement, no crystal melting peak was observed and the glass transition temperature was 255 ° C. The results are shown in Table 1.

Production Example 4

A polyarylate resin (b4) was obtained in the same manner as in Production Example 1, except that the dihydric phenol was changed to 1,1-bis (4-hydroxyphenyl) -1-phenylethane (BPAP). The polyarylate resin (b4) had an intrinsic viscosity of 0.49 dL / g. As a result of DSC measurement, no crystal melting peak was observed and the glass transition temperature was 240 ° C. The results are shown in Table 1.

Production Example 5

(4-hydroxyphenyl) -1-phenylethane (BPAP) was used as the dihydric phenol, and the amounts of the TPC and the IPC were changed to 0.14 mol and 0.06 mol, respectively, Relat resin (b5) was obtained. The inherent viscosity of the polyarylate resin (b5) was 0.48 dL / g. As a result of DSC measurement, no crystal melting peak was observed and the glass transition temperature was 265 ° C. The results are shown in Table 1.

Production Example 6

A polyarylate resin (b6) was obtained in the same manner as in Production Example 5 except that the blending amounts of TPC and IPC were changed to 0.06 mol and 0.14 mol, respectively. The polyarylate resin (b6) had an intrinsic viscosity of 0.49 dL / g. As a result of DSC measurement, no crystal melting peak was observed and the glass transition temperature was 220 ° C. The results are shown in Table 1.

Production Example 7

Dihydric phenol was reacted with 0.136 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC) and 2,0-bis (4-hydroxyphenyl) propane ) Was obtained in the same manner as in Preparation Example 1, except that the amount of the polyarylate resin (b7) was changed to 0.058 mol. The polyarylate resin (b7) had an intrinsic viscosity of 0.49 dL / g. As a result of DSC measurement, no crystal melting peak was observed and the glass transition temperature was 240 ° C. The results are shown in Table 1.

Production Example 8

Bisphenol was reacted with 0.058 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC) and 2,2-bis (4-hydroxyphenyl) propane ) Was obtained in the same manner as in Production Example 7, except that the amount of the polyarylate resin (b8) was changed to 0.136 mol. The polyarylate resin (b8) had an intrinsic viscosity of 0.48 dL / g. As a result of DSC measurement, no crystal melting peak was observed and the glass transition temperature was 215 ° C. The results are shown in Table 1.

Production Example 9

A polyarylate resin (b9) was obtained in the same manner as in Preparation Example 7 except that the dihydric phenol was changed to 0.194 mol of 2,2-bis (4-hydroxyphenyl) propane (BPA). The inherent viscosity of the polyarylate resin (b9) was 0.48 dL / g. As a result of DSC measurement, no crystal melting peak was observed and the glass transition temperature was 190 ° C. The results are shown in Table 1.

Example 1

A separator flask equipped with a stirrer and a cooling tube was used, and 250 parts by mass of N, N-dimethylformamide was used as an organic solvent. 50 parts by mass of the epoxy resin (a1) was dissolved by heating at 60 占 폚 and then 50 parts by mass of the polyarylate resin (b1). Then, 2.8 parts by mass of the epoxy resin curing agent (c1) 0.35 parts by mass of 2-ethyl-4-methylimidazole as a curing accelerator was dissolved. Thereafter, the stirring was stopped and deaerated to prepare a resin varnish made of a resin composition.

Using the resin varnish thus obtained, a film and a laminate were formed and various evaluations were conducted. The results are shown in Table 2.

Examples 2 to 11 and Comparative Examples 1 to 4

A film and a laminate were formed in the same manner as in Example 1 except that the types and blending amounts of the epoxy resin, the polyarylate resin and the curing agent were changed as shown in Table 2, and various evaluations were made. The results are shown in Tables 2 and 3.

Example 12

A separator flask equipped with a stirrer and a cooling tube was used, and 200 parts by mass of toluene was used as an organic solvent. First, 50 parts by mass of the epoxy resin (a1) was dissolved by heating at 60 캜, and then 50 parts by mass of the polyarylate resin (b4) was dissolved in the organic solvent. To this solution, 16.3 parts by mass of an epoxy resin curing agent (c2) was dissolved in 50 parts by mass of methyl ethyl ketone as an organic solvent in a separate container, and the whole amount of the solution was uniformly mixed. Thereafter, the stirring was stopped and the resin varnish was obtained by degassing. A film and a laminate were formed in the same manner as in Example 1, and various evaluations were conducted. The results are shown in Table 2.

Comparative Example 5

A separator flask equipped with a stirrer and a cooling tube was used, and 300 parts by weight of N, N-dimethylformamide was used as an organic solvent. 100 parts by mass of the polyarylate resin (b4) was dissolved by heating at 60 占 폚 with respect to the organic solvent. Thereafter, the stirring was stopped and the resin varnish was obtained by degassing. A film and a laminate were formed in the same manner as in Example 1, and various evaluations were conducted. The results are shown in Table 3.

Comparative Example 6

Except that 50 parts by weight of a polycarbonate resin (Yupilon S-3000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.: an inherent viscosity of 0.48 dL / g and a glass transition temperature of 145 캜) was used in place of the polyarylate resin I tried to make it.

However, although the test was tried to dissolve by heating at 60 캜, the test was stopped because insoluble matter occurred because it was hardly dissolved.

The evaluation results of the dielectric properties in the following examples / comparative examples were as follows.

Example 3: Specific dielectric constant 3.1, dielectric tangent 0.010;

Example 8: Specific dielectric constant 3.2, dielectric tangent 0.011;

Comparative Example 4: relative dielectric constant 3.3, dielectric tangent 0.012.

※ Test frequency = 1GHz

Since the resin compositions obtained in Examples 1 to 12 had a predetermined composition, adhesion to the copper foil or the polyimide film was good and the heat resistance was improved. Furthermore, it has excellent solder resistance after moisture absorption.

In Comparative Example 1, since the polyarylate resin was not contained, the heat resistance of the coating film was insufficient, and the solder resistance after moisture absorption was lowered, resulting in peeling.

In Comparative Example 2, since the content of the polyarylate resin was less than the lower limit, the heat resistance of the coating film was insufficient and the solder resistance after moisture absorption was lowered, resulting in peeling.

In Comparative Example 3, since the content of the epoxy resin was less than the lower limit value, adhesion to both the copper foil and the polyimide film was poor.

In Comparative Example 4, since the glass transition temperature of the polyarylate resin was low, the solder resistance after moisture absorption deteriorated.

In Comparative Example 5, since it did not contain an epoxy resin, it was easily peeled off in evaluation of adhesion with the copper foil or the polyimide film, and had no adhesion to both the copper foil and the polyimide film. Furthermore, in the solder bath test, the coating film of both the tight sample and the moisture absorption sample was peeled off from the CCL and had no solder resistance.

In Comparative Example 6, although a polycarbonate resin was used in place of the polyarylate resin, a resin composition with an epoxy resin could not be obtained because it was not dissolved in a solvent.

The resin composition of the present invention is useful for applications requiring both adhesiveness and heat resistance, and is useful, for example, in the formation of an adhesive layer in a wiring board, particularly a multilayer flexible printed wiring board and a flex-rigid printed wiring board.

Claims (9)

A resin composition comprising an epoxy resin (A) having at least two epoxy groups in a molecule, a polyarylate resin (B) and a curing agent (C)
Wherein the polyarylate resin (B) has a glass transition temperature of 200 DEG C or higher,
Wherein a content ratio (A) / (B) of the epoxy resin (A) to the polyarylate resin (B) is 30/70 to 90/10 (mass ratio). The method according to claim 1,
Wherein the epoxy equivalent of the epoxy resin (A) is 90 to 500 g / eq. 3. The method according to claim 1 or 2,
Wherein the polyarylate resin (B) comprises at least one divalent phenol moiety selected from the group consisting of aromatic dicarboxylic acid moieties and divalent phenol moieties represented by the following formulas (i) to (iv):

In formula (i), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, &Lt; / RTI &gt; to about 20 aromatic hydrocarbon groups;

In formula (ii), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, And R ¹⁵ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

In formula (iii), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, is selected from the group consisting of an aromatic hydrocarbon of ~20, R ²⁵ are each independently an aliphatic hydrocarbon group of 1 to 20 carbon atoms, having a carbon number of 3-20 alicyclic hydrocarbon group, aromatic hydrocarbon group of 6 to 20 carbon atoms, having 1 to 20 carbon atoms And k is an integer of 2 to 12, and m is an integer of 0 or more and 2k or less; And

R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, And R ³⁵ is selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms And R ³⁶ is selected from the group consisting of an aromatic hydrocarbon group having 6 to 20 carbon atoms. 4. The method according to any one of claims 1 to 3,
Wherein the polyarylate resin (B) further comprises a divalent phenol moiety represented by the following formula (v):

R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a carbon number of 6 &Lt; / RTI &gt; to about 20 aromatic hydrocarbon groups. 5. The method according to any one of claims 1 to 4,
Wherein the resin composition is a resin composition for an adhesive sheet. A resin varnish obtained by dissolving the resin composition according to any one of claims 1 to 5 in an organic solvent. A coating film formed by drying the resin varnish according to claim 5. A laminate obtained by forming the film according to claim 7 on a substrate. A wiring board using the laminate according to claim 8.