JP6676529B2 - Resin composition and laminate using the same - Google Patents

Description

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

  In recent years, the electronics field has been remarkably developed, and in particular, electronic devices have been reduced in size, weight, and density, and demands for these performances have been increasing. In order to respond to such demands, studies on thinning, multi-layering, and high-definition of electronic materials have been actively conducted. In many cases, a flexible printed wiring board is used as the printed wiring board, and further, it is often highly integrated and multilayered.

  As a technique for forming a multilayer printed wiring board, a manufacturing technique of a build-up type multilayer printed wiring board in which a conductor layer (mainly copper or silver is used) and an organic insulating layer are alternately laminated has attracted attention. . A general method of alternately stacking the conductor layers and the organic insulating layers is that in many cases, a laminate composed of the conductor layers and the organic insulating base material (mainly polyimide is used) is laminated by bonding with an insulating adhesive layer. . It is essential that the insulating adhesive layer adheres firmly to both the conductor layer forming the circuit and the organic insulating base material.Furthermore, it is necessary that the conductor layer in the circuit pattern be embedded in gaps between the conductor layers. ing.

  In order to meet such demands, various studies have been made, and adhesives for flexible wiring boards containing polyarylate and epoxy resin as essential components (Patent Documents 1 and 2), polyester / polyurethane having a specific acid value And an adhesive composition containing an epoxy resin as a main component (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, Patent Document 4). ing.

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

JP-A-5-263058 JP-A-5-271637 JP-A-11-116930 JP 2007-51212 A JP 2013-189544 A

The present inventors have found the following.
According to the techniques described in Patent Literatures 1 to 5, excellent adhesiveness to the conductor layer and / or the organic insulating base material may not be obtained. Even if excellent adhesion was obtained to both the conductor layer and the organic insulating substrate, the heat resistance was reduced. More specifically, flexible printed wiring boards have recently been used in a wide range of fields, taking advantage of their thinness and flexibility and the ability to produce fine circuits. However, for lighting and in-vehicle applications, heat resistance that can withstand a use temperature of 150 ° C. or more is required. However, flexible printed wiring boards using the compositions of Patent Documents 1 to 5 for an adhesive layer cannot withstand use in lighting or in-vehicle applications.

In addition, due to moisture absorption of the adhesive layer, the solder resistance was sometimes reduced. Specifically, after the adhesive layer absorbs moisture under high temperature and high humidity, when the solder is melted and heated, the evaporated moisture causes bubbles to be generated, causing the adhesive layer to swell or peel off from the conductive layer or the organic insulating base material. There was a problem that
Further, when hot pressing is performed to cure the adhesive layer, there is also a problem in that the resin composition has too much fluidity and thus often protrudes.

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

  The present invention also has excellent adhesiveness to both the conductive layer and the organic insulating base material, has high heat resistance, excellent solder resistance after moisture absorption, and has good resistance to run-out during hot pressing for curing. An object is to provide a resin composition capable of forming an adhesive layer.

［一般式（ｉ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は各々独立に水素原子、ハロゲン原子、炭素数１〜２０の脂肪族炭化水素基、炭素数３〜２０の脂環族炭化水素基、炭素数６〜２０の芳香族炭化水素基からなる群から選ばれる］；

［一般式（ｉｉ）中、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は各々独立に水素原子、ハロゲン原子、炭素数１〜２０の脂肪族炭化水素基、炭素数３〜２０の脂環族炭化水素基、炭素数６〜２０の芳香族炭化水素基からなる群から選ばれ、Ｒ^１５は水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、あるいは炭素数６〜２０のアリール基からなる群から選ばれる］；

［一般式（ｉｉｉ）中、Ｒ^２１、Ｒ^２２、Ｒ^２３およびＲ^２４は各々独立に水素原子、ハロゲン原子、炭素数１〜２０の脂肪族炭化水素基、炭素数３〜２０の脂環族炭化水素基、炭素数６〜２０の芳香族炭化水素基からなる群から選ばれ、Ｒ^２５は各々独立に、炭素数１〜２０の脂肪族炭化水素基、炭素数３〜２０の脂環族炭化水素基、炭素数６〜２０の芳香族炭化水素基、炭素数１〜２０のハロゲン化アルキル基からなる群より選ばれ、ｋは２〜１２の整数であり、ｍは０以上であって、２ｋ以下の整数である］；および

［一般式（ｉｖ）中、Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は各々独立に水素原子、ハロゲン原子、炭素数１〜２０の脂肪族炭化水素基、炭素数３〜２０の脂環族炭化水素基、炭素数６〜２０の芳香族炭化水素基からなる群から選ばれ、Ｒ^３５は水素原子、ハロゲン原子、炭素数１〜２０の脂肪族炭化水素基、炭素数３〜２０の脂環族炭化水素基、炭素数６〜２０の芳香族炭化水素基からなる群から選ばれ、Ｒ^３６は炭素数６〜２０の芳香族炭化水素基からなる群より選ばれる］。
（４）前記ポリアリレート樹脂（Ｂ）がさらに下記一般式（ｖ）で表される二価フェノール残基を含んでいる、（１）〜（３）のいずれかに記載の樹脂組成物：

［一般式（ｖ）中、Ｒ⁵、Ｒ⁶、Ｒ^７およびＲ^８は各々独立に水素原子、ハロゲン原子、炭素数１〜２０の脂肪族炭化水素基、炭素数３〜２０の脂環族炭化水素基、炭素数６〜２０の芳香族炭化水素基からなる群から選ばれる］。
（５）前記樹脂組成物が接着シート用樹脂組成物である、（１）〜（４）のいずれかに記載の樹脂組成物。
（６）（１）〜（５）のいずれかに記載の樹脂組成物を有機溶剤に溶解して得られる樹脂ワニス。
（７）（５）に記載の樹脂ワニスを乾燥してなる被膜。
（８）基材上に、（７）に記載の被膜を形成してなる積層体。
（９）（８）に記載の積層体を用いた配線板。Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have reached the present invention.
That is, the gist of the present invention is as follows.
(1) A resin composition containing an epoxy resin (A) having two or more epoxy groups in one molecule, a polyarylate resin (B), and a curing agent (C),
The glass transition temperature of the polyarylate resin (B) is 200 ° C. or higher,
A resin composition wherein the 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 resin (A) has an epoxy equivalent of 90 to 500 g / eq.
(3) The polyarylate resin (B) is at least one divalent resin selected from the group consisting of aromatic dicarboxylic acid residues and dihydric phenol residues represented by the following general formulas (i) to (iv). The resin composition according to (1) or (2), which contains a phenol residue:

[In the general formula (i), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an alicyclic group having 3 to 20 carbon atoms. A hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms]];

[In the general 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, or an alicyclic group having 3 to 20 carbon atoms. R ¹⁵ is selected from the group consisting of a hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 6 carbon atoms. ~ 20 aryl groups];

[In the general 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 group having 3 to 20 carbon atoms. R ²⁵ is independently selected from the group consisting of a hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ²⁵ is each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an alicyclic group having 3 to 20 carbon atoms. A hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, selected from the group consisting of a halogenated alkyl group having 1 to 20 carbon atoms, k is an integer of 2 to 12, m is 0 or more, , 2k or less]; and

[In the general 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, and an alicyclic group having 3 to 20 carbon atoms. R ³⁵ is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aliphatic hydrocarbon group having 3 to 20 carbon atoms, or a hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms. alicyclic hydrocarbon group, selected from the group consisting of an aromatic hydrocarbon group having 6 to 20 carbon atoms, 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 contains a dihydric phenol residue represented by the following general formula (v):

[In the general formula (v), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an alicyclic group having 3 to 20 carbon atoms. Hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms].
(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 obtained by drying the resin varnish according to (5).
(8) A laminate formed by forming the coating according to (7) on a substrate.
(9) A wiring board using the laminate according to (8).

According to the present invention, a resin composition having high heat resistance and capable of forming an adhesive layer having excellent solder resistance after moisture absorption is obtained.
A laminate using such a resin composition can be suitably used particularly for a wiring board and the like, and even when the wiring board is heated by melting of solder, occurrence of swelling or peeling of the adhesive insulating layer is prevented. Can be suppressed.
The resin composition of the present invention can form an adhesive layer having excellent adhesiveness to both the conductor layer and the organic insulating substrate.
The resin composition of the present invention can also form an adhesive layer having excellent resistance to run-out during 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 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. Preferably, an epoxy resin having two to five epoxy groups in one molecule is used. When the number of epoxy groups contained in one molecule exceeds 5, when a resin varnish is produced from the obtained resin composition, the increase in viscosity may be remarkable. The number of epoxy groups means an average of the number of epoxy groups per molecule because the epoxy resin has a molecular weight distribution.

  The epoxy resin (A) having two or more epoxy groups in one molecule preferably has an epoxy equivalent of 90 to 500 g / eq, more preferably 90 to 300 g / eq, and more preferably 90 to 250 g / eq. Is more preferable. When the epoxy equivalent is less than 90 g / eq, the reactivity of the resin varnish obtained by dissolving the resin composition in the organic solvent is reduced because the epoxy group is too dense and the reactivity with the curing agent is reduced. May be too high. When the epoxy equivalent exceeds 500 g / eq, the crosslinking density of the epoxy resin after the curing reaction becomes low, so that the glass transition temperature of the obtained resin composition does not become high and the heat resistance cannot be improved.

  Examples of the epoxy resin (A) having two or more epoxy groups in one molecule include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, Phenol novolak type epoxy resin, cresol novolak type epoxy resin, glycidylamine type epoxy resin, isocyanurate type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, acrylic acid modified epoxy resin, polyfunctional epoxy resin , Brominated epoxy resins and phosphorus-modified epoxy resins. Among them, bisphenol A type epoxy resin and phenol novolak type epoxy resin, particularly bisphenol A type epoxy resin can be preferably used. Such an epoxy resin is available as a commercial product. As specific examples of commercially available products, product name: GAN (manufactured by Nippon Kayaku), product name: jER630 (manufactured by Mitsubishi Chemical), product name: HP4032 (manufactured by DIC), product name: celloxide 2081 (daicel chemical industry) ), Product name: jER828 (manufactured by Mitsubishi Chemical), product name: jER807 (manufactured by Mitsubishi Chemical), product name: Epicron EXA-1514 (manufactured by DIC), product name: jER152 (manufactured by Mitsubishi Chemical), Product name: jER604 (Mitsubishi Chemical), product name: MY-0500 (Huntsman), product name: MY-0600 (Huntsman), product name: TETRAD-X (Mitsubishi Gas), product Name: SR-HHPA (manufactured by Sakamoto Pharmaceutical Co., Ltd.), Product name: EXA-4580-1000 (manufactured by DIC), Product name: Araldite AER4152 (Asahi Kasei E-material) It can be exemplified such as manufactured) Ltd., but is not limited thereto. The epoxy resins may be used alone or in combination of two or more. The epoxy resin (A) may have another functional group as long as it has two or more epoxy groups in one molecule.

  Among the above epoxy resins, bisphenol A type epoxy resin (commercial product: jER828, etc.), phenol novolak type epoxy resin (commercial product: jER152, etc.), bisphenol F epoxy resin (commercial product: jER807, etc.) And glycidylamine type epoxy resins (eg, commercially available products such as jER604) are preferred, and bisphenol A type epoxy resins and phenol novolak type epoxy resins are highly effective in improving the adhesion of the resulting coating to copper foil and polyimide films. Is particularly preferred.

  The above-mentioned bisphenol A type epoxy resin is classified into a liquid at room temperature and a solid at room temperature depending on the number of repeating units of the bisphenol skeleton. The bisphenol A type epoxy resin having 1 to 3 repeating units of the main chain bisphenol skeleton is liquid at room temperature, and the bisphenol A type epoxy resin having 2 to 10 repeating units of the main chain bisphenol skeleton at room temperature. It is solid. Therefore, in the step of forming a film on the substrate to obtain a laminate, the film adheres to the adherend by heating, and the film and the adherend are firmly adhered by solidification. Can be. In addition, such a relatively low-molecular-weight bisphenol A epoxy resin has a high crosslink density, and therefore has high mechanical strength, good chemical resistance, high curability, and high moisture absorption (because the free volume is small). ) Is also small.

  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 normal temperature as described above and a bisphenol A-type epoxy resin which is liquid at normal temperature. By using a combination of a solid and a liquid at room temperature, flexibility can be obtained while maintaining mechanical strength, and thus flexibility is obtained while maintaining the mechanical strength that the resin composition originally has. be able to. As a result, the bonding strength between the adherends can be improved. As the bisphenol A type epoxy resin which is solid at room temperature, those having a glass transition temperature in the range of 50 to 150 ° C. are preferable from the viewpoint of mechanical strength and heat resistance. Specifically, as a bisphenol A type epoxy resin which is liquid at room temperature and has 1 to 3 repeating units of a main chain bisphenol skeleton, jER828 (manufactured by Mitsubishi Chemical Corporation) is a solid at room temperature. Examples of the bisphenol A type epoxy resin having 2 to 10 repeating units having a bisphenol skeleton in the chain include jER1001 (manufactured by Mitsubishi Chemical Corporation).

  For the above reasons, 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, it is more preferably 10 to 20 Pa · s. The epoxy resin (A) may have a viscosity at 52 ° C within a predetermined range instead of the viscosity at 25 ° C 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 still 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 dihydric phenol and / or a derivative thereof, and includes solution polymerization, melt polymerization, and interface polymerization. It is produced by a method such as polymerization.

  The polyarylate raw material for introducing an aromatic dicarboxylic acid residue is not particularly limited. For example, terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, 2,5-naphthalenedicarboxylic acid, 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methyl terephthalic acid, 4,4′-biphenyldicarboxylic acid, 2,2′-biphenyldicarboxylic acid, 4,4′-diphenyl ether Dicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis (4-carboxyphenoxy) ethane, 5-sodium sulfo Isophthalic acid and the like. Among them, terephthalic acid and isophthalic acid are preferable, and from the viewpoint of solubility in a solvent, it is particularly preferable to use a mixture of both. In that case, the mixing ratio (terephthalic acid / isophthalic acid) is arbitrary within a range of 100/0 to 0/100 (mol%), but is preferably 80/20 to 10/90 (mol%), and more preferably 75/20. When the content is in the range of / 25 to 25/75 (mol%), the obtained polyarylate resin (B) has excellent solubility.

  An aliphatic dicarboxylic acid may be used together with the aromatic dicarboxylic acid as long as the properties and effects of the present invention are not impaired. The aliphatic dicarboxylic acids are not particularly limited, and include dicarboxymethylcyclohexane, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, glutaric acid, dodecane diacid, and the like.

  The polyarylate raw material for introducing a dihydric phenol residue is not particularly limited, but from the viewpoint of improving the heat resistance of the obtained resin composition and improving the solubility in an organic solvent, the following general formula (i) ) To (iv), it is preferable to introduce one or more dihydric phenol residues selected from the group consisting of the dihydric phenol residues (hereinafter sometimes referred to as bisphenol I residues).

In the general 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, or an alicyclic hydrocarbon having 3 to 20 carbon atoms. It is selected from the group consisting of a hydrogen group and an aromatic hydrocarbon group having 6 to 20 carbon atoms. 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. As the aliphatic hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, alkyl group such as decyl group, and vinyl group, allyl group and the like An alkenyl group is mentioned. The preferred aliphatic hydrocarbon group is an alkyl group, more preferably an alkyl group having 1 to 10, more preferably 1 to 5, and particularly 1 to 3 carbon atoms. Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. Preferred alicyclic hydrocarbon groups are cycloalkyl groups having 3 to 10 carbon atoms, particularly 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 having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.

In a preferred dihydric phenol residue of the general formula (i), R ¹ and R ³ are each independently, preferably simultaneously, a hydrogen atom, an alkyl group having 1 to 10, especially 1 to 3 carbon atoms, or a carbon atom having 1 to 3 carbon atoms. R ² and R ⁴ are each independently, preferably simultaneously, a hydrogen atom or an alkyl group having 1 to 10, particularly 1 to 3, carbon atoms.

In a more preferred dihydric phenol residue of formula (i), ^{R 1} and ^{R 3} are each independently a preferably simultaneously, from 1 to 10 carbon atoms, particularly 1 to 3 alkyl group; ^{R 2} and R ⁴ is at the same time a hydrogen atom.

  Examples of the compound for introducing the dihydric phenol residue of the general formula (i) include 9,9-bis (4-hydroxyphenyl) fluorene (BPF) and 9,9-bis (4-hydroxy-3). -Methylphenyl) fluorene (BCF), 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene and the like.

In the general 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, or an alicyclic hydrocarbon having 3 to 20 carbon atoms. It is selected from the group consisting of a hydrogen group and an aromatic hydrocarbon group having 6 to 20 carbon atoms. The halogen atom is the same as the halogen atom in the general 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 general formula (i), a preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 10 carbon atoms. 5, especially 1-3 alkyl groups. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in formula (i), and a preferred alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, particularly 3 to 6 carbon atoms. . The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in formula (i), and a 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 those having 1 to 5 carbon atoms, especially 1 to 3 carbon atoms. Examples of the alkenyl group include a vinyl group and an allyl group. Preferred alkenyl groups are alkenyl groups 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 having 6 to 14, particularly 6 to 10 carbon atoms.

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

In a more preferred dihydric phenol residue of the general formula ^{(ii), R} 11 ~R ¹⁴ is simultaneously hydrogen atom or 1 to 10 carbon atoms, particularly 1 to 3 alkyl ^{groups,; R 15} is a carbon It is an alkyl group having the number of 1 to 10, especially 1 to 3, or an aryl group having 6 to 20, particularly 6 to 10 carbon atoms.

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

In the general 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, or an alicyclic hydrocarbon having 3 to 20 carbon atoms. It is selected from the group consisting of a hydrogen group and an aromatic hydrocarbon group having 6 to 20 carbon atoms. The halogen atom is the same as the halogen atom in the general 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 general formula (i), a preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 10 carbon atoms. 5, especially 1-3 alkyl groups. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in formula (i), and a preferred alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, particularly 3 to 6 carbon atoms. . The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in formula (i), and a preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.

R ²⁵ represents 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, or a halogenated alkyl having 1 to 20 carbon atoms. Selected from the group consisting of The aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group in the general formula (i), a preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 10 carbon atoms. 5, especially 1-3 alkyl groups. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in formula (i), and a preferred alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, particularly 3 to 6 carbon atoms. . The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in formula (i), and a preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms. In the halogenated alkyl group, an alkyl group having 1 to 10, more preferably 1 to 5, and particularly 1 to 3 carbon atoms, wherein one or two hydrogen atoms are halogen atoms (for example, a fluorine atom, a chlorine atom, a bromine atom) ) Is an alkyl group. Preferred halogenated alkyl groups include a monofluoromethyl group, a difluoromethyl group, a monochloromethyl group, and a dichloromethyl group. When described later m is an integer of 2 or more, the two or more R ²⁵ may be made independently chosen from the group.

k is an integer of 2 to 12, preferably 4 to 11, and more preferably 4 to 6. In the carbon ring in which the number of constituent carbon atoms varies depending on the value of k, the hydrogen atoms of each carbon atom are omitted. When m is 1 or more, the one or more R ²⁵ is substituted with a hydrogen atom of a carbon atom constituting the carbon ring.
m is an integer of 0 or more and 2k or less, preferably 0 to 4, more preferably an integer of 1 to 4.

In a preferred dihydric phenol residue of the general formula (iii), R ²¹ and R ²³ are each independently, preferably simultaneously, a hydrogen atom or an alkyl group having 1 to 10, particularly 1 to 3 carbon atoms; R ²² and R ²⁴ are each independently, preferably simultaneously, a hydrogen atom or an alkyl group having 1 to 10, especially 1 to 3 carbon atoms; R ²⁵ is a group having 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 may be each independently the above-described alkyl group, and are preferably simultaneously an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms. K is an integer from 4 to 11, especially from 4 to 6; m is an integer from 0 to 4, especially from 1 to 4.

In a more preferred dihydric phenol residue of the general formula ^{(iii), R} 21 ~R ²⁴ is simultaneously hydrogen atom or 1 to 10 carbon atoms, is particularly 1-3 alkyl ^{group; R 25} is a carbon Especially when m is an integer of 2 or more, R ²⁵ of 2 or more is simultaneously an alkyl group having 1 to 10, especially 1 to 3 carbon atoms; k is an integer from 4 to 6; m is an integer from 2 to 4.

  Examples of the compound for introducing the dihydric phenol residue of the general formula (iii) include 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ) and 1,1-bis (4-hydroxy-3). , 5-Dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (DMBPC), 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4- Hydroxy-3,5-dimethylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC), 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclo Xane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxy -3,5-dimethylphenyl) cyclododecane and 1,1-bis (4-hydroxy-3-methylphenyl) cyclododecane.

In the general 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, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. It is selected from the group consisting of a hydrogen group and an aromatic hydrocarbon group having 6 to 20 carbon atoms. The halogen atom is the same as the halogen atom in the general 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 general formula (i), a preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 10 carbon atoms. 5, especially 1-3 alkyl groups. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in formula (i), and a preferred alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, particularly 3 to 6 carbon atoms. . The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in formula (i), and a 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. It is. The halogen atom is the same as the halogen atom in the general 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 general formula (i), a preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 10 carbon atoms. 5, especially 1-3 alkyl groups. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in formula (i), and a preferred alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, particularly 3 to 6 carbon atoms. . The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in formula (i), and a preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.

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 formula (i), and a 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 decreases, and in particular, the solder resistance decreases after the adhesive layer absorbs moisture.

In a preferred dihydric phenol residue of the general formula (iv), R ³¹ and R ³³ are each independently, preferably simultaneously, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10, particularly 1 to 3, carbon atoms, Or an aryl group having 6 to 20, especially 6 to 10 carbon atoms; R ³² and R ³⁴ are each independently, preferably simultaneously, a hydrogen atom, a halogen atom, or a C 1 to C 10, especially 1 to 3 carbon atom R ³⁵ is a hydrogen atom or an alkyl group having 1 to 10, particularly 1 to 3 carbon atoms; R ³⁶ is an aryl group having 6 to 20 carbon atoms, particularly 6 to 10 carbon atoms.

In a more preferred dihydric phenol residue of the general formula (iv), R ^{31 to} R ³⁴ are simultaneously a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10, particularly 1 to 3 carbon atoms; R ³⁵ is a hydrogen atom or a C1-10, particularly 1 to 3 alkyl ^{group; R 36} is 6 to 20 carbon atoms, in particular 6-10 aryl group.

  Examples of the compound for introducing the dihydric phenol residue of the general formula (iv) include bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane ( BPAP), 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -1-phenylethane, 1,1 -Bis (4-hydroxy-3,5-dibromophenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane and the like.

  Among the compounds for introducing the bisphenol I residue, from the viewpoint of improving the heat resistance and the solubility, 9,9-bis (4-hydroxyphenyl) fluorene (BPF) and 9,9-bis (4-hydroxy -3-methylphenyl) fluorene (BCF), N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine (PPPBP), 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 1,1 -Bis (4-hydroxy-3-methylphenyl) cyclohexane (DMBPC), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC), 1,1-bis (4-hydroxy (Phenyl) -1-phenylethane (BPAP) can be preferably used. These compounds may be used alone or as a mixture of two or more.

  In addition to one or more dihydric phenol residues represented by the above general formulas (i) to (iv), a dihydric phenol residue represented by the following general formula (v) (hereinafter referred to as bisphenol II residue) ), The solubility in organic solvents is increased, and the adhesion of the resulting coating to adherends can be increased.

In the general 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, or an alicyclic hydrocarbon having 3 to 20 carbon atoms. It is selected from the group consisting of a hydrogen group and an aromatic hydrocarbon group having 6 to 20 carbon atoms. The halogen atom is the same as the halogen atom in the general 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 general formula (i), a preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 10 carbon atoms. 5, especially 1-3 alkyl groups. The alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in formula (i), and a preferred alicyclic hydrocarbon group is a cycloalkyl group having 3 to 10 carbon atoms, particularly 3 to 6 carbon atoms. . The aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in formula (i), and a preferred aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.

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

  Examples of the compound for introducing the dihydric phenol residue of the general formula (v) include, for example, 2,2-bis (4-hydroxyphenyl) propane (BPA) and 2,2-bis (4-hydroxy-3 , 5-Dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane (BPC), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dichlorophenyl) propane and the like. These compounds may be used alone or as a mixture of two or more.

  Among the compounds for introducing a dihydric phenol residue of the general formula (v), from the viewpoint of further improving heat resistance, 2-bis (4-hydroxyphenyl) propane (BPA) and 2,2-bis ( 4-Hydroxy-3-methylphenyl) propane (BPC) and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane (TMBPA) can be preferably used, and the balance between heat resistance and economic efficiency can be obtained. 2-bis (4-hydroxyphenyl) propane (BPA) is particularly preferred for its superiority. Although it can be used by mixing with other bisphenols, from the viewpoint of heat resistance and economy of the resulting polyarylate resin (B), the dihydric phenol residues of the above general formulas (i) to (iv) are introduced. As a compound for introducing a dihydric phenol residue of the general formula (v) in addition to the above compound, it is preferable to use not more than two kinds, especially BPA, including BPA alone.

  When a dihydric phenol residue selected from bisphenol I residues is introduced into the polyarylate resin (B) and a bisphenol II residue is introduced as desired, (bisphenol I residue) / (bisphenol I residue + bisphenol II residue) (Moiety ratio) is preferably from 10/100 to 100/100 (molar ratio), and more preferably from 30/100 to 100/100 (molar ratio). If the amount of the bisphenol I residue is less than 10 mol% based on the total amount of the dihydric phenol component, the heat resistance of the polyarylate resin (B) may be poor. From the viewpoint of further improving economic efficiency, (bisphenol I residue) / (bisphenol I residue + bisphenol II residue) is preferably from 10/100 to 80/100 (molar ratio), and from 20/100 to More preferably, it is 80/100 (molar ratio).

  A bisphenol residue other than bisphenol I residue or bisphenol II residue may be introduced into the polyarylate resin (B) as long as the properties and effects of the present invention are not impaired. Examples of such bisphenols include 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 4-methyl-2, 2-bis (4-hydroxyphenyl) pentane and the like can be mentioned.

  Further, aliphatic glycols or dihydroxybenzene may be used for 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 ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, nonanediol, decanediol, cyclohexanedimethanol, ethylene oxide adducts of bisphenol A, and propylene oxide adducts thereof Examples of the ethylene oxide adduct of bisphenol S and dihydroxybenzene include hydroquinone, resorcinol and catechol.

  The inherent viscosity of the polyarylate resin (B) is preferably from 0.30 to 1.00 dL / g, and more preferably from 0.35 to 0.80 dL / g. When the inherent viscosity is less than 0.30 dL / g, the flexibility of the obtained resin composition becomes inferior, and the resin composition falls off in powder form from the end face of the laminate during punching or router processing. Sometimes. If the inherent viscosity exceeds 1.00 dL / g, the viscosity at the time of mixing with an epoxy resin or an organic solvent is increased, and the dispersibility and the coating property may be deteriorated. The inherent viscosity is an index of the molecular weight, and is dissolved in a mixture of phenol / 1,1,2,2-tetrachloroethane at a temperature of 25 ° C. so as to have a concentration of 1 g / dL in a 60/40 (mass ratio) mixture. It is measured using the resin solution obtained.

  In order to keep the inherent viscosity of the polyarylate resin (B), that is, the molecular weight within a predetermined range, a method of controlling the reaction rate by adjusting the polymerization time and adjusting the molecular weight, the method of controlling the aromatic dicarboxylic acid component or the dihydric phenol component. A method of adjusting the molecular weight by blending any one of the components in a slightly excessive amount and polymerizing the monomers, aliphatic monoalcohols having only one reactive functional group in the molecule, phenols, or A method in which a monocarboxylic acid is added as a terminal blocking agent together with a monomer to adjust the molecular weight is exemplified. Among these, the method of adding a terminal blocking agent is preferred because the molecular weight can be easily controlled.

  Examples of the terminal blocking agent include aliphatic monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, and phenethyl alcohol; Phenols such as phenol, cresol, 2,6-xylenol, 2,4-xylenol, p-tert-butylphenol (PTBP), p-tert-octylphenol, cumylphenol; and benzoic acid, methylbenzoic acid, naphthoic acid, Monocarboxylic acids such as 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 more, preferably 200 ° C. or more and less than 320 ° C., more preferably 210 ° C. or more and less than 310 ° C., and 220 ° C. or more and 300 ° C. or less. The temperature is more preferably lower than 230 ° C, and most preferably higher than 230 ° C and lower than 290 ° C. By setting the glass transition temperature within a predetermined range, the resulting resin composition has high heat resistance. When the glass transition temperature is lower than 200 ° C., the heat resistance of the resin composition becomes poor. When the glass transition temperature is 320 ° C. or higher, the glass transition temperature of the resin composition becomes too high, so that the curing reaction does not proceed sufficiently.

  The carboxyl number of the polyarylate resin (B) is preferably at least 10 mol / ton, more preferably at least 20 mol / ton, even more preferably at least 30 mol / ton. The carboxyl number of the polyarylate resin (B) indicates the content ratio of the terminal carboxyl group in the polyarylate resin (B), and the carboxyl group reacts with the epoxy group of the epoxy resin (A) to cure. The epoxy resin (A) and the polyarylate resin (B) in the product are easily compatible with each other. Examples of the method of introducing a terminal carboxyl group into the polyarylate resin (B) include a method of stopping the polymerization reaction before the reaction is completed, and a method of hydrolyzing an ester bond with an alkali or the like.

  In the resin composition of the present invention, the content ratio of the epoxy resin (A) to the polyarylate resin (B) is such that (A) / (B) is 30/70 to 90/10 (mass ratio), and 35/65. ８５85/15 (mass ratio), more preferably 40 / 60-80 / 20 (mass ratio), and even more preferably 40 / 60-70 / 30 (mass ratio). When the content of the epoxy resin (A) is less than 30% by mass, the adhesiveness of the resin composition to the adherend becomes insufficient. If the content of the epoxy resin (A) exceeds 90% by mass, heat resistance after wet heat treatment will not be sufficient.

  The curing agent (C) used in the present invention is not particularly limited as long as it cures by reacting with the epoxy resin (A). For example, fats such as diethylenetriamine, triethylenetetonramine and tetraethylenepentamine can be used. Alicyclic polyamine compounds such as aromatic polyamine compounds, mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane and bis (4-aminocyclohexyl) methane, metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone Polyamine compounds such as dimethyl cyanide and metaphenylenediamine; polyamine compounds such as dicyandiamide, adipic dihydrazide and polyamide polyamine; or phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Monofunctional acid anhydrides such as drophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecylsuccinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol Examples include bifunctional acid anhydrides such as bis (anhydrotrimate) and methylcyclohexanetetracarboxylic anhydride, and free acid carboxylic anhydrides such as trimellitic anhydride and polyazeleic 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. Generally, 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 preferably in the range of 0.5 to 1.5. The reaction mechanism and the stoichiometric amount differ depending on the type of the curing agent, and cannot be unconditionally determined. However, the content of the curing agent can be determined by the ratio of the equivalent of the active hydrogen contained in the curing agent to the epoxy equivalent. For example, when the curing agent is an amine compound, the amount of the amine compound can be calculated from the ratio between the equivalent of active hydrogen bonded to the amino group and 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 molecule. When the curing agent is an amine compound, the active hydrogen equivalent is a value obtained by dividing the average molecular weight of the amine compound by the number of hydrogens bonded to amino groups per molecule.

  In the resin composition of the present invention, a curing accelerator can be used instead of the curing agent or together with the curing agent. The curing accelerator is not particularly limited. Examples thereof include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, benzyldimethylamine, 2- (dimethylaminomethyl) phenol and the like. Tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol can be used. The compounding amount of the curing accelerator can also be set appropriately.

  In the resin composition of the present invention, a resin other than the polyarylate resin (B) may be blended within the range of the performance required in the present invention in order to impart 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 fluidity modifier, and a fine particle inorganic filler may be mixed and used.

The 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 at a predetermined ratio.

  As a method of dissolution, a method in which the epoxy resin (A), the polyarylate resin (B) and the curing agent (C) are collectively put into an organic solvent and mixed while being dissolved, the epoxy resin (A), the polyarylate resin (B) and a curing agent (C) are mixed and then poured into an organic solvent to dissolve the resin. After the epoxy resin (A) and the polyarylate resin (B) are mixed, the organic resin is added while adding the curing agent (C). Examples thereof include a method of dissolving the mixture in a solvent. The epoxy resin (A), the polyarylate resin (B) and the curing agent (C) are collectively used because it is easy to improve the workability at the time of dissolving and mixing and to increase the uniformity of the obtained resin composition. A method in which the mixture is put into an organic solvent and mixed while being dissolved is particularly preferable. In addition, a method of melting and mixing the epoxy resin (A), the polyarylate resin (B) and the curing agent (C) is also conceivable, but the viscosity of the obtained resin composition becomes too high and the resin composition is coated on a substrate in a thin film form. Since it is difficult to work, it should not be adopted in the present invention unless it is necessary.

  It is necessary to pay attention to the following points for the organic solvent used. That is, the epoxy resin (A) and the polyarylate resin (B) are different from each other in the type of easily soluble organic solvent. If one of them is difficult to dissolve, it is difficult to obtain a uniform resin composition.

  In a preferred embodiment, the epoxy resin (A) and polyarylate resin (B) used in the present invention can be dissolved in a common organic solvent and mixed in a resin solution to form a resin varnish. When preparing the resin varnish, it is preferable that a highly compatible resin varnish can be obtained without separating both 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) do not separate inside the resin composition, resulting in a uniform resin composition. It becomes possible. In other words, the polyarylate resin (B) must be dissolved in the same organic solvent that dissolves the epoxy resin (A), but the polyarylate resin (B) used in the present invention is particularly soluble. Since there are many types of solvents and a wide choice of solvents, it is possible to select various organic solvents and form various coatings according to the purpose.

  As the organic solvent to be used, those capable of dissolving the polyarylate resin (B) alone at a solid content concentration of 20% by mass or more are preferable, and those capable of dissolving at a solid content concentration of 30% by mass or more are more preferable.

  As the organic solvent, it is necessary to select an appropriate solvent depending on the type of the epoxy resin (A) to be used in combination and other resins used as necessary. However, 1,4-dioxane, dimethylacetamide, dimethylformamide, N- Examples thereof include methylpyrrolidone, dimethylsulfoxide, methylethylketone, cyclohexanone, toluene, and xylene. These may be used alone or in combination of two or more. Among these, 1,4-dioxane, dimethylformamide, N-methylpyrrolidone, toluene, and a mixture of at least one of them with methyl ethyl ketone are preferable.

  When the curing agent (C) is also dissolved in a solvent, the resin composition after curing tends to have excellent mechanical properties and heat resistance. However, the curing agent (C) is used together with the epoxy resin (A) and the polyarylate resin (B). Is often limited. In such a case, it is preferable to pulverize the curing agent (C) as finely as possible and to uniformly disperse the curing agent (C) in a solution in which the epoxy resin (A) and the polyarylate resin (B) are dissolved.

  When obtaining a resin varnish containing the resin composition by dissolving in the organic solvent, the solid content concentration is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, and more preferably 20 to 50% by mass. More preferably, When the solid content is less than 10% by mass, it is difficult to obtain a thickness necessary for forming a film, and when the solid content exceeds 70% by mass, not only is it difficult to form a film, but also the obtained film is obtained. Is not preferred because the thickness accuracy of the film decreases.

  As a method of forming a coating using the resin varnish, for example, using a known coating method such as Meyer bar coating, gravure coating, kiss coating, spin coating, can be applied to various substrates, dried to form a coating. . Specifically, a film made of a resin composition can be formed by applying the film on a film substrate made of a release-treated polyethylene terephthalate (PET) resin or the like, followed by drying.

  The coating can be peeled off from the film substrate and used as a resin composition coating alone or as a laminate having a coating formed on the substrate.

  The selection of the drying temperature during the formation of a coating made of the resin composition is very important since it greatly affects the adhesive properties when the coating or the laminate is used in applications such as bonding in the present invention.

  In the present invention, the heating temperature at the time of drying is not only a temperature that promotes the evaporation of the organic solvent from the resin varnish, but also a temperature at which the epoxy resin (A) and the curing agent (C) in the resin composition react. This reaction temperature differs depending on the combination of the epoxy resin (A) and the curing agent (C), and cannot be determined unequivocally, but is preferably in the range of 80 to 160 ° C. Therefore, it is preferable to select an organic solvent that can be dried in this temperature range, in addition to the above-mentioned solubility. The heating time should be set not only to remove the organic solvent but also to reach the desired reaction rate of the resin composition. However, the reaction rate depends on the heating temperature and cannot be unconditionally determined. As an example, when the heating temperature is 80 to 160 ° C., the heating time is 5 to 50 minutes. It is preferable that the reaction rate of the resin composition after heating is 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. Drying is preferably performed in multiple stages having different reaction temperatures (drying temperatures). In this case, drying may be performed in multiple stages so that the temperature rises stepwise within the above range, and the drying time in each stage 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, an antifoaming agent, a leveling agent, an ion repairing agent, and the like may be added as long as the object of the present invention is not impaired.

  The coating of the present invention or the laminate in which a coating is formed on a substrate can be used in various applications. In particular, it can be suitably used for electric and electronic parts. A specific example of use will be described using a bonding sheet as an example. A bonding sheet is a so-called adhesive layer for bonding circuits, components or other substrates to each other on a substrate, and usually an adhesive layer is formed on a film substrate, Its use varies in application. Taking the case of producing a multilayer printed wiring board as an example, first, after laminating on a patterned circuit board as a bonding sheet, the film base material is peeled from the adhesive layer, and the organic insulating layer, the conductor, or A separately manufactured circuit board is laminated. Thereafter, final curing is performed to complete the multilayer printed wiring board. Here, at the time of final curing, in order to prevent oxidation of the wiring and the like and to suppress a decrease in the adhesion between the wiring and the base material, it is preferable that the curing is promoted by heating at a low temperature. Therefore, in the present invention, the heat curing temperature is preferably from 100 ° C to 250 ° C, more preferably from 120 ° C to 200 ° C, even more preferably from 130 ° C to 190 ° C. If the final heating temperature exceeds 250 ° C., the oxidative deterioration of the wiring may progress. The heat-curing time is not particularly limited as long as sufficient curing is achieved. For example, in the case of the above-mentioned heat-curing temperature, it is 30 to 120 minutes, particularly 60 to 100 minutes.

  The coating or laminate formed from the resin composition of the present invention is excellent in heat resistance, chemical resistance, flexibility, and smoothness, and is used for build-up type multilayer printed wiring, particularly for bonding of multilayer flexible printed wiring boards for lamination. Suitable for sheets. By using the film or the laminate of the present invention, even if the flexible printed wiring board is heated to melt the solder, it is possible to suppress the occurrence of swelling and peeling of the adhesive insulating layer.

  To explain the wiring board specifically, in the manufacture of an example of a multilayer flexible printed wiring board, first, an inner layer circuit is formed by pattern etching on each of the copper foils attached to both sides of a flexible substrate material made of a polyimide resin. In some cases, a coverlay made of, for example, a polyimide resin is pressure-bonded so as to cover the entire interior circuit forming surface on both sides to obtain a flexible printed wiring board. Further, on both surfaces thereof, an outer flexible substrate copper-clad only on the opposite surface of the flexible printed wiring board of another base material made of, for example, a polyimide resin is joined by an adhesive, pressed by pressure processing, and mounted with electronic components. To obtain a multilayer flexible printed wiring board having a multilayer structure. The flex-rigid printed wiring board is a multilayer printed circuit board obtained by laminating a rigid board material obtained by laminating a prepreg obtained by impregnating a base material with a resin on the same flexible printed wiring board as described above. 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.

  Next, the present invention will be specifically described based on examples, but the present invention is not limited to only these examples.

1. Evaluation method (1) Inherent viscosity of polyarylate resin Polyarylate resin was dissolved in 1,1,2,2-tetrachloroethane to prepare a sample solution having a concentration of 1 g / dL. Subsequently, the falling time T ₀ of the sample solution and the falling time T _{0 of the} solvent were measured at a temperature of 25 ° C. using an Ubbelohde viscometer, and the inherent viscosity η was determined using the following equation.
Inherent viscosity η = Ln (η _rel ) / c
Here, η _rel is a relative viscosity and is calculated by the following equation. Also, c = 1 g / dL.
η _rel = T / T ₀

(2) Glass transition temperature Using a differential scanning calorimeter (DSC7 manufactured by Perkin Elmer), the temperature was raised from 40 ° C. to 340 ° C. at a rate of 20 ° C./min, and the glass transition in the obtained temperature rising curve. The onset temperature of the discontinuous change due to temperature was taken as the glass transition temperature.

(3) Adhesion to Copper Foil The resin varnish obtained in Examples or Comparative Examples described below is applied to a PET film substrate (Panack PET37SG-1) using an applicator to have a final dry thickness of 15 μm. It was drooling and applied.
After drying at 80 ° C. for 30 minutes, by heating at 120 ° C. or 150 ° C. for 10 minutes, the formed film of the resin composition was brought into a semi-cured B-stage state (hereinafter, referred to as a laminate [A]). The heating temperature for setting the B stage is 150 ° C. when the curing agent (c1) is used, and 120 ° C. when the curing agent (c2) is used. The film forming surface of the laminate is superimposed on the copper foil side of a copper-clad laminate (hereinafter referred to as single-sided CCL, manufactured by Sumitomo Metal Mining Co., Ltd., copper foil / polyimide film = 8/25 μm), and laminated using a vacuum laminator. After that, the PET film substrate was released from the laminate to obtain a laminate [B] in which a coating was laminated on the copper foil surface of the copper-clad laminate. Further, by laminating the film forming surface of the laminate [B] on the copper foil side of another single-sided CCL in the same manner as described above, the laminate [C] having a configuration in which the film is sandwiched between two single-sided CCL copper foils ] Was obtained. This laminate [C] was hot-pressed at a heating temperature of 190 ° C. under a pressure of 3 MPa for 90 minutes to completely cure the coating, thereby obtaining a sample for evaluating the adhesiveness. The sample was cut into a strip having a width of 10 mm, and the peel strength at an angle of 90 ° was measured under the test conditions of a tensile speed of 100 mm / min. Peeling strength was “◎” when it exceeded 2.0 N / cm, “○” when it exceeded 1.5 N / cm, and “△” when it exceeded 1.0 N / cm (no practical problem). , 1.0 N / cm or less was judged as “x”.
In the present invention, it is practically preferable that the evaluation result is “○” or more, particularly “◎”.

(4) Adhesion with polyimide film Same as the method for producing the laminate [C] in (3) above, except that a polyimide film having a thickness of 25 μm (Kapton manufactured by Du Pont-Toray Co., Ltd.) was used instead of the single-sided CCL. According to the method, a laminate [D] having a configuration in which the coating was sandwiched between two polyimide films was obtained. The laminate [D] was hot-pressed at a heating temperature of 190 ° C. under a 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 strip having a width of 10 mm, and a peeling test at an angle of 90 ° was performed under a test condition of a pulling speed of 100 mm / min to evaluate a breaking mode. The mode of failure is excellent, in the order of "material destruction" in which the polyimide film is destroyed, "cohesive failure" in which the adhesive layer is destroyed (no problem in practical use), and "interfacial peeling" in which the adhesive layer is separated from the polyimide film. .
In the present invention, it is practically preferable that the evaluation result is “material destruction”.

(5) Solder bath test The laminate [C] produced in (3) was hot-pressed at a heating temperature of 190 ° C. under a pressure of 3 MPa for 90 minutes, and then cut into a size of 50 mm × 50 mm to obtain a sample. The sample was stored for 24 hours in a desiccator containing a desiccant (hereinafter referred to as absolutely dry sample), and the sample was stored for 16 hours in a constant temperature and humidity chamber at 40 ° C. and 90% RH (hereinafter referred to as a moisture absorbing sample). Were prepared. The moisture content of the moisture-absorbing sample was 0.3%. Each of the absolutely dried sample and the moisture-absorbing sample was floated in a solder bath at 260 ° C. for 1 minute, and the appearance change before and after that was evaluated. After the solder bath, the case where no change in appearance was observed was evaluated as “O”, the case where small swelling was observed was evaluated as “Δ” (no problem in practical use), and the case where severe swelling or peeling was observed was evaluated as “X” .
In the present invention, “○” is practically preferable.
The heat resistance can be evaluated based on the evaluation result of the absolutely dry sample.
The solder resistance after moisture absorption can be evaluated based on the evaluation result of the moisture absorption sample.

(6) Dielectric properties A laminate was manufactured in the same manner as for the laminate [C] of “(3) Adhesion to copper foil” except that a glass substrate was used as the substrate. This laminate was hot-pressed at a heating temperature of 190 ° C. and a pressure of 3 MPa for 90 minutes, and then the coating was peeled off from the glass substrate. A sample was cut out to a size of 50 mm × 50 mm. The obtained coating alone was set in the following jig for measurement, and the relative permittivity and the dielectric loss tangent were measured at room temperature by the following apparatus.
<Apparatus> Impedance / material analyzer E4991A manufactured by Agilent Technologies (currently Keysight Technologies)
<Measurement jig> 16453A made by the company

2. Raw material (1) epoxy resin (a1) bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 184-194 g / eq, viscosity 120-150P (= 12-15 Pa · s) (25 ° C), in one molecule (A2) phenol novolak type epoxy resin (jER152 manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 176-178 g / eq, viscosity 14-18P (= 1.4-1.8 Pa · s) (52 ° C), 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 described below.

(3) Curing agent (c1) Dicyandiamide (DD manufactured by Nippon Carbide Industry Co., Ltd.)
(C2) diaminodiphenylsulfone (Kanto Chemical's special grade reagent)

Production Example 1
1.2 L of water is put in a reaction vessel equipped with a stirrer, 0.79 mol of sodium hydroxide, and 0.194 mol of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (BCF) which is a dihydric phenol. Then, 0.0116 mol of p-tert-butylphenol (PTBP) as a molecular weight modifier was dissolved, 0.0013 mol of a polymerization catalyst (tributylbenzylammonium chloride) was added, and the mixture was vigorously stirred (aqueous alkaline solution). In another container, 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 aqueous alkali solution to be stirred, and polymerization was started. The polymerization reaction temperature was adjusted to be around 20 ° C. The polymerization was carried out for 2 hours under stirring, then the stirring was stopped, the reaction solution was allowed to stand, the aqueous phase and the organic phase were separated, only the aqueous phase was withdrawn from the reaction vessel, and 2 g of acetic acid was added to the remaining organic phase. Was added. 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 reached about 7. The obtained organic phase is gradually poured into a 50 ° C. hot water tank equipped with a homomixer to evaporate methylene chloride, thereby precipitating a powdery polymer, taking out the polymer, and performing dehydration and drying. A polyarylate resin (b1) was obtained. The inherent viscosity of this polyarylate resin (b1) was 0.49 dL / g, and DSC measurement showed that no crystal melting peak was observed and the glass transition temperature was 285 ° C. Table 1 shows the results.

Production Example 2
A polyarylate resin (b2) was obtained in the same manner as in Production Example 1, except that the dihydric phenol was changed to N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine (PPPBP). The inherent viscosity of this polyarylate resin (b2) was 0.49 dL / g, and DSC measurement showed that no crystal melting peak was observed and the glass transition temperature was 300 ° C. Table 1 shows the results.

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 inherent viscosity of this polyarylate resin (b3) was 0.49 dL / g, and DSC measurement showed that no crystal melting peak was observed and the glass transition temperature was 255 ° C. Table 1 shows the results.

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 inherent viscosity of this polyarylate resin (b4) was 0.49 dL / g, and DSC measurement showed that no crystal melting peak was observed and the glass transition temperature was 240 ° C. Table 1 shows the results.

Production Example 5
Same as Production Example 1 except that the dihydric phenol was 1,1-bis (4-hydroxyphenyl) -1-phenylethane (BPAP) and the amounts of TPC and IPC were 0.14 mol and 0.06 mol, respectively. Thus, a polyarylate resin (b5) was obtained. The inherent viscosity of this polyarylate resin (b5) was 0.48 dL / g, and DSC measurement showed that no crystal melting peak was observed and the glass transition temperature was 265 ° C. Table 1 shows the results.

Production Example 6
A polyarylate resin (b6) was obtained in the same manner as in Production Example 5, except that the amounts of TPC and IPC were changed to 0.06 mol and 0.14 mol, respectively. The inherent viscosity of this polyarylate resin (b6) was 0.49 dL / g, and the DSC measurement showed that no crystal melting peak was observed and the glass transition temperature was 220 ° C. Table 1 shows the results.

Production Example 7
The dihydric phenol was combined with 0.136 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC) and 0.058 mol of 2,2-bis (4-hydroxyphenyl) propane (BPA). A polyarylate resin (b7) was obtained in the same manner as in Production Example 1 except that the above procedure was repeated. This polyarylate resin (b7) had an inherent viscosity of 0.49 dL / g, and was subjected to DSC measurement. As a result, no crystal melting peak was observed and the glass transition temperature was 240 ° C. Table 1 shows the results.

Production Example 8
The dihydric phenol was combined with 0.058 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC) and 0.136 mol of 2,2-bis (4-hydroxyphenyl) propane (BPA). A polyarylate resin (b8) was obtained in the same manner as in Production Example 7 except for the above. The inherent viscosity of this polyarylate resin (b8) was 0.48 dL / g, and DSC measurement showed that no crystal melting peak was observed and the glass transition temperature was 215 ° C. Table 1 shows the results.

Production Example 9
A polyarylate resin (b9) was obtained in the same manner as in Production Example 7, except that the dihydric phenol was changed to 0.194 mol of 2,2-bis (4-hydroxyphenyl) propane (BPA). The polyarylate resin (b9) had an inherent viscosity of 0.48 dL / g, and was subjected to DSC measurement. As a result, no crystal melting peak was observed and the glass transition temperature was 190 ° C. Table 1 shows the results.

Example 1
A separable flask equipped with a stirrer and a condenser was used, and 250 parts by mass of N, N-dimethylformamide was used as an organic solvent. In the organic solvent, first, 50 parts by mass of the epoxy resin (a1) was heated and dissolved at 60 ° C., and then 50 parts by mass of the polyarylate resin (b1) was dissolved, and then the epoxy resin curing agent (c1) 2. 8 parts by mass and 0.35 parts by mass of 2-ethyl-4-methylimidazole as a curing accelerator were dissolved. Thereafter, the stirring was stopped and degassing was performed to prepare a resin varnish made of the resin composition.

  Using the obtained resin varnish, a coating and a laminate were formed and various evaluations were made. Table 2 shows the results.

Examples 2 to 11 and Comparative Examples 1 to 4
Except for changing the types and blending amounts of the epoxy resin, polyarylate resin and curing agent as shown in Table 2, a coating and a laminate were formed in the same manner as in Example 1 to perform various evaluations. The results are shown in Tables 2 and 3.

Example 12
A separable flask equipped with a stirrer and a condenser 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 heated and dissolved in the organic solvent at 60 ° C., and then 50 parts by mass of the polyarylate resin (b4) was dissolved. Into this solution, a solution obtained by dissolving 16.3 parts by mass of the epoxy resin curing agent (c2) in 50 parts by mass of methyl ethyl ketone as an organic solvent was added in a separate container, and the mixture was uniformly mixed. Thereafter, stirring was stopped and degassing was performed to obtain a resin varnish. In the same manner as in Example 1, a coating and a laminate were formed and various evaluations were performed. Table 2 shows the results.

Comparative Example 5
A separable flask equipped with a stirrer and a condenser was used, and 300 parts by mass of N, N-dimethylformamide was used as an organic solvent. 100 parts by mass of the polyarylate resin (b4) was heated and dissolved at 60 ° C. in the organic solvent. Thereafter, stirring was stopped and degassing was performed to obtain a resin varnish. In the same manner as in Example 1, a coating and a laminate were formed and various evaluations were performed. Table 3 shows the results.

Comparative Example 6
In the same manner as in Example 1 except that 50 parts by mass of a polycarbonate resin (Iupilon S-3000 manufactured by Mitsubishi Engineering-Plastics Co., Ltd .; inherent viscosity: 0.48 dL / g, glass transition temperature: 145 ° C.) is used instead of the polyarylate resin. Production of resin varnish was attempted.
However, an attempt was made to dissolve by heating at 60 ° C., but the test was stopped because an insoluble component was generated with almost no dissolution.

The evaluation results of the dielectric properties in the following Examples / Comparative Examples were as follows.
Example 3: relative permittivity 3.1, dielectric loss tangent 0.010;
Example 8: dielectric constant 3.2, dielectric loss tangent 0.011;
Comparative Example 4: dielectric constant 3.3, dielectric loss tangent 0.012.
* Test frequency = 1 GHz

  Since the resin compositions obtained in Examples 1 to 12 had a predetermined composition, the adhesiveness to a copper foil or a polyimide film was good, and the heat resistance was improved. It also had 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, the solder resistance after moisture absorption was reduced, and blistering occurred.

  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, the solder resistance after absorbing moisture was reduced, and swelling occurred.

  In Comparative Example 3, since the content of the epoxy resin was less than the lower limit, the adhesiveness 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 was reduced.

  In Comparative Example 5, since no epoxy resin was contained, in the evaluation of the adhesiveness with the copper foil or the polyimide film, each was easily peeled off, and had no adhesiveness to both the copper foil and the polyimide film. Furthermore, in the solder bath test, the coating was peeled off from the CCL in both the absolutely dry sample and the moisture-absorbing sample, and had no solder resistance.

  In Comparative Example 6, a polycarbonate resin was used in place of the polyarylate resin, but 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 where adhesiveness and heat resistance are required at the same time, and is useful, for example, for forming an adhesive layer in a wiring board, particularly a multilayer flexible printed wiring board and a flex-rigid printed wiring board. .

Claims (8)

A resin composition containing an epoxy resin (A) having two or more epoxy groups in one molecule, a polyarylate resin (B), and a curing agent (C),
The glass transition temperature of the polyarylate resin (B) is 200 ° C. or higher,
Ri said polyarylate resin (B) content ratio with respect to (A) / (B) is 30 / 70-90 / 10 (weight ratio) der of the epoxy resin (A), the
A resin composition wherein the polyarylate resin (B) contains an aromatic dicarboxylic acid residue and a 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane residue .   The resin composition according to claim 1, wherein the epoxy resin (A) has an epoxy equivalent of 90 to 500 g / eq. The polyarylate resin (B) further contains a dihydric phenol residue represented by the following general formula (v), according to claim 1 or according to 2 resin composition:

[In the general formula (v), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an alicyclic group having 3 to 20 carbon atoms. Hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms]. The resin composition according to any one of claims 1 to 3 , 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 4 in an organic solvent.   A coating obtained by drying the resin varnish according to claim 5. A laminate comprising the film according to claim 6 formed on a substrate. A wiring board using the laminate according to claim 7 .