WO2016024569A1 - Composition de résine et stratifié l'utilisant - Google Patents

Composition de résine et stratifié l'utilisant Download PDF

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Publication number
WO2016024569A1
WO2016024569A1 PCT/JP2015/072648 JP2015072648W WO2016024569A1 WO 2016024569 A1 WO2016024569 A1 WO 2016024569A1 JP 2015072648 W JP2015072648 W JP 2015072648W WO 2016024569 A1 WO2016024569 A1 WO 2016024569A1
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Prior art keywords
carbon atoms
group
hydrocarbon group
resin
resin composition
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PCT/JP2015/072648
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English (en)
Japanese (ja)
Inventor
浩治 今西
穣 鍋島
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ユニチカ株式会社
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Priority to JP2016542578A priority Critical patent/JP6676529B2/ja
Priority to CN201580043146.7A priority patent/CN106661197B/zh
Priority to KR1020177000936A priority patent/KR102376600B1/ko
Publication of WO2016024569A1 publication Critical patent/WO2016024569A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
    • C08G63/197—Hydroxy compounds containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins

Definitions

  • the present invention relates to a resin composition having high heat resistance and capable of forming an adhesive layer having excellent solder resistance after moisture absorption.
  • a build-up type multilayer printed wiring board manufacturing technique 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 a conductor layer and an organic insulating layer is to laminate a laminate composed of a conductor layer and an organic insulating base material (mainly polyimide is used) with an insulating adhesive layer.
  • This insulating adhesive layer must be firmly bonded to both the conductor layer forming the circuit and the organic insulating base material, and further, it must be embedded in the gap of the conductor layer in the circuit pattern. ing.
  • 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 urethane-modified carboxyl group-containing polyester resin, an adhesive composition containing an epoxy resin and a curing agent (for example, Patent Document 4), and the like are disclosed. ing.
  • thermosetting elastomer excellent in heat resistance and flexibility obtained by heat curing a resin composition containing epoxy resin, polyarylate resin and amine-based curing agent in specific ratios is disclosed. .
  • JP-A-5-263058 Japanese Patent Laid-Open No. 5-271737 Japanese Patent Laid-Open No. 11-116930 JP 2007-51212 A JP 2013-189544 A
  • solder resistance may decrease due to moisture absorption of the adhesive layer. Specifically, after the adhesive layer absorbs moisture under high temperature and high humidity, when heated due to melting of the solder, bubbles are generated due to evaporated water, causing the adhesive layer to swell or peel off from the conductor layer or organic insulating substrate. There was a problem. Furthermore, when the hot pressing is performed to cure the adhesive layer, the flowability of the resin composition is too good, so that a large amount of protrusion occurs.
  • An object of the present invention is to provide a resin composition that is excellent in adhesion to both a conductor layer and an organic insulating substrate, has high heat resistance, and can form an adhesive layer with excellent solder resistance after moisture absorption.
  • the present invention is also excellent in adhesion to both the conductor layer and the organic insulating substrate, has high heat resistance, excellent solder resistance after moisture absorption, and good anti-extrusion characteristics during hot pressing for curing.
  • An object is to provide a resin composition capable of forming an adhesive layer.
  • the gist of the present invention is as follows.
  • the polyarylate resin (B) is one or more divalents selected from the group consisting of aromatic dicarboxylic acid residues and dihydric phenol residues represented by the following general formulas (i) to (iv):
  • 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, or an alicyclic group having 3 to 20 carbon atoms.
  • R 11 , R 12 , R 13 and R 14 are each independently 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.
  • R 21 , R 22 , R 23 and R 24 are each independently 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 25 independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an alicyclic group having 3 to 20 carbon atoms.
  • R 31 , R 32 , R 33 and R 34 are each independently 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 35 is selected from the group consisting of a hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 35 is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an oil having 3 to 20 carbon atoms
  • the cyclic hydrocarbon group is selected from the group consisting of 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].
  • the resin composition which has high heat resistance and can form the contact bonding layer excellent in the solder tolerance 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, the adhesive insulating layer swells or peels off. Can be suppressed.
  • the resin composition of this invention can form the contact bonding layer excellent also in the adhesiveness with respect to both a conductor layer and an organic insulating base material.
  • the resin composition of the present invention can also form an adhesive layer excellent in the anti-extrusion 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.
  • 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 2 or more per molecule.
  • the epoxy resin (A) a known epoxy resin can be used, and an epoxy resin having 2 or more and 5 or less epoxy groups in one molecule is preferably used. When the number of epoxy groups contained in one molecule exceeds 5, when the resin varnish is produced from the resulting resin composition, the increase in viscosity may be significant.
  • the number of epoxy groups means the average number of epoxy groups per molecule because the epoxy resin has a molecular weight distribution.
  • the epoxy equivalent of the epoxy resin (A) having two or more epoxy groups in one molecule is preferably 90 to 500 g / eq, more preferably 90 to 300 g / eq, and 90 to 250 g / eq. More preferably. If the epoxy equivalent is less than 90 g / eq, the epoxy group is too dense to reduce the reactivity with the curing agent, while the crosslinking density is too high, so the viscosity of the resin varnish in which the resin composition is dissolved in an organic solvent is low. May be excessively high. When the epoxy equivalent exceeds 500 g / eq, the crosslink 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 cannot be improved.
  • Examples of the epoxy resin (A) having two or more epoxy groups in one 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, Phenol novolac type epoxy resin, cresol novolac 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.
  • bisphenol A type epoxy resins and phenol novolac type epoxy resins can be suitably used.
  • Such an epoxy resin is commercially available.
  • Commercially available products include: product name: GAN (manufactured by Nippon Kayaku Co., Ltd.), product name: jER630 (manufactured by Mitsubishi Chemical), product name: HP4032 (manufactured by DIC), product name: Celoxide 2081 (Daicel Chemical Industries)
  • Product name: jER828 Mitsubishi Chemical
  • product name: jER807 Mitsubishi Chemical
  • product name: Epicron EXA-1514 DIC Corporation
  • product name: jER152 Mitsubishi Chemical Corporation
  • Product name: jER604 Mitsubishi Chemical
  • Product name: MY-0500 Huntsman
  • Product: TETRAD-X Mitsubishi Gas Chemical
  • Product Name: SR-HHPA Sakamoto Pharmaceutical Co., Ltd.
  • Product name: EXA-4580-1000 DIC Corporation
  • bisphenol A type epoxy resins examples of commercial products: jER828, etc.
  • phenol novolac type epoxy resins examples of commercial products: jER152, etc.
  • bisphenol F type epoxy resins examples of commercial products: jER807, etc.
  • Glycidylamine type epoxy resins examples of commercial products: jER604, etc.
  • bisphenol A type epoxy resins and phenol novolac type epoxy resins are highly effective in improving adhesion to the copper foil and polyimide film of the resulting coating. Is particularly preferred.
  • the above-mentioned bisphenol A type epoxy resin may be liquid at room temperature or solid at room temperature depending on the number of repeating units of the bisphenol skeleton.
  • a bisphenol A type epoxy resin having 1 to 3 repeating units of the main chain bisphenol skeleton is liquid at room temperature, and a 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 a substrate to obtain a laminate, the film adheres to the adherend by heating and solidifies by solidifying the film and the adherend, thereby increasing the adhesive strength. Can do.
  • such a relatively low molecular weight bisphenol A type epoxy resin has a high crosslink density, and therefore has high mechanical strength, good chemical resistance, high curability, and hygroscopicity (because the free volume is small). ) Is also small.
  • the bisphenol A type epoxy resin that is solid at room temperature and a bisphenol A type epoxy resin that is liquid at room temperature, as described above, as the bisphenol A type epoxy resin.
  • a solid and a liquid at room temperature it is possible to obtain flexibility while maintaining mechanical strength, so that flexibility is obtained while maintaining the mechanical strength inherent in the resin composition. be able to.
  • the bonding strength between adherends can be improved.
  • the bisphenol A type epoxy resin that is solid at normal 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.
  • 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 of the chain bisphenol skeleton include jER1001 (manufactured by Mitsubishi Chemical Corporation).
  • the viscosity of the epoxy resin (A) having two or more epoxy groups in one molecule is preferably 5 to 30 Pa ⁇ s, and more preferably 8 to 25 Pa ⁇ s at 25 ° C. More preferably, it is 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.
  • 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 comprising an aromatic dicarboxylic acid and / or a derivative thereof and a dihydric phenol and / or a derivative thereof. It is produced by a method such as polymerization.
  • the polyarylate raw material for introducing the aromatic dicarboxylic acid residue is not particularly limited.
  • terephthalic acid and isophthalic acid are preferable, and it is particularly preferable to use a mixture of both from the viewpoint of solubility in a solvent.
  • the mixing ratio (terephthalic acid / isophthalic acid) is arbitrarily in the range of 100/0 to 0/100 (mol%), preferably 80/20 to 10/90 (mol%), more preferably 75.
  • the ratio is in the range of / 25 to 25/75 (mol%), the resulting polyarylate resin (B) has excellent solubility.
  • aliphatic dicarboxylic acids may be used together with the aromatic dicarboxylic acids.
  • the aliphatic dicarboxylic acids are not particularly limited, and examples thereof include dicarboxymethylcyclohexane, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, glutaric acid, and dodecanedioic acid.
  • the polyarylate raw material for introducing the dihydric phenol residue is not particularly limited, but from the viewpoint of improving the heat resistance of the resulting resin composition and improving the solubility in organic solvents, the following general formula (i It is preferable to introduce one or more dihydric phenol residues (hereinafter sometimes referred to as bisphenol I residues) selected from the group consisting of dihydric phenol residues represented by) to (iv).
  • 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, or an alicyclic carbon atom having 3 to 20 carbon atoms. Selected from the group consisting of a hydrogen group and an aromatic hydrocarbon group having 6 to 20 carbon atoms.
  • 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 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 an alkyl group such as a decyl group, and a vinyl group and an allyl group.
  • An alkenyl group is mentioned.
  • a preferred aliphatic hydrocarbon group is an alkyl group, more preferably an alkyl group having 1 to 10, more preferably 1 to 5, 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 aryl groups 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.
  • R 1 and R 3 are each independently, preferably simultaneously, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms, or a carbon number. 6-14, especially 6-10 aryl groups; R 2 and R 4 are each independently, preferably simultaneously a hydrogen atom or an alkyl group having 1-10 carbon atoms, especially 1-3.
  • R 1 and R 3 are each independently and preferably simultaneously an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms; R 2 and R 4 is simultaneously 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), 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.
  • R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic carbon atom having 3 to 20 carbon atoms. 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), and the preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 1 carbon atom. 5, especially 1-3 alkyl groups.
  • the alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the general 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 the general formula (i), and a preferable 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, or an aryl group having 6 to 20 carbon atoms.
  • 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.
  • alkenyl group examples include a vinyl group and an allyl group.
  • a preferred alkenyl group is an alkenyl group having 2 to 3 carbon atoms.
  • the aryl group examples include a phenyl group, a naphthyl group, and an anthranyl group. Preferred aryl groups are those having 6 to 14 carbon atoms, especially 6 to 10 carbon atoms.
  • R 11 and R 13 are each independently, preferably simultaneously a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, 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 carbon atoms, particularly 1 to 3 carbon atoms;
  • R 15 is a group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms.
  • R 11 to R 14 are simultaneously a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms;
  • R 15 is a carbon atom An alkyl group having 1 to 10, particularly 1 to 3, or an aryl group having 6 to 20 carbon atoms, 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.
  • R 21 , R 22 , R 23 and R 24 are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic carbon atom having 3 to 20 carbon atoms. 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), and the preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 1 carbon atom. 5, especially 1-3 alkyl groups.
  • the alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the general 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 the general formula (i), and a preferable 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 an alkyl halide having 1 to 20 carbon atoms. Selected from the group consisting of groups.
  • the aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group in the general formula (i), and the preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 1 carbon atom. 5, especially 1-3 alkyl groups.
  • the alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the general 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 the general formula (i), and a preferable aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.
  • the halogenated alkyl group has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms, and 1 to 2 hydrogen atoms are halogen atoms (for example, fluorine atom, chlorine atom, bromine atom). ) Substituted with an alkyl group.
  • Preferred halogenated alkyl groups include a monofluoromethyl group, a difluoromethyl group, a monochloromethyl group, and a dichloromethyl group.
  • the R 25 of 2 or more may be independently selected from the above group.
  • k is an integer of 2 to 12, preferably 4 to 11, more preferably an integer of 4 to 6.
  • the hydrogen atom of each carbon atom is omitted.
  • m is 1 or more, the one or more R 25 is substituted with a hydrogen atom of a carbon atom constituting the carbocycle.
  • m is an integer of 0 or more and 2k or less, preferably 0 to 4, more preferably 1 to 4.
  • R 21 and R 23 are each independently, preferably simultaneously 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 simultaneously, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms;
  • R 25 is a group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms.
  • K is an integer from 4 to 11, in particular from 4 to 6;
  • m is an integer from 0 to 4, in particular from 1 to 4.
  • R 21 to R 24 are simultaneously a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms;
  • R 25 is carbon An alkyl group having a number of 1 to 10, particularly 1 to 3; particularly when m is an integer of 2 or more, the R 25 of 2 or more is an alkyl group having 1 to 10 carbon atoms, particularly 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), 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-trimethylcycle Hexane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane
  • R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic carbon atom having 3 to 20 carbon atoms. 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 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), and the preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 1 carbon atom. 5, especially 1-3 alkyl groups.
  • the alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the general 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 the general formula (i), and a preferable 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), and the preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 1 carbon atom. 5, especially 1-3 alkyl groups.
  • the alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the general 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 the general formula (i), and a preferable 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 aromatic hydrocarbon groups having 6 to 20 carbon atoms.
  • the aromatic hydrocarbon group is the same as the aromatic hydrocarbon group in the general formula (i), and a preferable aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.
  • R 36 is a hydrogen atom or an alkyl group, the heat resistance is lowered, and particularly after the moisture absorption of the adhesive layer, the solder resistance is lowered.
  • R 31 and R 33 are each independently and preferably simultaneously a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms, Or an aryl group having 6 to 20 carbon atoms, particularly 6 to 10 carbon atoms;
  • R 32 and R 34 are each independently, preferably simultaneously, a hydrogen atom, a halogen atom, or a carbon atom having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms.
  • R 35 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms;
  • R 36 is an aryl group having 6 to 20 carbon atoms, particularly 6 to 10 carbon atoms.
  • R 31 to R 34 are simultaneously a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms;
  • R 35 Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, particularly 1 to 3 carbon atoms;
  • R 36 is an aryl group having 6 to 20 carbon atoms, particularly 6 to 10 carbon atoms.
  • 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.
  • 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-phenyle
  • 9,9-bis (4-hydroxyphenyl) fluorene (BPF), 9,9-bis (4-hydroxy) is used from the viewpoint of improving heat resistance and solubility.
  • BCF -3-methylphenyl) fluorene
  • PPPBP N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine
  • BPZ 1,1-bis (4-hydroxyphenyl) cyclohexane
  • DMBPC 1,1 -Bis (4-hydroxy-3-methylphenyl) cyclohexane
  • BPTMC 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane
  • BPAP 1,1-bis (4-hydroxy) Phenyl) -1-phenylethane
  • a dihydric phenol residue represented by the following general formula (v) (hereinafter referred to as bisphenol II residue).
  • bisphenol II residue a dihydric phenol residue represented by the following 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, or an alicyclic carbon atom having 3 to 20 carbon atoms. 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), and the preferred aliphatic hydrocarbon group is an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 1 carbon atom. 5, especially 1-3 alkyl groups.
  • the alicyclic hydrocarbon group is the same as the alicyclic hydrocarbon group in the general 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 the general formula (i), and a preferable aromatic hydrocarbon group is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms.
  • R 5 and R 7 are each independently, preferably simultaneously, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, particularly 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 carbon atoms, particularly 1 to 3 carbon atoms.
  • Examples of the compound for introducing the dihydric phenol residue of the general formula (v) include 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 in combination of two or more.
  • 2-bis (4-hydroxyphenyl) propane (BPA), 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 economical efficiency In view of superiority, 2-bis (4-hydroxyphenyl) propane (BPA) is particularly preferred.
  • BPA 2,2-bis ( 4-hydroxy-3-methylphenyl) propane
  • TMBPA 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane
  • BPA 2-bis (4-hydroxyphenyl) propane
  • the divalent phenol residues represented by the above general formulas (i) to (iv) are introduced from the viewpoint of heat resistance and economy of the polyarylate resin (B) obtained.
  • (bisphenol I residue) / (bisphenol I residue + bisphenol II) The residue is preferably 10/100 to 100/100 (molar ratio), more preferably 30/100 to 100/100 (molar ratio).
  • the heat resistance of the polyarylate resin (B) may be inferior.
  • (bisphenol I residue) / (bisphenol I residue + bisphenol II residue) is preferably 10/100 to 80/100 (molar ratio), and 20/100 to More preferably, it is 80/100 (molar ratio).
  • a bisphenol residue other than the bisphenol I residue or the bisphenol II residue may be introduced as long as the characteristics and effects of the present invention are not impaired.
  • bisphenols include 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 4-methyl-2, And 2-bis (4-hydroxyphenyl) pentane.
  • aliphatic glycols or dihydroxybenzene may be used as long as the characteristics and effects of the present invention are not impaired.
  • Aliphatic glycols are not particularly limited, but ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, nonanediol, decanediol, cyclohexanedimethanol, ethylene oxide adducts of bisphenol A, and propylene oxide adducts thereof
  • dihydroxybenzenes such as ethylene oxide adducts of bisphenol S, hydroquinone, resorcinol, and catechol.
  • the inherent viscosity of the polyarylate resin (B) is preferably 0.30 to 1.00 dL / g, and more preferably 0.35 to 0.80 dL / g.
  • the inherent viscosity is less than 0.30 dL / g, the resulting resin composition has inferior flexibility, and the resin composition falls off in powder form from the end face of the laminate when punching or router processing.
  • the inherent viscosity exceeds 1.00 dL / g, the viscosity at the time of mixing with an epoxy resin or an organic solvent increases, so that dispersibility and coatability may deteriorate, which is not preferable.
  • Inherent viscosity is an index of molecular weight, and dissolved at a concentration of 1 g / dL in a 60/40 (mass ratio) mixture of phenol / 1,1,2,2-tetrachloroethane under a temperature of 25 ° C. Measured using the prepared resin solution.
  • a method of adjusting the molecular weight by controlling the reaction rate by adjusting the polymerization time, an aromatic dicarboxylic acid component or a dihydric phenol component A method of adjusting the molecular weight by polymerizing by adding a slight excess of any of the components in the blending ratio of the monomer, aliphatic monoalcohols having only one reactive functional group in the molecule, phenols, or Examples thereof include a method of adjusting the molecular weight by adding monocarboxylic acids together with monomers as end-capping agents. Among these, the method of adding a terminal blocking agent is preferable because the molecular weight can be easily controlled.
  • Examples of the end-capping 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, Examples thereof include monocarboxylic acids such as acetic acid, propionic acid, butyric acid, oleic acid and stearic acid, and derivatives thereof.
  • monocarboxylic acids such as acetic acid, propionic acid, butyric acid, oleic
  • 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., 220 ° C. or higher and 300 ° C. or higher. It is more preferable that the temperature is lower than °C, and it is most preferable that the temperature is 230 ° C or higher and lower than 290 ° C.
  • the resulting resin composition has high heat resistance. When the glass transition temperature is less than 200 ° C., the heat resistance of the resin composition is inferior. 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 value of the polyarylate resin (B) is preferably 10 mol / ton or more, more preferably 20 mol / ton or more, and further preferably 30 mol / ton or more.
  • the carboxyl value of the polyarylate resin (B) represents the content ratio of the terminal carboxyl group in the polyarylate resin (B), but it is cured by reacting the carboxyl group with the epoxy group of the epoxy resin (A). It becomes easy to compatibilize the epoxy resin (A) and the polyarylate resin (B) in the product.
  • Examples of the method for introducing a terminal carboxyl group into the polyarylate resin (B) include a method in which the polymerization reaction is stopped before the reaction is completed, and a method in which an ester bond is hydrolyzed with an alkali or the like.
  • the content ratio of the epoxy resin (A) and the polyarylate resin (B) is (A) / (B) of 30/70 to 90/10 (mass ratio), and 35/65 Is preferably 85/15 (mass ratio), more preferably 40/60 to 80/20 (mass ratio), and still more preferably 40/60 to 70/30 (mass ratio).
  • the content of the epoxy resin (A) is less than 30% by mass, the adhesion of the resin composition to the adherend is insufficient.
  • the content of the epoxy resin (A) exceeds 90% by mass, the heat resistance after the wet heat treatment is not 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).
  • a fat such as diethylenetriamine, triethylenetetonlamine or tetraethylenepentamine.
  • polyamine compounds such as metaphenylenediamine, polyamine compounds such as dicyandiamide, adipic dihydrazide and polyamide polyamine, or phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tet Monofunctional acid anhydrides such as hydrophthalic anhydride,
  • the content of the curing agent (C) is not particularly limited, and is generally a ratio of the stoichiometric amount of the epoxy group of the epoxy resin (A) and the stoichiometric amount of the functional group of the curing agent (epoxy / curing).
  • the 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, it cannot be generally stated, but the content of the curing agent can be determined by the ratio of the equivalent of active hydrogen and the epoxy equivalent of the curing agent.
  • the compounding amount of the amine compound can be calculated based on the ratio between the equivalent of active hydrogen bonded to the amino group and the epoxy equivalent.
  • 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.
  • 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.
  • a curing accelerator can be used instead of or together with the curing agent.
  • the curing accelerator is not particularly limited, and examples thereof include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, Tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol can be used.
  • the compounding quantity of a hardening accelerator can also be set suitably.
  • 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.
  • other resins include polycarbonate, polystyrene, polyester, acrylic resin, polyphenylene ether, polysulfone, polyethersulfone, and polyetherimide.
  • 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 manufacturing method of the resin composition of this invention is demonstrated.
  • the resin composition of the present invention can be prepared by dissolving and mixing at least the epoxy resin (A), the polyarylate resin (B), and the curing agent (C) in an organic solvent so as to have a predetermined ratio.
  • the epoxy resin (A), the polyarylate resin (B) and the curing agent (C) are collectively put in an organic solvent and mixed while being dissolved, the epoxy resin (A), the polyarylate resin (B) and the curing agent (C) are mixed and then dissolved in an organic solvent.
  • the organic compound is added while adding the curing agent (C).
  • a method of charging in a solvent and dissolving The epoxy resin (A), the polyarylate resin (B) and the curing agent (C) are collectively treated in that it is easy to improve the workability during dissolution and mixing and to increase the uniformity of the resulting resin composition.
  • a method of mixing while dissolving in an organic solvent is particularly preferred.
  • a method of melt-mixing the epoxy resin (A), the polyarylate resin (B), and the curing agent (C) is also conceivable.
  • the resulting resin composition becomes too viscous and is applied in a thin film on the substrate. Since it becomes difficult to work, it should not be employed in the present invention unless necessary.
  • the organic solvent to be used That is, the epoxy resin (A) and the polyarylate resin (B) are different from each other in the kind of organic solvent that is easily dissolved. If an organic solvent in which one of them is difficult to dissolve is used, it becomes difficult to make the resulting resin composition uniform.
  • 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 obtain a resin varnish.
  • a resin varnish it is preferable that a highly compatible resin varnish can be obtained without the components of the epoxy resin (A) and the polyarylate resin (B) being separated from each other.
  • the epoxy resin (A) and the polyarylate resin (B) are not separated inside the resin composition, resulting in a uniform resin composition. Can be made.
  • the polyarylate resin (B) must be dissolved in the same organic solvent as the 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 kinds of solvents and there are a wide range of solvent options, various organic solvents can be selected according to the purpose, and various coatings can be formed.
  • organic solvent to be used those capable of dissolving the polyarylate resin (B) alone at a solid concentration of 20% by mass or more are preferable, and those capable of dissolving at 30% by mass or more are more preferable.
  • the cured resin composition tends to have excellent mechanical properties and heat resistance, but the curing agent (C) together with the epoxy resin (A) and the polyarylate resin (B). Soluble organic solvents are often limited. In such a case, it is preferable to pulverize the curing agent (C) as finely as possible and uniformly disperse it in a solution in which the epoxy resin (A) and the polyarylate resin (B) are dissolved.
  • the solid content concentration is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, and 20 to 50% by mass. More preferably.
  • the solid content concentration is less than 10% by mass, it is difficult to obtain a thickness necessary for forming a film, and when the solid content concentration exceeds 70% by mass, not only the formation of the film becomes difficult, but also the obtained film. This is not preferable because the thickness accuracy is reduced.
  • a film can be formed by applying and drying on various substrates using a known coating method such as Meyer bar coating, gravure coating, kiss coating, spin coating, and the like. .
  • a coating film made of a resin composition can be formed by coating on a film substrate made of polyethylene terephthalate (PET) resin or the like that has been subjected to a mold release treatment and then drying.
  • PET polyethylene terephthalate
  • the coating can be peeled off from the film substrate and used as a resin composition coating alone or as a laminate in which a coating is formed on the substrate.
  • the drying temperature at the time of forming the coating film made of the resin composition has a great influence on the adhesive properties when used in applications such as adhesion as a coating film or a laminate in the present invention, its selection is very important.
  • the heating temperature at the time of drying is a temperature that promotes evaporation of the organic solvent from the resin varnish, and 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 generally determined, but it is preferably performed 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 solubility.
  • the heating time should be set not only to remove the organic solvent but also to allow the resin composition to reach a desired reaction rate. However, since the reaction rate depends on the heating temperature, it cannot be determined unconditionally.
  • 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. Drying is preferably performed in multiple stages with different reaction temperatures (drying temperatures). In this case, drying may be performed in multiple stages so that the temperature increases stepwise within the above range, and the drying time for each stage may be set so that the total time is within the above range.
  • an antifoaming agent When dissolving the resin composition of the present invention in an organic solvent, an antifoaming agent, a leveling agent, an ion repairing agent, or the like may be added as long as the object of the present invention is not impaired.
  • the laminate of the present invention or a laminate having a coating formed on a substrate can be used for various purposes. In particular, it can be suitably used for electrical and electronic component applications.
  • a specific example of use will be described using a bonding sheet as an example.
  • the 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 base material. Its usage varies in application. Taking the case of producing a multilayer printed wiring board as an example, first, after laminating on a circuit board patterned as a bonding sheet, the film substrate is peeled off from the adhesive layer, and an organic insulating layer, conductor, or A separately manufactured circuit board is stacked.
  • the heat curing temperature is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, further preferably 130 ° C. or higher and 190 ° C. or lower.
  • the heat curing time is not particularly limited as long as sufficient curing is achieved. For example, in the case of the above 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 used for laminating a multilayer printed wiring of a build-up system, particularly a multilayer flexible printed wiring board. Suitable for sheets.
  • the inner layer circuit is formed by pattern etching on each of the copper foils attached to both surfaces of the flexible substrate material made of polyimide resin.
  • a cover lay made of a polyimide resin is pressure-bonded so as to cover the entire inner circuit forming surfaces on both sides to obtain a flexible printed wiring board.
  • an outer layer flexible board that is copper-plated only on the opposite surface of the flexible printed wiring board of another base material made of polyimide resin, for example, is bonded to the both surfaces by an adhesive, and is pressure-bonded by pressure processing to mount an electronic component. Therefore, a multilayer flexible printed wiring board having a multilayer structure is obtained.
  • the flex-rigid printed wiring board is a multilayer wiring board in which a rigid board material obtained by laminating a prepreg obtained by impregnating a base material with a resin is laminated 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.
  • the PET film substrate was released from the laminate to obtain a laminate [B] in which a film was laminated on the copper foil surface of the copper-clad laminate.
  • the laminated body [B] is laminated on the copper foil side of another single-sided CCL in the same manner as described above, so that the laminated body [C] is sandwiched between two single-sided CCL copper foils [C] ] Was obtained.
  • This laminate [C] was hot-pressed at a heating temperature of 190 ° C. and a press pressure of 3 MPa for 90 minutes to completely cure the coating film, and used as a sample for evaluating adhesiveness.
  • the sample was cut into a strip shape 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.
  • the peel strength is “ ⁇ ” when it exceeds 2.0 N / cm, “ ⁇ ” when it exceeds 1.5 N / cm, “ ⁇ ” when it exceeds 1.0 N / cm (no problem in practical use)
  • the case of 1.0 N / cm or less was determined as “x”.
  • it is practically preferable that the evaluation result is “ ⁇ ” or more, particularly “ ⁇ ”.
  • the sample was cut into a strip shape having a width of 10 mm, and a peeling test at an angle of 90 ° was performed under the test condition of a tensile speed of 100 mm / min to evaluate the fracture mode.
  • the failure mode is from excellent to "material destruction” where the polyimide film breaks, “cohesive failure” where the adhesive layer breaks (no problem in practical use), and “interface peeling” where the adhesive layer peels from the polyimide film. .
  • the evaluation result is “material destruction”.
  • 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.
  • a laminate was produced in the same manner as the laminate [C] in “(3) Adhesiveness with copper foil” except that a glass substrate was used as the substrate. The laminate was hot-pressed at a heating temperature of 190 ° C. and a press pressure of 3 MPa for 90 minutes, and then the film was peeled from the glass substrate. A sample was cut into a size of 50 mm ⁇ 50 mm. The obtained coating film alone was set in the following measurement jig, and the relative dielectric constant and dielectric loss tangent were measured at room temperature using the following apparatus. ⁇ Device> Impedance / Material Analyzer E4991A manufactured by Agilent Technologies (currently Keysight Technology) ⁇ Jig for measurement> 16453A
  • Number of epoxy groups present in 2 2
  • Curing agent (c1) Dicyandiamide (DD manufactured by Nippon Carbide Industries Co., Ltd.) (C2) Diaminodiphenyl sulfone (special grade reagent manufactured by Kanto Chemical Co., Inc.)
  • Production Example 1 A reaction vessel equipped with a stirrer was charged with 1.2 L of water, 0.79 mol of sodium hydroxide, and 0.194 mol of divalent phenol 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (BCF). Then, 0.0116 mol of p-tert-butylphenol (PTBP) was dissolved as a molecular weight modifier, 0.0013 mol of a polymerization catalyst (tributylbenzylammonium chloride) was added, and the mixture was vigorously stirred (alkaline aqueous solution).
  • PTBP p-tert-butylphenol
  • TPC terephthalic acid chloride
  • IPC isophthalic acid chloride
  • the methylene chloride is evaporated while gradually adding the obtained organic phase into a 50 ° C. hot water tank equipped with a homomixer to precipitate a powdered polymer, which is taken out and dehydrated and dried.
  • a polyarylate resin (b1) was obtained.
  • the inherent viscosity of this polyarylate resin (b1) was 0.49 dL / g.
  • DSC measurement was performed, 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 N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine (PPPBP) was used as the dihydric phenol.
  • PPPBP N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine
  • the inherent viscosity of this polyarylate resin (b2) was 0.49 dL / g. When DSC measurement was performed, 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 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC) was used as the dihydric phenol.
  • BPTMC 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane
  • the inherent viscosity of the polyarylate resin (b3) was 0.49 dL / g. When DSC measurement was performed, 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 1,1-bis (4-hydroxyphenyl) -1-phenylethane (BPAP) was used as the dihydric phenol.
  • the inherent viscosity of the polyarylate resin (b4) was 0.49 dL / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 240 ° C. The results are shown in Table 1.
  • Production Example 5 The same procedure as in Production Example 1 except that 1,1-bis (4-hydroxyphenyl) -1-phenylethane (BPAP) was used as the dihydric phenol, 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 the polyarylate resin (b5) was 0.48 dL / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 265 ° C. The results are shown in Table 1.
  • BPAP 1,1-bis (4-hydroxyphenyl) -1-phenylethane
  • 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 0.06 mol and 0.14 mol, respectively.
  • the inherent viscosity of the polyarylate resin (b6) was 0.49 dL / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 220 ° C. The results are shown in Table 1.
  • Production Example 8 Dihydric phenol was mixed 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). Except that, polyarylate resin (b8) was obtained in the same manner as in Production Example 7. The inherent viscosity of this polyarylate resin (b8) was 0.48 dL / g. When DSC measurement was performed, 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 Production 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. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 190 ° C. The results are shown in Table 1.
  • 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 the organic solvent. First, 50 parts by mass of the epoxy resin (a1) is heated and dissolved at 60 ° C. in the organic solvent, and then 50 parts by mass of the polyarylate resin (b1) is dissolved. 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. Then, the resin varnish which consists of a resin composition was prepared by stopping stirring and deaeration.
  • Examples 2 to 11 and Comparative Examples 1 to 4 A coating and a laminate were formed in the same manner as in Example 1 except that the types and blending amounts of the epoxy resin, polyarylate resin, and curing agent were changed as shown in Table 2, and various evaluations were performed. The results are shown in Tables 2 and 3.
  • Example 12 A separable 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 heated and dissolved at 60 ° C. in the organic solvent, and then 50 parts by mass of the polyarylate resin (b4) was dissolved. Into this solution, an entire amount of a solution obtained by dissolving 16.3 parts by mass of the epoxy resin curing agent (c2) was added to 50 parts by mass of methyl ethyl ketone as an organic solvent in another container and uniformly mixed. Then, the resin varnish was obtained by stopping stirring and deaeration. In the same manner as in Example 1, a film and a laminate were formed and various evaluations were performed. The results are shown in Table 2.
  • 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 the organic solvent. In the organic solvent, 100 parts by mass of polyarylate resin (b4) was dissolved by heating at 60 ° C. Then, the resin varnish was obtained by stopping stirring and deaeration. In the same manner as in Example 1, a film and a laminate were formed and various evaluations were performed. The results are shown in Table 3.
  • Comparative Example 6 Except for using 50 parts by mass of a polycarbonate resin (Iupilon S-3000 manufactured by Mitsubishi Engineering Plastics, Inc., inherent viscosity is 0.48 dL / g, glass transition temperature 145 ° C.) instead of the polyarylate resin, the same procedure as in Example 1 was performed. An attempt was made to produce a resin varnish. However, although an attempt was made to dissolve by heating at 60 ° C., the test was stopped because insoluble matter was generated with almost no dissolution.
  • a polycarbonate resin Iupilon S-3000 manufactured by Mitsubishi Engineering Plastics, Inc., inherent viscosity is 0.48 dL / g, glass transition temperature 145 ° C.
  • Example 3 relative dielectric constant 3.1, dielectric loss tangent 0.010;
  • Example 8 dielectric constant 3.2, dielectric loss tangent 0.011;
  • the resin compositions obtained in Examples 1 to 12 had a predetermined composition, they had good adhesion to copper foil or polyimide film and improved heat resistance. Furthermore, it had excellent solder resistance after moisture absorption.
  • Comparative Example 6 a polycarbonate resin was used instead of the polyarylate resin, but the 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 in which adhesiveness and heat resistance are required at the same time.
  • it is useful for forming an adhesive layer in a wiring board, in particular, a multilayer flexible printed wiring board and a flex-rigid printed wiring board. .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une composition de résine permettant de former une couche adhésive qui a une excellente adhésivité à la fois à une couche conductrice et une substance isolante organique, et qui a une résistance à la chaleur élevée et une excellente résistance de soudure après absorption d'humidité. Cette composition de résine contient une résine époxy (A) ayant deux groupes époxy ou plus dans une molécule, une résine de polyarylate (B) et un agent de durcissement (C), la température de transition vitreuse de la résine de polyarylate (B) étant supérieure ou égale à 200 °C, et le rapport de teneur (A)/(B) de la résine époxy (A) à la résine de polyarylate (B) étant de 30/70 à 90/10 (rapport en masse).
PCT/JP2015/072648 2014-08-15 2015-08-10 Composition de résine et stratifié l'utilisant WO2016024569A1 (fr)

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WO2017142004A1 (fr) * 2016-02-19 2017-08-24 ユニチカ株式会社 Résine de polyarylate et film la comprenant
WO2017175716A1 (fr) * 2016-04-05 2017-10-12 ユニチカ株式会社 Résine de polyarylate, et composition de résine associée
WO2018186030A1 (fr) * 2017-04-07 2018-10-11 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, stratifié plaqué de métal, carte de circuit imprimé, et carte de circuit imprimé flexorigide
CN108794978A (zh) * 2017-04-27 2018-11-13 台燿科技股份有限公司 树脂组成物、及使用该树脂组成物所制得的预浸渍片、金属箔积层板及印刷电路板
JP2019137622A (ja) * 2018-02-07 2019-08-22 Dic株式会社 ポリエステル樹脂
CN112745737A (zh) * 2020-12-27 2021-05-04 贵州龙科生产力促进中心 一种电子产品外壳的高效散热涂料
JP2021155680A (ja) * 2020-03-30 2021-10-07 リンテック株式会社 フィルム状接着剤
JP2021155679A (ja) * 2020-03-30 2021-10-07 リンテック株式会社 フィルム状接着剤
JP2021191866A (ja) * 2016-07-28 2021-12-16 Jsr株式会社 組成物、硬化物及び積層体
CN114616096A (zh) * 2019-10-29 2022-06-10 帝人株式会社 天线用导电薄膜和天线
WO2024090396A1 (fr) * 2022-10-24 2024-05-02 太陽ホールディングス株式会社 Composition de résine durcissable, structure multicouche, produit durci, et composant électronique

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WO2017142004A1 (fr) * 2016-02-19 2017-08-24 ユニチカ株式会社 Résine de polyarylate et film la comprenant
CN108699227B (zh) * 2016-04-05 2021-05-14 尤尼吉可株式会社 聚芳酯树脂及其树脂组合物
WO2017175716A1 (fr) * 2016-04-05 2017-10-12 ユニチカ株式会社 Résine de polyarylate, et composition de résine associée
CN108699227A (zh) * 2016-04-05 2018-10-23 尤尼吉可株式会社 聚芳酯树脂及其树脂组合物
TWI746536B (zh) * 2016-04-05 2021-11-21 日商尤尼吉可股份有限公司 聚芳酯樹脂及其樹脂組成物
KR102313046B1 (ko) * 2016-04-05 2021-10-14 유니티카 가부시끼가이샤 폴리아릴레이트 수지 및 그 수지 조성물
KR20180133390A (ko) * 2016-04-05 2018-12-14 유니티카 가부시끼가이샤 폴리아릴레이트 수지 및 그 수지 조성물
JPWO2017175716A1 (ja) * 2016-04-05 2019-02-14 ユニチカ株式会社 ポリアリレート樹脂およびその樹脂組成物
JP2021191866A (ja) * 2016-07-28 2021-12-16 Jsr株式会社 組成物、硬化物及び積層体
JP7147940B2 (ja) 2016-07-28 2022-10-05 Jsr株式会社 組成物、硬化物及び積層体
WO2018186030A1 (fr) * 2017-04-07 2018-10-11 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, stratifié plaqué de métal, carte de circuit imprimé, et carte de circuit imprimé flexorigide
JP2018177906A (ja) * 2017-04-07 2018-11-15 パナソニックＩｐマネジメント株式会社 樹脂組成物、プリプレグ、金属張積層板、プリント配線板及びフレックスリジッドプリント配線板
CN108794978A (zh) * 2017-04-27 2018-11-13 台燿科技股份有限公司 树脂组成物、及使用该树脂组成物所制得的预浸渍片、金属箔积层板及印刷电路板
JP7056196B2 (ja) 2018-02-07 2022-04-19 Dic株式会社 ポリエステル樹脂
JP2019137622A (ja) * 2018-02-07 2019-08-22 Dic株式会社 ポリエステル樹脂
CN114616096A (zh) * 2019-10-29 2022-06-10 帝人株式会社 天线用导电薄膜和天线
CN114616096B (zh) * 2019-10-29 2023-11-10 帝人株式会社 天线用导电薄膜和天线
JP2021155680A (ja) * 2020-03-30 2021-10-07 リンテック株式会社 フィルム状接着剤
JP2021155679A (ja) * 2020-03-30 2021-10-07 リンテック株式会社 フィルム状接着剤
JP7446887B2 (ja) 2020-03-30 2024-03-11 リンテック株式会社 フィルム状接着剤
CN112745737A (zh) * 2020-12-27 2021-05-04 贵州龙科生产力促进中心 一种电子产品外壳的高效散热涂料
WO2024090396A1 (fr) * 2022-10-24 2024-05-02 太陽ホールディングス株式会社 Composition de résine durcissable, structure multicouche, produit durci, et composant électronique

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