WO2013191012A1 - エポキシ樹脂及びその製造方法、エポキシ樹脂組成物並びに硬化物 - Google Patents
エポキシ樹脂及びその製造方法、エポキシ樹脂組成物並びに硬化物 Download PDFInfo
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- WO2013191012A1 WO2013191012A1 PCT/JP2013/065806 JP2013065806W WO2013191012A1 WO 2013191012 A1 WO2013191012 A1 WO 2013191012A1 JP 2013065806 W JP2013065806 W JP 2013065806W WO 2013191012 A1 WO2013191012 A1 WO 2013191012A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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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
- 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
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- 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
- C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
- C08G10/02—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only of aldehydes
- C08G10/04—Chemically-modified polycondensates
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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
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- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- 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
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- 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
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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- 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
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
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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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
- H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
Definitions
- the present invention relates to an epoxy resin and a method for producing the same, an epoxy resin composition, and a cured product.
- Patent Document 1 is excellent in flame retardancy obtained by reacting an aromatic hydrocarbon formaldehyde resin with a novolak-type phenol resin obtained by reacting a phenol containing at least naphthol and another phenol compound with an epihalohydrin.
- An epoxy resin is disclosed.
- a copper clad laminate is usually manufactured using a prepreg formed by impregnating a thermosetting resin into a reinforcing base material as an insulating layer.
- glass-based epoxy resin copper-clad laminates are mainly used in industrial electronic devices such as computers and control devices, and consumer electronic devices such as video cameras and video games.
- conventional glass-based epoxy resin copper-clad laminates cannot satisfy the requirements in terms of heat resistance, high adhesion, etc.
- the above-mentioned novolac type epoxy resin improves the heat resistance, which is a disadvantage of the conventional epi-bis type epoxy resin, but when used alone or when blended in a large amount in the epi-bis type resin, delamination While strength falls, it has the faults, such as copper foil peel strength falling and moisture resistance falling.
- the epoxy resin described in Patent Document 1 has a defect that heat resistance, high adhesiveness and moisture resistance are not sufficient.
- the present invention aims to eliminate the drawbacks of conventional epoxy resins, and is useful for composite materials in the aircraft field and laminates in the electronics field, coating materials, semiconductor encapsulants, and molding materials. It aims at obtaining the epoxy resin excellent in heat resistance, high adhesiveness, and moisture resistance.
- an epoxy resin obtained by reacting with an epihalohydrin through a modification treatment with a compound represented by the formula (3) after performing a specific treatment in (3) can solve the above-mentioned problems. Reached.
- Y 1 independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group, q represents a number of 0 to 3, and A represents 0 to Represents the number of 2.
- Y 2 independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group, and r represents a number of 0 to 3).
- X independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group
- Y 3 independently represents one having 1 to 10 carbon atoms.
- the compound represented by the formula (1) is benzene, toluene, xylene, mesitylene, ethylbenzene, propylbenzene, decylbenzene, cyclohexylbenzene, biphenyl, methylbiphenyl, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, anthracene, methylanthracene.
- the compound represented by the formula (3) is phenol, methoxyphenol, benzoxyphenol, catechol, resorcinol, hydroquinone, cresol, phenylphenol, naphthol, methoxynaphthol, benzoxynaphthol, dihydroxynaphthalene, hydroxyanthracene, methoxyanthracene, benzo
- the amount of the acidic catalyst used is 0.0001 to 100 parts by mass with respect to 100 parts by mass of the aromatic hydrocarbon formaldehyde resin, and the amount of water used is the aromatic hydrocarbon formaldehyde resin.
- the amount of the compound represented by the formula (3) used is 0.1 to 5 mol with respect to 1 mol of oxygen contained in the acid-treated resin.
- a method for producing an epoxy resin comprising the following steps (a) to (d): (A): a step of obtaining an aromatic hydrocarbon formaldehyde resin by reacting a compound represented by the following formula (1) and / or (2) with formaldehyde in the presence of a catalyst; (B): a step of obtaining an acid-treated resin by treating the aromatic hydrocarbon formaldehyde resin obtained in step (a) with an acidic catalyst and water; (C): a step of obtaining a modified resin by treating the acid-treated resin obtained in step (b) with an acidic catalyst and a compound represented by the following formula (3); (D): A step of obtaining an epoxy resin by reacting the modified resin obtained in the step (c) with epihalohydrin.
- Y 1 independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group, q represents a number of 0 to 3, and A represents 0 to Represents the number of 2.
- Y 2 independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group, and r represents a number of 0 to 3).
- X independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group
- Y 3 independently represents one having 1 to 10 carbon atoms.
- An alkyl group, an aryl group having 6 to 10 carbon atoms or a cyclohexyl group, p represents a number of 1 to 3, s represents a number of 0 to 3, and B represents a number of 0 to 3)
- the epoxy resin of the present invention has excellent heat resistance, high adhesion, and excellent moisture resistance, so it is useful as a resin for laminates, semiconductor sealing, molding materials, adhesives, coatings, etc. It is.
- the epoxy resin in this embodiment is An epoxy resin obtained through the following steps (a) to (d).
- Step (a) is a step of obtaining an aromatic hydrocarbon formaldehyde resin by reacting the compound represented by the formula (1) and / or (2) with formaldehyde in the presence of a catalyst.
- the production method of the aromatic hydrocarbon formaldehyde resin used in the present embodiment is not particularly limited, and by applying a known method from the compounds represented by the following formulas (1) and / or (2) Obtainable.
- a resin can be obtained.
- the aromatic hydrocarbon formaldehyde resin obtained by the method as described above can be identified by measuring gel permeation chromatography, organic element analysis, softening point, hydroxyl value and the like.
- Y 1 independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group, q represents a number of 0 to 3, and A represents 0 to Represents the number of 2.
- Y 2 independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group, and r represents a number of 0 to 3).
- Examples of the compound represented by the formula (1) include benzene, toluene, xylene, mesitylene, ethylbenzene, propylbenzene, decylbenzene, cyclohexylbenzene, biphenyl, methylbiphenyl, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, anthracene, methylanthracene. , Dimethylanthracene, ethylanthracene, binaphthyl and the like.
- biphenyl naphthalene, methylnaphthalene, dimethylnaphthalene, anthracene, methylanthracene, and dimethylanthracene are preferable, and from the viewpoint of industrial use, biphenyl is more preferable.
- Naphthalene, methylnaphthalene and dimethylnaphthalene are preferable.
- Examples of the compound represented by the formula (2) include phenanthrene, methylphenanthrene, dimethylphenanthrene, ethylphenanthrene, decylphenanthrene, cyclohexylphenanthrene, phenylphenanthrene, naphthylphenanthrene and the like. Moreover, from the viewpoint of combining heat resistance and solubility in a balanced manner, phenanthrene, cyclohexylphenanthrene, and phenylphenanthrene are preferable, and phenanthrene is more preferable.
- Step (b) is a step of obtaining an acid-treated resin by treating the aromatic hydrocarbon formaldehyde resin obtained in step (a) with an acidic catalyst and water.
- the acid-treated resin used in this embodiment can be obtained by treating the aromatic hydrocarbon formaldehyde resin using an acidic catalyst and water.
- the naphthalene ring is crosslinked with — (CH 2 ) 1 — and / or CH 2 A—.
- A represents — (OCH 2 ) m —
- l represents a number from 1 to 10
- m represents a number from 0 to 10.
- the acid-treated resin is also referred to as “deacetal-bonded aromatic hydrocarbon formaldehyde resin”.
- the deacetal-bonded aromatic hydrocarbon formaldehyde resin has further improved thermal decomposition resistance as compared with the resin not subjected to the acid treatment.
- the acidic catalyst and the acidic catalyst that can be used for the treatment with water can be appropriately selected from known inorganic acids and organic acids.
- inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid; oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluene
- Organic acids such as sulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid; zinc chloride, aluminum chloride, iron chloride, trifluoride
- Lewis acids such as boron
- solid acids such as silicotungstic acid, phosphotungstic acid,
- sulfuric acid oxalic acid, citric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, and phosphotungstic acid are preferable from the viewpoint of production.
- the treatment with the acidic catalyst and water is usually carried out at normal pressure in the presence of the acidic catalyst, and the water used is dropped into the system or as water vapor at a temperature higher than the temperature at which the raw materials used are compatible (usually 80 to 300 ° C.) Perform while spraying.
- the water in the system may be distilled off or refluxed. However, it is preferable that the water is distilled off together with low-boiling components such as formaldehyde generated in the reaction because the acetal bond can be efficiently removed.
- the pressure may be normal pressure or increased pressure. Moreover, you may ventilate inert gas, such as nitrogen, helium, and argon, in a system as needed.
- a solvent inert to the reaction can be used.
- the solvent include aromatic hydrocarbons such as toluene, ethylbenzene and xylene; saturated aliphatic hydrocarbons such as heptane and hexane; alicyclic hydrocarbons such as cyclohexane; ethers such as dioxane and dibutyl ether; 2-propanol Alcohols such as methyl isobutyl ketone; carboxylic acid esters such as ethyl propionate; carboxylic acids such as acetic acid.
- the amount of the acidic catalyst used is preferably 0.0001 to 100 parts by mass, more preferably 0.001 to 85 parts by mass, and still more preferably 0.001 to 70 parts by mass with respect to 100 parts by mass of the aromatic hydrocarbon formaldehyde resin. Part.
- the acidic catalyst may be charged all at once or charged in parts.
- the water that can be used for the treatment is not particularly limited as long as it can be used industrially, and examples thereof include tap water, distilled water, ion-exchanged water, pure water, and ultrapure water.
- the amount of water used is preferably 0.1 to 10000 parts by mass, more preferably 1 to 5000 parts by mass, and even more preferably 10 to 3000 parts by mass with respect to 100 parts by mass of the aromatic hydrocarbon formaldehyde resin.
- the treatment time is preferably 0.5 to 20 hours, more preferably 1 to 15 hours, and further preferably 2 to 10 hours. By setting the treatment time within the above range, a resin having the desired properties tends to be obtained economically and industrially.
- the treatment temperature is preferably 80 to 300 ° C, more preferably 85 to 270 ° C, and further preferably 90 to 240 ° C. By setting the treatment temperature within the above range, a resin having the desired properties tends to be obtained economically and industrially.
- the acidic catalyst is completely removed by washing with water, and the two phases are separated by standing, and the resin phase and the aqueous phase are oil phases. Then, the added solvent and the like are removed by a general method such as distillation to obtain a deacetal-bonded aromatic hydrocarbon formaldehyde resin (acid-treated resin).
- the deacetal-bonded aromatic hydrocarbon formaldehyde resin has a lower oxygen concentration and a higher softening point than the aromatic hydrocarbon formaldehyde resin.
- the amount of the acidic catalyst used is 0.05 parts by mass with respect to 100 parts by mass of the aromatic hydrocarbon formaldehyde resin
- the amount of water used is 2000 parts by mass with respect to 100 parts by mass of the aromatic hydrocarbon formaldehyde resin.
- Step (c) is a step of obtaining a modified resin by treating the acid-treated resin obtained in step (b) with an acidic catalyst and a compound represented by the following formula (3).
- Modified resin modified deacetal bonded aromatic hydrocarbon formaldehyde resin
- the modified resin used in this embodiment is a modification of the deacetal-bonded aromatic hydrocarbon formaldehyde resin (acid-treated resin) and the compound represented by the formula (3) by heating in the presence of an acidic catalyst. Is obtained.
- the modified resin is also referred to as “modified deacetal-bonded aromatic hydrocarbon formaldehyde resin”.
- X independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group
- Y 3 independently represents one having 1 to 10 carbon atoms.
- An alkyl group, an aryl group having 6 to 10 carbon atoms or a cyclohexyl group, p represents a number of 1 to 3, s represents a number of 0 to 3, and B represents a number of 0 to 3)
- X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group from the viewpoint of production.
- Y 3 is preferably an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclohexyl group.
- p is preferably 1 to 2
- s is preferably 0 to 2.
- Examples of the compound represented by the formula (3) include phenol, methoxyphenol, benzoxyphenol, catechol, resorcinol, hydroquinone, cresol, phenylphenol, naphthol, methoxynaphthol, benzoxynaphthol, dihydroxynaphthalene, hydroxyanthracene, and methoxyanthracene. , Benzoxyanthracene, dihydroxyanthracene and the like.
- a phenol derivative containing a conjugated structure involving at least two unshared electron pairs of a benzene ring is preferable because of excellent thermal decomposition resistance, and phenylphenol, naphthol, methoxynaphthol, benzoxynaphthol, dihydroxynaphthalene, hydroxy Anthracene, methoxyanthracene, benzoxyanthracene, and dihydroxyanthracene are more preferable.
- a compound having a hydroxy group is preferable because of its excellent crosslinkability with an acid crosslinking agent, and phenylphenol, naphthol, dihydroxynaphthalene, hydroxyanthracene, and dihydroxyanthracene are more preferable.
- the amount of the compound represented by the formula (3) is preferably 0.1 to 5 moles per mole of oxygen contained in the deacetal-bonded aromatic hydrocarbon formaldehyde resin (acid-treated resin).
- the amount is preferably 0.2 to 4 mol, more preferably 0.3 to 3 mol.
- the modification treatment is usually performed at normal pressure in the presence of an acidic catalyst, and heated at reflux or higher (usually 80 to 300 ° C.) or higher while distilling off generated water.
- the pressure may be normal pressure or increased pressure.
- an inert gas such as nitrogen, helium, or argon may be passed through the system.
- a solvent inert to the condensation reaction can also be used.
- the solvent include aromatic hydrocarbons such as toluene, ethylbenzene and xylene; saturated aliphatic hydrocarbons such as heptane and hexane; alicyclic hydrocarbons such as cyclohexane; ethers such as dioxane and dibutyl ether; 2-propanol Alcohols such as methyl isobutyl ketone; carboxylic acid esters such as ethyl propionate; carboxylic acids such as acetic acid.
- the acidic catalyst that can be used for the modification treatment can be appropriately selected from known inorganic acids and organic acids.
- inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid; oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluene
- Organic acids such as sulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid; zinc chloride, aluminum chloride, iron chloride, trifluoride
- Lewis acids such as boron
- solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic
- sulfuric acid oxalic acid, citric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, and phosphotungstic acid are preferable from the viewpoint of production.
- the amount of the acidic catalyst used is preferably 0.0001 to 100 parts by mass, more preferably 0.001 to 85 parts by mass with respect to 100 parts by mass of the deacetal-bonded aromatic hydrocarbon formaldehyde resin (acid-treated resin). More preferably, it is 0.001 to 70 parts by mass.
- the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 15 hours, and further preferably 2 to 10 hours. By making reaction time into the said range, it exists in the tendency which can obtain resin which has the target property economically and industrially.
- the reaction temperature is preferably 80 to 300 ° C, more preferably 85 to 270 ° C, and further preferably 90 to 240 ° C. By setting the reaction temperature within the above range, a resin having the desired properties tends to be obtained economically and industrially.
- the acidic catalyst is completely removed by washing with water, and the two phases are separated by standing, and the resin phase and the aqueous phase are oil phases. Then, the added solvent and / or unreacted raw material is removed by a general method such as distillation to obtain a modified deacetal-bonded aromatic hydrocarbon formaldehyde resin.
- the modified deacetal-bonded aromatic hydrocarbon formaldehyde resin has improved thermal decomposition resistance as compared with a modified aromatic hydrocarbon formaldehyde resin obtained by directly modifying the aromatic hydrocarbon formaldehyde resin without acid treatment.
- the modified deacetal-bonded aromatic hydrocarbon formaldehyde resin has higher heat decomposability and hydroxyl value than the deacetal-bonded aromatic hydrocarbon formaldehyde resin.
- the amount of the acidic catalyst used is 0.05 parts by mass with respect to 100 parts by mass of the deacetal-bonded aromatic hydrocarbon formaldehyde resin, and the reaction time is 5 hours and the reaction temperature is 200 ° C.
- the thermal decomposition resistance is 1 to About 50%
- the hydroxyl value [mgKOH / g] increases by about 1 to 300.
- Step (d) is a step of obtaining an epoxy resin by reacting the modified resin obtained in step (c) with epihalohydrin.
- Epoxy resin The epoxy resin in the present embodiment is obtained by reacting the modified deacetal-bonded aromatic hydrocarbon formaldehyde resin with epihalohydrin, the phenolic hydroxyl group of the modified deacetal-bonded aromatic hydrocarbon formaldehyde resin, epihalohydrin, and Can be obtained by reacting and epoxidizing by a known method. Specifically, for example, the reaction can be carried out according to the method described in JP-A-2009-108147.
- the epoxy resin composition in this embodiment contains the epoxy resin in this embodiment mentioned above.
- the epoxy resin composition may contain an epoxy resin other than the epoxy resin in the present embodiment, and such an epoxy resin is used for a laminated board, a sealing resin, an adhesive, a paint, and the like.
- a publicly known thing can be used, and what is generally used conventionally can be used, without limiting in particular, in the range which does not impair the effect of the present invention.
- the epoxy resin that can be used by being mixed with the epoxy resin in the present embodiment is not particularly limited.
- a novolac type epoxy resin a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, Examples thereof include phenol aralkyl type epoxy resins.
- bisphenol A bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxy
- the proportion of the epoxy resin of the present embodiment in the total epoxy resin is preferably 30% by mass or more, and more preferably 40% by mass or more. However, when the epoxy resin of this embodiment is used as a modifier for the epoxy resin composition, it is preferably added in a proportion of 1 to 30% by mass.
- curing agent, etc. can be mix
- a hardening accelerator and a catalyst you may use what is generally used for an epoxy resin, such as imidazoles or imidazolines, amines.
- the blending amount of the curing accelerator and the catalyst can be used within a range that does not impair the effects of the present invention, but is usually required within a range of 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the epoxy resin. Depending on the use.
- curing agent various known curing agents can be used depending on the use of the epoxy resin composition.
- the curing agent for sealing include novolak type phenol resins.
- the curing agent for the laminate include dicyandiamide and the like, and may be used in combination with the above catalyst.
- the curing agent for casting and filament winding include acid anhydrides such as phthalic anhydride.
- the curing agent for adhesives and anticorrosion coatings include low-temperature curing curing agents such as aromatic amines such as metaxylenediamine, aliphatic amines, and polyamines.
- the blending amount of the curing agent can be used within a range that does not impair the effects of the present invention, but is usually preferably used within a range of 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. . When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
- the epoxy resin composition is applied or impregnated on a predetermined substrate and then dried to produce a B-stage prepreg.
- a plurality of sheets are overlapped, and copper foils are further overlapped appropriately, and are manufactured by pressurizing and heating.
- glass fiber cloth is generally used as the reinforcing substrate, but in addition, aromatic polyamide fiber, aromatic polyester fiber, aromatic polyesterimide fiber, and the like can be used. Polyester, aromatic polyamide, aromatic polyester fiber, aromatic polyesterimide fiber and the like can also be used.
- the blending amount of the reinforcing substrate can be used within a range that does not impair the effects of the present invention, but is usually used in a range of 0.05 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin composition, From the viewpoint of flame retardancy and heat resistance of the cured product, it is preferably used in the range of 0.05 to 20 parts by mass.
- Application and impregnation to the reinforcing substrate are carried out under normal conditions, for example, about room temperature to 60 ° C., and dried at 100 ° C. to 180 ° C. for 3 minutes to 20 minutes to obtain a B-stage prepreg.
- the heating and pressurization is usually performed by appropriately selecting from a temperature range of 120 ° C. to 230 ° C., a pressure of 5 kg / cm 2 to 150 kg / cm 2 , and a range of 30 minutes to 240 minutes.
- the epoxy resin composition in the present embodiment is used as a sealing resin, it is usually difficult to use inorganic fillers such as silica, mold release agents such as carnauba wax, coupling agents such as epoxy silane, antimony trioxide, and halogen compounds.
- Additives such as a flame retardant are selected according to the purpose of use, added to the epoxy resin composition, and heated and kneaded using a biaxial kneader, a heat roll, a Hensyl mixer, or the like. Further, the obtained molded powder is appropriately tableted, and is first cured at 20 kg / cm 2 to 100 kg / cm 2 and 150 ° C. to 200 ° C. by compression or transfer molding using a mold, and then 180 Post-curing is performed for 2 hours to 12 hours at a temperature of 230 ° C. to 230 ° C.
- the above additives may be used alone or in combination of two or more.
- the additive can be used in a range that does not impair the effects of the present invention, but is usually used in the range of 0 to 95% by mass in the epoxy resin composition, from the viewpoint of flame retardancy and mechanical strength. , Preferably 50% by mass or more, more preferably 70% by mass or more.
- the epoxy resin composition in the present embodiment is excellent in heat resistance, high adhesiveness, moisture resistance, plasticity during heating, stress relaxation, etc., and further excellent in electrical performance, particularly high frequency characteristics. Therefore, in addition to the above, it can be suitably used as a resin composition for adhesion and heat-resistant coating.
- Carbon and oxygen concentrations (mass%) in the resin were measured by organic elemental analysis.
- the softening point of the resin was measured according to JIS-K5601.
- Example 1 Preparation of naphthalene formaldehyde resin
- 150 g of a mass% formalin aqueous solution (2 mol as formaldehyde, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 79.7 g of 98 mass% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged, stirred at 100 ° C. under normal pressure, and refluxed for 6 hours.
- the carbon concentration was 86.4% by mass
- the oxygen concentration was 8.0% by mass (the number of moles of oxygen contained per 1 g of resin was 0.0050 mol / g).
- the softening point was 84 ° C. and the hydroxyl value was 25 mgKOH / g.
- the carbon concentration was 87.9% by mass and the oxygen concentration was 5.9% by mass (the number of moles of oxygen contained per 1 g of resin was 0.0037 mol / g).
- the softening point was 107 ° C. and the hydroxyl value was 32 mgKOH / g.
- Example 2 Manufacture of copper-clad laminate
- 30 parts of the epoxy resin obtained in Example 1 was blended with 70 parts of a brominated epoxy compound (manufactured by Tohto Kasei Co., Ltd., product number: FX132, epoxy equivalent 485 WPE), and further 3.1 parts of dicyandiamide (abbreviated DICY) as a curing agent
- An epoxy resin composition was prepared by adding 0.08 part of 2-ethyl-4-methylimidazole (abbreviation 2E4MZ) as a catalyst, 32 parts of methyl ethyl ketone and 8 parts of dimethylformamide as a solvent.
- 2E4MZ 2-ethyl-4-methylimidazole
- the resin composition was impregnated into a glass cloth (# 7628-SV657, 0.2 mm thickness) and dried in a dryer at 150 ° C. for 15 minutes to obtain a prepreg. 4 sheets of this prepreg are stacked, both sides of 18 ⁇ m and 35 ⁇ m roughened copper foils are stacked, and pressure forming is performed at a pressure of 80kg / cm 2 and a temperature of 170 ° C for 90 minutes. I got a plate.
- the obtained double-sided copper clad laminate was tested in accordance with JIS S-6481, K-6911, and as a result, it was confirmed that it had high heat resistance, low water absorption, solder crack resistance, and high adhesion.
- Example 3 Manufacture of resin composition for semiconductor encapsulation 60 parts of the epoxy resin obtained in Example 1 was blended with 20 parts of a brominated phenol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name: BREN, epoxy equivalent 285), and bisphenol A novolac (as a curing agent) Dainippon Ink Co., Ltd., product name: LF7911) 41 parts, 2,4,6-tris (diaminomethyl) phenol (abbreviation DMP-30) 1 part as a curing accelerator, carnauba wax 2 parts as a release agent, The binder was pulverized and mixed.
- ⁇ -glycidoxypropyltrimethoxysilane manufactured by Nippon Unicar Co., Ltd., product name: A-187
- carbon black 1 part
- antimony trioxide powder 5 parts
- a filler composed of 350 parts of synthetic silica powder as a filler was mixed with a Hensyl mixer.
- roll kneading at 70 to 80 ° C. for 10 minutes, coarse pulverization, and tableting were performed to obtain a resin composition for semiconductor encapsulation.
- the obtained resin composition was transfer-molded on a mold having an upper mold with an aluminum foil attached at 180 ° C. for 2 minutes at 70 kg / cm 2 to obtain a cured resin test piece.
- the workability during molding was good, and high heat resistance and high moisture resistance. Furthermore, it was confirmed that no cracks were generated due to the cold-resistant cycle.
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Abstract
Description
[1]
以下の工程(a)~(d)を経て得られるエポキシ樹脂。
(a):下記式(1)及び/又は(2)で示される化合物とホルムアルデヒドとを触媒の存在下で反応させることにより芳香族炭化水素ホルムアルデヒド樹脂を得る工程、
(b):工程(a)において得られた芳香族炭化水素ホルムアルデヒド樹脂を、酸性触媒及び水を用いて処理することにより酸性処理した樹脂を得る工程、
(c):工程(b)において得られた酸性処理した樹脂を、酸性触媒及び下記式(3)で示される化合物を用いて処理することにより変性樹脂を得る工程、
(d):工程(c)において得られた変性樹脂を、エピハロヒドリンと反応させることによりエポキシ樹脂を得る工程。
[2]
前記式(1)で示される化合物が、ベンゼン、トルエン、キシレン、メシチレン、エチルベンゼン、プロピルベンゼン、デシルベンゼン、シクロヘキシルベンゼン、ビフェニル、メチルビフェニル、ナフタレン、メチルナフタレン、ジメチルナフタレン、エチルナフタレン、アントラセン、メチルアントラセン、ジメチルアントラセン、エチルアントラセン及びビナフチルからなる群より選ばれる少なくとも1種である、上記[1]記載のエポキシ樹脂。
[3]
前記式(2)で示される化合物が、フェナントレン、メチルフェナントレン、ジメチルフェナントレン、エチルフェナントレン、デシルフェナントレン、シクロヘキシルフェナントレン、フェニルフェナントレン及びナフチルフェナントレンからなる群より選ばれる少なくとも1種である、上記[1]又は[2]記載のエポキシ樹脂。
[4]
前記式(3)で示される化合物が、フェノール、メトキシフェノール、ベンゾキシフェノール、カテコール、レゾルシノール、ヒドロキノン、クレゾール、フェニルフェノール、ナフトール、メトキシナフトール、ベンゾキシナフトール、ジヒドロキシナフタレン、ヒドロキシアントラセン、メトキシアントラセン、ベンゾキシアントラセン及びジヒドロキシアントラセンからなる群より選ばれる少なくとも1種である、上記[1]~[3]のいずれか記載のエポキシ樹脂。
[5]
前記工程(b)において、前記酸性触媒の使用量が前記芳香族炭化水素ホルムアルデヒド樹脂100質量部に対して0.0001~100質量部であり、前記水の使用量が前記芳香族炭化水素ホルムアルデヒド樹脂100質量部に対して0.1~10000質量部である、上記[1]~[4]のいずれか記載のエポキシ樹脂。
[6]
前記工程(c)において、前記式(3)で示される化合物の使用量が前記酸性処理した樹脂中の含有酸素モル数1モルに対して0.1~5モルである、上記[1]~[5]のいずれか記載のエポキシ樹脂。
[7]
上記[1]~[6]のいずれか記載のエポキシ樹脂を含有するエポキシ樹脂組成物。
[8]
上記[7]記載のエポキシ樹脂組成物を硬化してなる硬化物。
[9]
上記[1]~[6]のいずれか記載のエポキシ樹脂を含有する銅張積層板。
[10]
上記[1]~[6]のいずれか記載のエポキシ樹脂を含有する半導体封止用樹脂組成物。
[11]
以下の工程(a)~(d)を含むエポキシ樹脂の製造方法。
(a):下記式(1)及び/又は(2)で示される化合物とホルムアルデヒドとを触媒の存在下で反応させることにより芳香族炭化水素ホルムアルデヒド樹脂を得る工程、
(b):工程(a)において得られた芳香族炭化水素ホルムアルデヒド樹脂を、酸性触媒及び水を用いて処理することにより酸性処理した樹脂を得る工程、
(c):工程(b)において得られた酸性処理した樹脂を、酸性触媒及び下記式(3)で示される化合物を用いて処理することにより変性樹脂を得る工程、
(d):工程(c)において得られた変性樹脂を、エピハロヒドリンと反応させることによりエポキシ樹脂を得る工程。
以下の工程(a)~(d)を経て得られるエポキシ樹脂である。
(a):上記式(1)及び/又は(2)で示される化合物とホルムアルデヒドとを触媒の存在下で反応させることにより芳香族炭化水素ホルムアルデヒド樹脂を得る工程、
(b):工程(a)において得られた芳香族炭化水素ホルムアルデヒド樹脂を、酸性触媒及び水を用いて処理することにより酸性処理した樹脂を得る工程、
(c):工程(b)において得られた酸性処理した樹脂を、酸性触媒及び上記式(3)で示される化合物を用いて処理することにより変性樹脂を得る工程、
(d):工程(c)において得られた変性樹脂を、エピハロヒドリンと反応させることによりエポキシ樹脂を得る工程。
工程(a)は、式(1)及び/又は(2)で示される化合物とホルムアルデヒドを触媒の存在下で反応させることにより芳香族炭化水素ホルムアルデヒド樹脂を得る工程である。
本実施形態において用いられる芳香族炭化水素ホルムアルデヒド樹脂の製造方法としては、特に制限されるものではなく、下記式(1)及び/又は(2)で示される化合物から公知の方法を適用することにより得ることができる。
工程(b)は、工程(a)において得られた芳香族炭化水素ホルムアルデヒド樹脂を、酸性触媒及び水を用いて処理することにより酸性処理した樹脂を得る工程である。
本実施形態で用いられる酸性処理した樹脂は、前述の芳香族炭化水素ホルムアルデヒド樹脂を、酸性触媒及び水を使用して処理することにより得ることができる。酸性処理した樹脂は、ナフタレン環が、―(CH2)l―及び/又はCH2A―で架橋されている。ここで、Aは-(OCH2)m-を、lは1~10の数を、mは0~10の数をそれぞれ表す。酸性触媒及び水を使用して処理することによりナフタレン環を介さないオキシメチレン等同士の結合が減り、l及び/又はmが少なくなる。即ち、ナフタレン環を介する位置にあるアセタール結合が減少する。
工程(c)は、工程(b)において得られた酸性処理した樹脂を、酸性触媒及び下記式(3)で示される化合物を用いて処理することにより変性樹脂を得る工程である。
本実施形態において用いられる変性樹脂は、前記脱アセタール結合芳香族炭化水素ホルムアルデヒド樹脂(酸性処理した樹脂)と、式(3)で示される化合物とを、酸性触媒の存在下で加熱し変性させることにより得られる。本明細書においては、該変性樹脂を「変性脱アセタール結合芳香族炭化水素ホルムアルデヒド樹脂」とも言う。
工程(d)は、工程(c)において得られた変性樹脂を、エピハロヒドリンと反応させることによりエポキシ樹脂を得る工程である。
本実施形態におけるエポキシ樹脂は、上記変性脱アセタール結合芳香族炭化水素ホルムアルデヒド樹脂をエピハロヒドリンと反応させることによって得られるものであり、変性脱アセタール結合芳香族炭化水素ホルムアルデヒド樹脂のフェノール性水酸基と、エピハロヒドリンとを公知の方法で反応させ、エポキシ化させることにより得られる。具体的には、例えば、特開2009-108147号公報に記載された方法に従って反応させることができる。
本実施形態におけるエポキシ樹脂組成物は、上述した本実施形態におけるエポキシ樹脂を含有するものである。エポキシ樹脂組成物には、本実施形態におけるエポキシ樹脂以外のエポキシ樹脂を含有していてもよく、そのようなエポキシ樹脂としては、積層板や、封止用樹脂、接着剤、塗料等に用いられる公知のものを用いることができ、本発明の効果を損なわない範囲で、従来一般に使用されているものを特に限定することなく用いることができる。
硬化促進剤及び触媒としては、イミダゾール類又はイミダゾリン類、アミン類等の、一般にエポキシ樹脂に用いられるものを使用してもよい。代表的なものとしては、2-エチル-4-メチルイミダゾール、2,4,6-トリス(ジアミノメチル)フェノール(略称 DMP-30)などが挙げられる。
硬化促進剤及び触媒の配合量については、本発明の効果を損なわない範囲で用いることができるが、通常、エポキシ樹脂100質量部に対して0.1~5.0質量部の範囲で、必要に応じて用いられる。
ゲル浸透クロマトグラフィー(GPC)分析により、ポリスチレン換算の質量平均分子量(Mw)、数平均分子量(Mn)を求め、分散度(Mw/Mn)を求めた。
装置:Shodex GPC-101型(昭和電工(株)製)
カラム:LF-804×3
溶離液:THF 1ml/min
温度:40℃
有機元素分析により樹脂中の炭素及び酸素濃度(質量%)を測定した。また、樹脂1g当たりの含有酸素モル数を下記計算式に従って算出した。
装置:CHNコーダーMT-6(ヤナコ分析工業(株)製)
計算式:樹脂1g当たりの含有酸素モル数(mol/g)=酸素濃度(質量%)/16
JIS-K5601に従って樹脂の軟化点を測定した。
JIS-K1557に従って樹脂の水酸基価を測定した。
JIS-K0064に従って樹脂の融点を測定した。
(ナフタレンホルムアルデヒド樹脂の調製)
ジムロート冷却管、温度計及び攪拌翼を備えた、底抜きが可能な内容積1Lの四つ口フラスコに、窒素気流中、ナフタレン64.1g(0.5mol、関東化学(株)製)、40質量%ホルマリン水溶液150g(ホルムアルデヒドとして2mol、三菱ガス化学(株)製)及び98質量%硫酸(関東化学(株)製)79.7gを仕込み、常圧下、100℃で撹拌、還流しながら6時間反応させた。希釈溶媒としてエチルベンゼン(関東化学(株)製)150gを加え、静置後、下相の水相を除去した。さらに、中和及び水洗を行い、エチルベンゼン及び未反応のナフタレンを減圧下に留去し、淡黄色固体のナフタレンホルムアルデヒド樹脂69.7gを得た。
GPC測定の結果、Mn:459、Mw:882、Mw/Mn:1.92であった。有機元素分析の結果、炭素濃度は86.4質量%、酸素濃度は8.0質量%(樹脂1g当たりの含有酸素モル数は0.0050mol/g)であった。軟化点は84℃で、水酸基価は25mgKOH/gであった。
ジムロート冷却管を設置したディーンスターク管、温度計及び攪拌翼を備えた内容積0.5Lの四つ口フラスコに、上記ナフタレンホルムアルデヒド樹脂50.0g、エチルベンゼン(関東化学(株)製)50g及びメチルイソブチルケトン(関東化学(株)製)50gを仕込んで120℃で溶解後、撹拌しながら水蒸気流通下でパラトルエンスルホン酸(和光純薬工業(株)製)2.5mgを加えて反応を開始した。2時間後、さらにパラトルエンスルホン酸(和光純薬工業(株)製)1.3mgを加えてさらに3時間(計5時間)反応させた。エチルベンゼン(関東化学(株)製)150gで希釈後、中和及び水洗を行い、溶剤を減圧下に除去して、淡赤色固体の酸性処理した樹脂(脱アセタール結合ナフタレンホルムアルデヒド樹脂)40.9gを得た。
GPC測定の結果、Mn:290、Mw:764、Mw/Mn:2.63であった。有機元素分析の結果、炭素濃度は87.9質量%、酸素濃度は5.9質量%(樹脂1g当たりの含有酸素モル数は0.0037mol/g)であった。軟化点は107℃で、水酸基価は32mgKOH/gであった。
リービッヒ冷却管、温度計及び攪拌翼を備えた内容積0.3Lの四つ口フラスコに、窒素気流下で、上記酸性処理した樹脂40.5g(含有酸素モル数0.15mol)、1-ナフトール43.3g(0.30mol、東京化成工業(株)製)を仕込み、120℃で加熱溶融させた後、撹拌しながらパラトルエンスルホン酸(和光純薬工業(株)製)2.3mgを加え、反応を開始した。直ちに190℃まで昇温して3時間攪拌保持した後、パラトルエンスルホン酸(和光純薬工業(株)製)1.5mgを加え、さらに220℃まで昇温させて2時間反応させた(計5時間)。混合溶剤(メタキシレン(三菱ガス化学(株)製)/メチルイソブチルケトン(関東化学(株)製)=1/1(質量比))180gで希釈後、中和及び水洗を行い、溶剤を減圧下に除去して、黒褐色固体の変性樹脂(変性脱アセタール結合ナフタレンホルムアルデヒド樹脂)48.1gを得た。
GPC分析の結果、Mn:493、Mw:750、Mw/Mn:1.52であった。有機元素分析の結果、炭素濃度は89.9質量%、酸素濃度は4.9質量%であった。水酸基価は192mgKOH/gであった。
リービッヒ冷却管、温度計及び攪拌翼を備えた内容積0.3Lの四つ口フラスコに、窒素気流下で、上記変性樹脂40.0g、水酸化ナトリウム6.4gを水60.0gに溶解し、強く撹拌しながら50℃に加熱させた後、エピクロルヒドリン15.0gを撹拌混合し、温度を80℃に保ち6時間反応させた。反応終了後、未反応のエピクロルヒドリンを減圧除去した後、キシレンを添加して撹拌、静置し、水を除去した。再び純水を添加して洗浄し、水を除去する操作を繰り返して精製した。ついで減圧蒸留にてキシレンを除去し、黒褐色固体のエポキシ樹脂40.1gを得た。
GPC分析の結果、Mn:720、Mw:1100、Mw/Mn:1.53であった。また、樹脂の融点は124℃であった。
酸性処理を行わなかったこと以外は実施例1と同様にして黒褐色固体のエポキシ樹脂40.1gを得た。
GPC分析の結果、Mn:700、Mw:980、Mw/Mn:1.96であった。また、樹脂の融点は114℃であった。
実施例1と同様にして酸性処理した樹脂を調製した。得られた酸性処理した樹脂を用いて、変性処理を行わずにエピクロルヒドリンと撹拌混合したが、反応は進行しなかった。
(銅張積層板の製造)
ブロム化エポキシ化合物(東都化成社製、品番;FX132,エポキシ当量485WPE)70部に、実施例1で得たエポキシ樹脂30部を配合し、更に硬化剤としてジシアンジアミド(略号 DICY)3.1部、触媒として2-エチル-4-メチルイミダゾール(略号 2E4MZ)0.08部、溶媒としてメチルエチルケトン32部、ジメチルホルムアミド8部を加えてエポキシ樹脂組成物を調製した。
該樹脂組成物をガラス布(#7628-SV657,0.2mm厚)に含浸させ、150℃の乾燥機中で15分間乾燥させてプリプレグを得た。このプリプレグを4枚重ね、その両面に18μm及び35μmの両面粗面化銅箔を重ね、圧力80kg/cm2、温度170℃で90分間の積層成形を行ない、0.8mm厚の両面銅張積層板を得た。得られた両面銅張積層板の試験をJIS S C-6481,K-6911に従って実施した結果、高耐熱性、低吸水性、耐半田クラック性、高接着性を有することが確認された。
(半導体封止用樹脂組成物の製造)
ブロム化フェノールノボラック型エポキシ樹脂(日本化薬(株)製、品名;BREN,エポキシ当量285)20部に、実施例1で得たエポキシ樹脂60部を配合し、更に硬化剤としてビスフェノールAノボラック(大日本インキ社製、品名;LF7911)41部、硬化促進剤として2,4,6-トリス(ジアミノメチル)フェノール(略称DMP-30)1部、離型剤としてカルナバワックス2部を配合し、バインダーの粉砕及び混合を行った。また、カップリング剤として、γ-グリシドキシプロピルトリメトキシシラン(日本ユニカー社製、品名;A-187)1部、着色材としてカーボンブラック1部、難燃助材として三酸化アンチモン粉末5部、充填材として合成シリカ粉末350部からなるフィラーをヘンシル・ミキサーにて混合した。上記で製造したバインダーとフィラーとを用いて、70~80℃で10分間ロール混練し、粗粉砕した後、タブレット化して、半導体封止用樹脂組成物を得た。
得られた樹脂組成物を、上型にアルミニウム箔を装着した金型に180℃、2分、70kg/cm2の条件でトランスファー成形することにより硬化樹脂試験片を得た。得られた試験片について、成形時の作業性、耐熱性、耐湿性、耐冷熱サイクルによるクラック発生の有無の試験を実施した結果、成形時の作業性が良好であり、高耐熱性、高耐湿性を有し、さらに、耐冷熱サイクルによるクラック発生がないことが確認された。
Claims (11)
- 以下の工程(a)~(d)を経て得られるエポキシ樹脂。
(a):下記式(1)及び/又は(2)で示される化合物とホルムアルデヒドとを触媒の存在下で反応させることにより芳香族炭化水素ホルムアルデヒド樹脂を得る工程、
(b):工程(a)において得られた芳香族炭化水素ホルムアルデヒド樹脂を、酸性触媒及び水を用いて処理することにより酸性処理した樹脂を得る工程、
(c):工程(b)において得られた酸性処理した樹脂を、酸性触媒及び下記式(3)で示される化合物を用いて処理することにより変性樹脂を得る工程、
(d):工程(c)において得られた変性樹脂を、エピハロヒドリンと反応させることによりエポキシ樹脂を得る工程。
- 前記式(1)で示される化合物が、ベンゼン、トルエン、キシレン、メシチレン、エチルベンゼン、プロピルベンゼン、デシルベンゼン、シクロヘキシルベンゼン、ビフェニル、メチルビフェニル、ナフタレン、メチルナフタレン、ジメチルナフタレン、エチルナフタレン、アントラセン、メチルアントラセン、ジメチルアントラセン、エチルアントラセン及びビナフチルからなる群より選ばれる少なくとも1種である、請求項1記載のエポキシ樹脂。
- 前記式(2)で示される化合物が、フェナントレン、メチルフェナントレン、ジメチルフェナントレン、エチルフェナントレン、デシルフェナントレン、シクロヘキシルフェナントレン、フェニルフェナントレン及びナフチルフェナントレンからなる群より選ばれる少なくとも1種である、請求項1又は2記載のエポキシ樹脂。
- 前記式(3)で示される化合物が、フェノール、メトキシフェノール、ベンゾキシフェノール、カテコール、レゾルシノール、ヒドロキノン、クレゾール、フェニルフェノール、ナフトール、メトキシナフトール、ベンゾキシナフトール、ジヒドロキシナフタレン、ヒドロキシアントラセン、メトキシアントラセン、ベンゾキシアントラセン及びジヒドロキシアントラセンからなる群より選ばれる少なくとも1種である、請求項1~3のいずれか1項記載のエポキシ樹脂。
- 前記工程(b)において、前記酸性触媒の使用量が前記芳香族炭化水素ホルムアルデヒド樹脂100質量部に対して0.0001~100質量部であり、前記水の使用量が前記芳香族炭化水素ホルムアルデヒド樹脂100質量部に対して0.1~10000質量部である、請求項1~4のいずれか1項記載のエポキシ樹脂。
- 前記工程(c)において、前記式(3)で示される化合物の使用量が前記酸性処理した樹脂中の含有酸素モル数1モルに対して0.1~5モルである、請求項1~5のいずれか1項記載のエポキシ樹脂。
- 請求項1~6のいずれか1項記載のエポキシ樹脂を含有するエポキシ樹脂組成物。
- 請求項7記載のエポキシ樹脂組成物を硬化してなる硬化物。
- 請求項1~6のいずれか1項記載のエポキシ樹脂を含有する銅張積層板。
- 請求項1~6のいずれか1項記載のエポキシ樹脂を含有する半導体封止用樹脂組成物。
- 以下の工程(a)~(d)を含むエポキシ樹脂の製造方法。
(a):下記式(1)及び/又は(2)で示される化合物とホルムアルデヒドとを触媒の存在下で反応させることにより芳香族炭化水素ホルムアルデヒド樹脂を得る工程、
(b):工程(a)において得られた芳香族炭化水素ホルムアルデヒド樹脂を、酸性触媒及び水を用いて処理することにより酸性処理した樹脂を得る工程、
(c):工程(b)において得られた酸性処理した樹脂を、酸性触媒及び下記式(3)で示される化合物を用いて処理することにより変性樹脂を得る工程、
(d):工程(c)において得られた変性樹脂を、エピハロヒドリンと反応させることによりエポキシ樹脂を得る工程。
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JPH10168147A (ja) * | 1996-12-06 | 1998-06-23 | Mitsubishi Gas Chem Co Inc | 低粘度芳香族炭化水素ホルムアルデヒド樹脂 |
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JPH10168147A (ja) * | 1996-12-06 | 1998-06-23 | Mitsubishi Gas Chem Co Inc | 低粘度芳香族炭化水素ホルムアルデヒド樹脂 |
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