CN103958561B - Lacquer resins and employ the composition epoxy resin of this lacquer resins - Google Patents

Lacquer resins and employ the composition epoxy resin of this lacquer resins Download PDF

Info

Publication number
CN103958561B
CN103958561B CN201280052226.5A CN201280052226A CN103958561B CN 103958561 B CN103958561 B CN 103958561B CN 201280052226 A CN201280052226 A CN 201280052226A CN 103958561 B CN103958561 B CN 103958561B
Authority
CN
China
Prior art keywords
general formula
epoxy resin
lacquer resins
integer
carbonatoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201280052226.5A
Other languages
Chinese (zh)
Other versions
CN103958561A (en
Inventor
冈本慎司
藤永匡敏
木村绘梨奈
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Meiwa Plastic Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Meiwa Plastic Industries Ltd filed Critical Meiwa Plastic Industries Ltd
Publication of CN103958561A publication Critical patent/CN103958561A/en
Application granted granted Critical
Publication of CN103958561B publication Critical patent/CN103958561B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • 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
    • 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
    • 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
    • B32B5/28—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 impregnated with or embedded in a plastic substance
    • 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
    • C08G59/62—Alcohols or phenols
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • 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
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • 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
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • 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
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/76—Post-treatment crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/04—Epoxynovolacs
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Problem of the present invention is the lacquer resins providing a kind of composition epoxy resin and can be suitably used for this composition epoxy resin, this composition epoxy resin is for comprising the composition epoxy resin of lacquer resins (being more particularly phenol-naphthol novolac varnish resin) and epoxy resin, and this composition epoxy resin significantly improves thermotolerance and the resistance to flame of obtained cured article.Lacquer resins of the present invention is made up of the chemical structure represented with following general formula (1). (in formula, A represents 1 valency of 1 valency of following general formula (2) or the unit of divalent or general formula (3) or the unit of divalent independently of one another, n is the integer of 0 ~ 20, and R1 represents that carbonatoms is the alkyl of 1 ~ 8 independently of one another, p and q is the integer of 0 ~ 2 independently of one another.)。

Description

Lacquer resins and employ the composition epoxy resin of this lacquer resins
Technical field
The present invention relates to composition epoxy resin and be suitably used for the lacquer resins (phenolnovolakresin) of this composition epoxy resin.Composition epoxy resin of the present invention improves thermotolerance and the resistance to flame of obtained cured article.In addition, for composition epoxy resin of the present invention, because the solvability of the lacquer resins preferably used is excellent, is thus easily dissolved in solvent equably, thus the purposes of such as fabrication layer lamination can be suitably used for.
Background technology
The workability of composition epoxy resin is good, and its cured article has excellent electrical characteristic, thermotolerance, cementability, wet fastness etc., is therefore widely used in the fields such as electrical and electronic parts, structure material, caking agent, coating.
But, in recent years, along with the progress of the technology in the electric and electronic such as semiconductor-encapsulating material, plywood field, require to improve various characteristic further to composition epoxy resin.
Such as, owing to adopting unleaded scolding tin, Reflow Soldering temperature becomes higher, therefore requires the thermotolerance higher than currently available products to the composition epoxy resin used in the semiconductor packages such as plywood, interlayer dielectic, sealing material.In addition, as the countermeasure for environmental problem, require may to produce when not using burning the halogen of dioxin and under a cloudly improve resistance to flame (flame retardant resistance) when there is the fire retardants such as the antimony of carinogenicity.In addition, when using composition epoxy resin as the body material of plywood or interlayer dielectic, use by composition epoxy resin being dissolved in varnish in solvent, therefore to the solubility that composition epoxy resin requires in a solvent.
Patent Document 1 discloses a kind of phenol novolacs condensation body and comprise the composition epoxy resin of this phenol novolacs condensation body and epoxy resin, described phenol novolacs condensation body makes the mixture of the isomer of two (methoxymethyl) biphenyl and oxybenzene compound react to obtain, and the mixture of the isomer of described pair of (methoxymethyl) biphenyl synthesizes by making the reaction product obtained by the halogenating reaction of methoxymethyl benzene carry out dehalogenation linked reaction.For this phenol novolacs condensation body, as epoxy curing agent, its water absorbability, thermotolerance and pliability are excellent.But, the concrete disclosed phenol novolacs condensation body in this place is only the use of the mixture of the isomer of two (methoxymethyl) biphenyl, according to embodiment, the second-order transition temperature of the cured article formed by the composition epoxy resin comprising obtained phenol novolacs condensation body and epoxy resin is about 140 DEG C, and it also exists room for improvement in thermotolerance.
Patent Document 2 discloses a kind of phenol-naphthol novolac varnish condensation body and comprise the composition epoxy resin of this phenol-naphthol novolac varnish condensation body and epoxy resin, described phenol-naphthol novolac varnish condensation body is obtained by the condensation reaction of the biphenol compound of phenol and aphthols and two (methoxymethyl) biphenyl and so on.But the concrete disclosed phenol-naphthol novolac varnish condensation body in this place is also only the use of the mixture of the isomer of two (methoxymethyl) biphenyl as biphenol compound.Although this phenol-naphthol novolac varnish condensation body improves low water absorbable and thermotolerance compared with the phenol novolacs condensation body of patent documentation 1, but according to embodiment, the second-order transition temperature of the cured article formed by the composition epoxy resin comprising phenol-naphthol novolac varnish condensation body and epoxy resin is about 150 DEG C, and it also exists room for improvement in thermotolerance.
The mixture of the isomer preferably using specified proportion is disclosed as biphenol compound in patent documentation 1,2.But, in patent documentation 1,2 not concrete open and teaching when be used alone 4,4 '-bis-(methoxymethyl) biphenyl such 4, which kind of 4 '-body can have affect on thermotolerance, resistance to flame, solvability etc. as during biphenol compound.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 8-143648 publication
Patent documentation 2: Japanese Unexamined Patent Publication 9-176262 publication
Summary of the invention
The problem that invention will solve
The invention provides a kind of composition epoxy resin and the lacquer resins of this composition epoxy resin can be suitably used for, this composition epoxy resin is for comprising the composition epoxy resin of lacquer resins (being more particularly phenol-naphthol novolac varnish resin) and epoxy resin, and this composition epoxy resin significantly improves thermotolerance and the resistance to flame of obtained cured article.In addition, the invention provides a kind of composition epoxy resin and the lacquer resins of this composition epoxy resin can be suitably used for, this composition epoxy resin due to the solvability of lacquer resins preferably used excellent, thus be easily dissolved in solvent equably, thus the purposes of such as fabrication layer lamination can be suitably used for.
For the means of dealing with problems
The present invention relates to the following.
(1) lacquer resins, it is made up of the chemical structure represented with following general formula (1).
(in formula, A represents 1 valency of 1 valency of following general formula (2) or the unit of divalent or general formula (3) or the unit of divalent independently of one another, n is the integer of 0 ~ 20, and R1 represents that carbonatoms is the alkyl of 1 ~ 8 independently of one another, p and q is the integer of 0 ~ 2 independently of one another.)
Wherein, overall as lacquer resins, A is made up of 1 valency of following general formula (2) or both 1 valency of the unit of divalent and following general formula (3) or the unit of divalent.
(in formula, R2 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, i is the integer of 1 ~ 3, and j is the integer of 0 ~ 2, and i and j adds up to less than 4.)
(in formula, R3 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, k is the integer of 1 ~ 3, and l is the integer of 0 ~ 4, and k and l adds up to less than 6.)
(2) lacquer resins according to above-mentioned item 1, it is characterized in that, the ratio [unit of the unit/general formula (3) of general formula (2)] of the unit of described general formula (2) and the unit of described general formula (3) is in the scope of 10/90 ~ 90/10.
(3) lacquer resins according to above-mentioned item 1 or 2, is characterized in that, forms the composition represented with following general formula (4) in whole compositions of lacquer resins and counts less than 27% according to area ratio when being measured by HPLC.
(in formula, R1 represents that carbonatoms is the alkyl of 1 ~ 8 independently of one another, p and q is the integer of 0 ~ 2 independently of one another, R3 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, k is the integer of 1 ~ 3, l is the integer of 0 ~ 4, and k and l adds up to less than 6.)
(4) a kind of manufacture method of lacquer resins, it is characterized in that, make the phenol that represents with following general formula (5) and react with the biphenol compound represented with following general formula (7) with the aphthols that following general formula (6) represents.
(in formula, R2 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, i is the integer of 1 ~ 3, and j is the integer of 0 ~ 2, and i and j adds up to less than 4.)
(in formula, R3 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, k is the integer of 1 ~ 3, and l is the integer of 0 ~ 4, and k and l adds up to less than 6.)
(in formula, R1 represents that carbonatoms is the alkyl of 1 ~ 8 independently of one another, p and q is the integer of 0 ~ 2 independently of one another, and X represents that carbonatoms is alkoxyl group or the halogen atom of 1 ~ 4.)
(5) composition epoxy resin, it comprises lacquer resins (A) according to any one of above-mentioned item 1 ~ 3 and epoxy resin (B).
(6) composition epoxy resin according to above-mentioned item 5, is characterized in that, the second-order transition temperature of the cured article obtained is more than 155 DEG C, is preferably more than 170 DEG C, is more preferably more than 180 DEG C.
(7) composition epoxy resin according to above-mentioned item 5 or 6, is characterized in that, the flame retardant resistance based on UL-94 of the cured article obtained is V-0.
(8) a kind of composition epoxy resin, it is characterized in that, it comprises lacquer resins (A), epoxy resin (B) and solvent (C) according to any one of above-mentioned item 1 ~ 3, wherein, lacquer resins (A) and epoxy resin (B) are dissolved in solvent (C) equably.
(9) cured article, its be make in the composition epoxy resin of above-mentioned item 5 ~ 8 any one solidification.
(10) plywood, it uses the composition epoxy resin of above-mentioned item 8 to define matrix resin.
In addition, " independently of one another " refers to herein: when representing that the symbol of corresponding substituting group or numeral exists multiple, each symbol of multiple expression substituting group or numeral can be different substituting groups or numeral independently of one another.Such as, (R1) in described general formula (1) pin R1 and (R1) qin R1 can be identical alkyl, also can be the different alkyl of carbonatoms; And, as (R1) pin R1 when being multiple, each R1 can be identical alkyl respectively, also can be the different alkyl of carbonatoms.
In addition, in the present invention, as the measuring method of second-order transition temperature, measuring by two kinds of methods for the ease of comparing, when contingency can produce difference because of measuring method, preferentially utilizing the measuring method of Measurement of Dynamic Viscoelasticity device.
Invention effect
According to the present invention, a kind of composition epoxy resin can be provided and the lacquer resins of this composition epoxy resin can be suitably used for, this composition epoxy resin is for comprising the composition epoxy resin of lacquer resins (being more particularly phenol-naphthol novolac varnish resin) and epoxy resin, and this composition epoxy resin significantly improves thermotolerance and the resistance to flame of obtained cured article.In addition, according to the present invention, a kind of composition epoxy resin can be provided and the lacquer resins of this composition epoxy resin can be suitably used for, this composition epoxy resin due to the solvability of lacquer resins preferably used excellent, thus be easily dissolved in solvent equably, thus the purposes of such as fabrication layer lamination, interlayer dielectic can be suitably used for.
Accompanying drawing explanation
The HPLC figure of the reaction mixture before unreacting material composition is removed when Fig. 1 is reaction terminating in embodiment 1.
Fig. 2 is the HPLC figure of the lacquer resins obtained in embodiment 1.
The HPLC figure of the reaction mixture before unreacting material composition is removed when Fig. 3 is reaction terminating in embodiment 2.
Fig. 4 is the HPLC figure of the lacquer resins obtained in embodiment 2.
Embodiment
Lacquer resins of the present invention can by making the phenol that represents with following general formula (5) and reacting with the biphenol compound represented with following general formula (7) with the aphthols that following general formula (6) represents and obtain aptly.
(in formula, R2 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, i is the integer of 1 ~ 3, and j is the integer of 0 ~ 2, and i and j adds up to less than 4.)
(in formula, R3 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, k is the integer of 1 ~ 3, and l is the integer of 0 ~ 4, and k and l adds up to less than 6.)
(in formula, R1 represents that carbonatoms is the alkyl of 1 ~ 8 independently of one another, p and q is the integer of 0 ~ 2 independently of one another, and X represents that carbonatoms is alkoxyl group or the halogen atom of 1 ~ 4.)
As the phenol represented with general formula (5), as long as compound phenyl ring with more than one hydroxyl just, be not particularly limited, the substituting group such as alkyl, alkoxyl group can also be had.Such as, for phenol, Resorcinol, Resorcinol, cresols, ethylphenol, n-propyl phenol, isopropyl-phenol, tertiary propylphenol, octyl phenol, phenylphenol, methyl catechol, Pyrocatechol monoethyl ether (guethol), xylenol, methylethyl phenol, methyl butyl phenol, methylhexyl phenol, dipropyl phenol, dibutylphenol etc., be preferably phenol.These phenol can be one matter, also can be multiple mixture.
As the aphthols represented with general formula (6), as long as compound naphthalene nucleus with more than one hydroxyl just, be not particularly limited, the substituting group such as alkyl, alkoxyl group can also be had.Such as, for naphthyl alcohol, 2-Naphthol, dihydroxy naphthlene class, trihydroxynaphthalene class, methyl naphthols, ethyl naphthols, propyl group naphthols, allyl group naphthols, tertiary butyl naphthols, octyl group naphthols, methylethyl naphthols, methyl-propyl naphthols, methyl butyl naphthols, methylhexyl naphthols, dimethyl naphthols, diethyl naphthols, dibutyl naphthols etc., be preferably naphthyl alcohol.These aphthols can be one matter, also can be two or more mixtures.
As the biphenol compound represented with general formula (7), 4 can be listed aptly, 4 '-bis-(methoxymethyl) biphenyl, 4,4 '-bis-(ethoxyl methyl) biphenyl, 4,4 '-bis-(chloromethyl) biphenyl, 4,4 '-bis-(brooethyl) biphenyl, 4,4 '-bis-(methyl fluoride) biphenyl etc.These biphenol compounds can also have the alkyl alternatively base that carbonatoms is 1 ~ 8.These biphenol compounds can be one matter, also can be two or more mixtures.
When making phenol and aphthols and biphenol compound react, can not catalyzer be used, but usually use acid catalyst.As acid catalyst, the Friedel-Craft type catalyzer such as the organic acids such as oxalic acid, formic acid, acetic acid or sulfuric acid, tosic acid, ethyl sulfate are suitable.In addition, particularly use there is halogenated methyl biphenol compound as biphenol compound time, also can react aptly under the condition that there is not acid catalyst.
In the reaction, with regard to the mol ratio [(phenol and aphthols)/biphenol compound] of the total of the biphenol compound as raw material and phenol as raw material and aphthols, preferably the scope of 20 ~ 1.5, more preferably 6.0 ~ 2.0 is suitable.When mol ratio is less than 1.5, the viscosity of resin becomes too high, likely can damage operability; When mol ratio is more than 20, most product becomes low-molecular weight, thus the second-order transition temperature of the cured article obtained becomes insufficient, or unreacting material also remains in a large number, thus unfavorable economically.
In addition, with regard to regard to the phenol of raw material and the mol ratio [phenol/aphthols] of aphthols, preferably the scope of 10/90 ~ 90/10, more preferably 40/60 ~ 90/10 is suitable.By making as the phenol of raw material and the mol ratio of aphthols within the scope of this, as explained below, the unit of general formula (2) of phenol of resulting from that can make obtained lacquer resins is preferable range of the present invention with resulting from the ratio of unit of general formula (3) of aphthols.That is, if naphthols composition is very few, then the unit of the general formula (3) imported in resin reduces, thus is sometimes difficult to obtain sufficient thermotolerance.In addition, if naphthols composition is too much, then the unit of the general formula (3) imported in resin increases, and the unit represented by general formula (4) also increases, and solvent solubility thus can be caused impaired.
At 0 DEG C ~ 150 DEG C, 0.5 hour ~ 10 hours are carried out when reaction when there is not solvent or can exist water and/or organic solvent equal solvent usually, but in order to regulate the ratio of composition that forms lacquer resins and the polymerization degree etc., aptly the reaction conditions etc. of temperature of reaction, reaction times and so on is regulated.
In addition, preferably after termination of the reaction, unreacted phenol and aphthols etc. are under reduced pressure heated or injects ripple gas of not living and heat, distilled thus except going to system.In addition, acid catalyst can be removed by cleanings such as washings.
By this reaction, biphenol compound forms crosslinking structure and bonding between the multiple unit formed by phenol and/or aphthols, generates the lacquer resins formed by the chemical structure represented with general formula (1).
Therefore, in general formula (1), when the phenol represented with general formula (5) and general formula (6), aphthols constitute molecular end, the A in general formula (1) becomes 1 valency unit of general formula (2) and general formula (3); Under being entered intramolecular situation by group, the A in general formula (1) becomes the divalent unit of general formula (2) and general formula (3).
In addition, in the reaction, the n first generating general formula (1) is the composition of 0.Then, the composition that the part of the composition that the n generated is 0 is 0 with biphenol compound or the n that generates further reacts.Like this, generating n further is successively 1 and composition more than 1.On the other hand, be 1 and during the reaction of composition more than 1 carries out generating n, generate n be the reaction of the composition of 0 also in continuation, the thus aggregate of the Multiple components that the n value of lacquer resins of the present invention normally general formula (1) is different.
One of feature of the lacquer resins of the present invention be obtained by reacting by this is: make phenol and aphthols and by 4 of 4,4 '-bis-(chloromethyl) biphenyl and so on, the biphenol compound that 4 '-body is formed combinationally uses.Further, the cured article formed by the composition epoxy resin employing lacquer resins of the present invention improves thermotolerance and resistance to flame aptly.
In the present invention, with regard to the lacquer resins formed by the chemical structure represented with general formula (1), result from phenol general formula (2) unit with result from aphthols general formula (3) unit ratio [unit of the unit/general formula (3) of general formula (2)] be preferably 10/90 ~ 90/10 scope in, be more preferably in the scope of 10/90 ~ 60/40, more preferably 10/90 ~ 50/50 scope in, be particularly preferably in the scope of 10/90 ~ 40/60.
By the ratio of the unit of the unit and general formula (3) that make general formula (2) within the scope of this, thermotolerance and the resistance to flame of the cured article formed by composition epoxy resin of the present invention can be improved aptly.
By combining the biphenol compound formed by 4,4 '-body in resin, and import the unit represented with general formula (3), the thermotolerance of the resin obtained is improved effectively, effectively can suppress burning thus improve resistance to flame.But when the ratio of the unit of general formula (3) is too high, cause the viscosity of resin, softening temperature rises, thus damage operability sometimes, in addition, the unit of the general formula (4) in resin increases, thus is difficult to the solvability controlling resin.
Therefore, in the reaction of preparation lacquer resins of the present invention, preferably to make the mode of the ratio of the unit of the unit of general formula (2) and general formula (3) in described scope regulate the phenol represented with general formula (5) as raw material and the usage ratio of aphthols that represents with general formula (6).Certainly, the usage ratio that hope can be improved the raw material of the unit of the ratio imported in lacquer resins improves, but with regard to its ratio, because the reactivity of these phenol, aphthols and biphenol compound is different separately, therefore also its ratio to be regulated with reference to the mol ratio [(phenol and aphthols)/biphenol compound] of the total of their reactive size and then biphenol compound and phenol and aphthols and the reaction conditions etc. adopted.To those skilled in the art, its control method is apparent, can find out simply if desired by carrying out preparative experiment.
In the present invention, one of preferred configuration of lacquer resins is: make the composition represented with general formula (4) in whole compositions of the aggregate represented with general formula (1) of formation lacquer resins count less than 27% according to area ratio when being measured by HPLC, be preferably less than 20%.If the Composition Control represented with general formula (4) is become to count less than 27% according to area ratio when being measured by HPLC in whole composition, solvability then for organic solvent improves, even if such as methylethylketone make resin/solvent be in mass 50/50 ratio also can dissolve equably.
On the other hand, if the composition represented in general formula (4) in whole composition according to area ratio when being measured by HPLC more than 27%, solvability then for organic solvent reduces, such as, be difficult to dissolve equably when making resin/solvent be the ratio of 50/50 in mass for methylethylketone.
Even if if such as use methylethylketone and make resin/solvent be that the ratio of the high density of 50/50 also can be dissolved equably in mass, then easily composition epoxy resin of the present invention be dissolved in methylethylketone and varnish thus be used as body material and the interlayer dielectic of plywood.When cannot dissolve equably, cannot varnish, be not easily used as body material and the interlayer dielectic of plywood.
The adjustment of the amount of the composition represented with general formula (4) in the composition of lacquer resins is carried out as follows: with reference to their reactive size and the reaction conditions etc. that adopts, while regulate the mol ratio [(phenol and aphthols)/biphenol compound] of total of the biphenol compound used as raw material and phenol and aphthols and the mol ratio [phenol/aphthols] of phenol and aphthols.
When being than usually less value (value closer to 1) when making the mol ratio of the total of biphenol compound and phenol and aphthols [(phenol and aphthols)/biphenol compound], composition polymer quantification on the whole can be made, thus reduce general formula (4) composition, because of but be suitable for.In addition, with regard to the mol ratio of phenol and aphthols, because the reactivity of aphthols is higher than phenol, thus reaction is advanced further when enabling the ratio of aphthols relatively high, make composition polymer quantification on the whole, thus reduce general formula (4) composition, because of but be suitable for; On the other hand, when the ratio of aphthols is too high, the composition of general formula (4) increases, thus has detrimentally affect to solvability.Such as, if make aphthols be 100%, be certainly difficult to the amount of the composition reducing general formula (4) significantly, thus be difficult to improve solubleness.
The adjustment of these ratios will be carried out with reference to their reactive size and the reaction conditions etc. adopted.To those skilled in the art, its control method is apparent, can find out simply if desired by carrying out preparative experiment.
The lacquer resins (A) be made up of the chemical structure represented with general formula (1) of the present invention preferably softening temperature is 60 DEG C ~ 150 DEG C, is more preferably 70 DEG C ~ 140 DEG C.When softening temperature is less than 60 DEG C, easily produce adhesion etc.; If more than 150 DEG C, then operability has problems sometimes.In addition, the weight-average molecular weight of the lacquer resins (A) be made up of the chemical structure represented with general formula (1) of the present invention is preferably the scope of 500 ~ 10000, be more preferably 500 ~ 5000, more preferably the scope of 500 ~ 2000.
Next, composition epoxy resin of the present invention is described.
Composition epoxy resin of the present invention comprises the lacquer resins (A) that is made up of the chemical structure represented with general formula (1) and epoxy resin (B).
As the epoxy resin used in composition epoxy resin of the present invention (B), such as, can list: the epoxy resin etc. in glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, the halogenated epoxy resin equimoleculars such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aralkyl type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, tris-phenol type epoxy resin, biphenyl type epoxy resin with two or more epoxy group(ing).These epoxy resin can be used alone one, also can share two or more.
Among them, from the viewpoint of improving thermotolerance, resistance to flame, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, triphenylmethane type epoxy resin, cresol novolak type epoxy resin etc. be suitable for especially.
As the adding proportion of the epoxy resin used in composition epoxy resin of the present invention (B), the ratio [hydroxyl equivalent/epoxy equivalent (weight)] of the epoxy equivalent (weight) in the hydroxyl equivalent of solidifying agent and epoxy resin is preferably the scope of about 0.5 ~ 2.0, is more preferably the scope of about 0.8 ~ 1.2.When this scope is outer, due to curing reaction fully do not carry out, unreacted solidifying agent and the reason such as epoxy resin is remaining, sometimes cannot play effect of the present invention.
The lacquer resins (A) be made up of the chemical structure represented with general formula (1) has the effect of the solidifying agent of epoxy resin in composition epoxy resin of the present invention, but in composition epoxy resin of the present invention, also can comprise other solidifying agent except the lacquer resins (A) except being made up of the chemical structure represented with general formula (1).
Other solidifying agent except lacquer resins (A) is not particularly limited, various epoxy curing agent can be used according to the application target of composition.Such as, the epoxy curing agent that amine system solidifying agent, acid amides system solidifying agent, acid anhydrides system solidifying agent, resol system solidifying agent except the lacquer resins (A) be made up of the chemical structure represented with general formula (1) etc. are conventional can be used aptly.
In addition, in composition epoxy resin of the present invention, the ratio of the lacquer resins (A) be made up of the chemical structure represented with general formula (1) in solidifying agent is not particularly limited, but in order to improve cured article thermotolerance, resistance to flame and preferably higher ratio, be more than 30 quality %, be preferably more than 50 quality %, be more preferably more than 70 quality %, more preferably 90 quality %, are particularly preferably 100 quality %.
Composition epoxy resin of the present invention preferably contains solvent (C) further, and preferably lacquer resins (A) and epoxy resin (B) are dissolved in solvent (C) equably.
As long as the composition epoxy resin of the thermotolerance of obtained cured article, resistance to flame excellence can be made uniform lacquer solutions with high density, body material and the interlayer dielectic of plywood just can be used as aptly.
Described solvent (C), as long as make composition epoxy resin dissolve, is not particularly limited, and preferably can use organic solvent used when the body material of plywood and interlayer dielectic varnish aptly usually.Such as, can list aptly: the ketones such as methylethylketone, acetone, diethyl ketone, mibk, pimelinketone; The ethers such as propylene glycol monomethyl ether; The amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE; The sulfoxide types such as dimethyl sulfoxide (DMSO); The lactone such as gamma-butyrolactone; The pyrrolidinone compounds such as N-Methyl pyrrolidone; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based.Among them, particularly preferably methylethylketone, dimethyl formamide.These solvents can be used alone, and also can be used in combination of two or more.
Not not limiting during composition epoxy resin varnish of the present invention, the concentration of preferred resin composition is 10 quality % ~ 90 about quality %, and soltion viscosity is about 1cP ~ 5000cP at 30 DEG C.
In composition epoxy resin of the present invention, can use according to its purposes other composition usually used in composition epoxy resin aptly.
Such as, the curing catalyst in order to be made epoxy resin cure by resol can be used.As curing catalyst, known organic phosphine compound and boron salt, tertiary amine, quaternary ammonium salt, imidazoles and tetraphenyl boron salt thereof etc. can be listed aptly.Among them, from the viewpoint of solidified nature, wet fastness, triphenylphosphine.In addition, when composition epoxy resin is required higher mobility, manifest the curing catalyst of active latent heat preferably by heat treated, wherein the more preferably tetraphenylphosphonium derivative such as tetraphenylphosphonium tetraphenyl borate.The addition of curing catalyst is identical with the ratio in known composition epoxy resin just.
In addition, the weighting agents such as inorganic filler can also be used aptly.As inorganic filler, amorphism silicon-dioxide, crystallinity silicon-dioxide, aluminum oxide, Calucium Silicate powder, calcium carbonate, talcum, mica, barium sulfate etc. can be used, particularly more preferably amorphism silicon-dioxide, crystallinity silicon-dioxide.Particle diameter as inorganic filler is not particularly limited, if but consider filling ratio, be preferably 0.01 μm ~ 150 μm.
The mixed ratio of inorganic filler is not particularly limited, and is 70 in composition epoxy resin % by weight ~ 95 % by weight, is preferably 75 % by weight ~ 90 % by weight, is more preferably 80 % by weight ~ 90 % by weight.If the ratio of inorganic filler is outside above-mentioned scope, then the water-intake rate of the cured article of composition epoxy resin increases, and not preferred.In addition, if the ratio of inorganic filler is too much, then likely mobility is damaged.
In addition, for composition epoxy resin of the present invention, can add or react releasing agent, tinting material, coupling agent, fire retardant etc. in advance using as required.In addition, the mixed ratio of these additives is identical with the ratio in known composition epoxy resin just.In composition epoxy resin of the present invention, the phosphorus flame retardants such as the nitrogenated flame retardant such as trimeric cyanamide, isocyanuric acid compound, red phosphorus, phosphate cpd, organo phosphorous compounds can also be added in addition as required aptly as flame retardant.
Composition epoxy resin of the present invention can be manufactured by following manner: use such as mixing tank etc., by Homogeneous phase mixing such as lacquer resins (A), epoxy resin (B) and the curing catalyst added as required, inorganic filler, other additives, utilize the mixing rolls such as warming mill, kneader or forcing machine and carry out mixing, cooling with molten state, and pulverizing as required.
Such composition epoxy resin is not limited, but semiconductor-encapsulating material etc. can be used as aptly.
In addition, for composition epoxy resin of the present invention, add in methylethylketone, propylene glycol monomethyl ether or dimethyl formamide equal solvent (C) be made up of the chemical structure represented with general formula (1) lacquer resins (A), epoxy resin (B) and other solidifying agent, curing catalyst, inorganic filler, additive etc. of adding as required, carry out as required heating, stirring, the lacquer solutions of at least lacquer resins (A) and epoxy resin (B) uniform dissolution in solvent (C) can be manufactured thus.
Epoxy resin (solution) composition to this varnish does not limit, and can be used as body material and the interlayer dielectic of plywood aptly.
For composition epoxy resin of the present invention, as required by after solvent seasoning, carry out heat treated, cured article can be obtained aptly thus.
Although the heat treated condition for obtaining cured article also depends on presence or absence, their addition etc. of curing catalysts and curing catalyst, usually 100 DEG C ~ about 300 DEG C, preferably at the temperature of 120 DEG C ~ about 200 DEG C, heat treated 1 minute is suitable to 10 hours.
Composition epoxy resin of the present invention can be used as the sealing material sealed semiconductor element aptly.Such as, the lead frame etc. being mounted with this semiconductor element is arranged in metal chamber, utilize the forming methods such as transfer mould, compressed moulding, injection moulding that composition epoxy resin is shaping afterwards, at the temperature of 120 DEG C to about 300 DEG C, make epoxy resin composition by heat treated etc., semiconductor device can be obtained aptly thus.
In addition, for composition epoxy resin of the present invention, preferred uniform dissolution is varnish in methylethylketone equal solvent, and with the coating of its lacquer solutions or porous glass base material or glass fibre, paper, the aramid fiber etc. such as impregnate glass, then carry out heat treated (semicure), printed base plate prepreg can be manufactured thus.In addition, by obtained printed base plate prepreg, multiple are stacked, pressurize as required and carry out heat treated and make it solidify, thus can fabrication layer lamination.
In addition, for plywood or prepreg, stacked tinsel in one or two sides, pressurizes as required and carries out heat treated (such as 180 DEG C, the heating under pressure process of 4MPa 60 minutes), can obtain metal-clad thus.This metal-clad forms circuit pattern by etch processes, and it can be used as printed circuit board (PCB) aptly.
In addition, for composition epoxy resin of the present invention, preferred uniform dissolution is varnish in methylethylketone equal solvent, and utilize mould painting machine (diecoater) etc. that its lacquer solutions is spread evenly across the such as supporting body surface such as PET film or Copper Foil, heat drying is carried out to obtained coated film, form the duplexer sheet material with resin layer thus, it can be used as interlayer dielectic aptly.
Embodiment
Below, the present invention will be described in more detail in citing.In addition, the invention is not restricted to these examples.
[1] preparation of lacquer resins
The material used in example to the preparation of lacquer resins is below described.
(1) phenol: manufacture with light pure pharmaceutical worker's industry company
(2) naphthyl alcohol (1-naphthols): manufacture with light pure pharmaceutical worker's industry company
(3) 4,4 '-bis-(chloromethyl) biphenyl: manufacture with light pure pharmaceutical worker's industry company
The analytical procedure used in example to the preparation of lacquer resins below and evaluation method are described.
(1) softening temperature: undertaken by measuring based on the ring and ball softening point of JISK6910.
(2) hydroxyl equivalent: undertaken by measuring based on the hydroxyl equivalent of JISK0070.
(3) mensuration of the ratio [unit of the unit/general formula (3) of general formula (2)] of the unit of general formula (2) and the unit of general formula (3): in the preparation of lacquer resins, measure the charging capacity of raw material, the lacquer resins amount generated and amount of by-products, gone out the amount of unreacting material by reaction budget analysis.The whole amount of biphenol compound is reacted, therefore unreacting material by as form general formula (2) unit raw material phenol and formed as the aphthols of raw material of the unit forming general formula (3).With regard to the ratio of the unreacted phenol in reaction mixture and aphthols, measure by the HPLC by condition shown below the HPLC figure obtained and obtain.In addition, ratio (mol ratio) is area ratio.According to following mathematical expression, calculated the ratio [unit of the unit/general formula (3) of general formula (2)] of the unit of general formula (2) and the unit of general formula (3) by above data.
The condition determination of HPLC
Machine: the HPLC that company of Shimadzu Seisakusho Ltd. manufactures
Post: STRODS-H post (letter and chemical company manufacture)
Column oven temperature: 40 DEG C
Fluidised bed: acetonitrile, 5% phosphoric acid solution
With regard to the concentration adjustment of fluidised bed, the volume fraction using acetonitrile/5% phosphoric acid solution when measuring and starting is the mixed solution of 20/60, after mensuration starts be 60/40 with ratio to the volume fraction increasing acetonitrile for 10 minutes linearly, then being 100/0 with ratio to the volume fraction increasing acetonitrile for 5 minutes linearly, using acetonitrile to measuring end afterwards in this condition.
Flow: 1.00mL/ minute
Determined wavelength: 220nm
Mathematical expression 1
Import charging capacity-(in unreacting material amount × unreacting material the aphthols ratio) of aphthols amount=aphthols
Import charging capacity-(in unreacting material amount × unreacting material the phenol ratio) of phenol amount=phenol
(4) ratio of the composition represented with general formula (4): measure by the HPLC by condition shown below the HPLC obtained and scheme, obtain as its area ratio.
The condition determination of HPLC
Machine: the HPLC that company of Shimadzu Seisakusho Ltd. manufactures
Post: STRODS-H post (letter and chemical company manufacture)
Column oven temperature: 40 DEG C
Fluidised bed: acetonitrile, 5% phosphoric acid solution
With regard to the concentration adjustment of fluidised bed, the volume fraction using acetonitrile/5% phosphoric acid solution when measuring and starting is the mixed solution of 50/50, after mensuration starts be 75/25 with ratio to the volume fraction increasing acetonitrile for 20 minutes linearly, then being 100/0 with ratio to the volume fraction increasing acetonitrile for 20 minutes linearly, using acetonitrile to measuring end afterwards in this condition.
Flow: 1.00mL/ minute
Determined wavelength: 220nm
(5) solvability:
Utilize method shown below, evaluated by dissolubility test.
Solvent: methylethylketone
Dissolving ratio (quality): lacquer resins/solvent=50/50
Dissolution conditions: add resin and solvent in encloses container, stirring and dissolving at 60 DEG C.
Evaluate and judge: leave standstill after 12 hours upon dissolution and under normal temperature (23 DEG C), observed by range estimation.By resin uniform dissolution and the average evaluation also maintaining uniform solution after leaving standstill is zero, by resin uniform dissolution but the average evaluation that after leaving standstill, a part for resin is separated out is △, the average evaluation that cannot obtain uniform solution for ×.
(embodiment 1)
Phenol 188.0g (2.0 moles), naphthyl alcohol 123.4g (0.9 mole) is added to possessing thermometer, in glass flask that the capacity of the mouth that feeds intake/distillate, water cooler and stirrer is 1000mL, be warming up to till interior temperature is 60 DEG C under nitrogen flowing, make material dissolution thus.Add 4,4 '-bis-(chloromethyl) biphenyl 179.3g (0.7 mole), react 4 hours at interior temperature is 60 DEG C ~ 100 DEG C, and then react 3 hours at 165 DEG C, removed the unreacted component of raw material afterwards by decompression-steam treatment.
The softening temperature of the lacquer resins obtained is 113 DEG C, hydroxyl equivalent is 263g/eq, the ratio [unit of the unit/general formula (3) of general formula (2)] of the unit of the general formula (2) recorded by HPLC and the unit of general formula (3) is 30/70, and the ratio of the composition represented with general formula (4) is for 15%.The deliquescent evaluation of this lacquer resins is judged to be zero.
In addition, the HPLC of the unreacting material of this reaction is illustrated in Fig. 1.The ratio being calculated phenol in unreacting material and aphthols by this figure is 82% and 18%.Use this ratio, according to described method of calculation, calculate the ratio [unit of the unit/general formula (3) of general formula (2)] of the unit of the general formula (2) imported in resin and the unit of general formula (3).
In addition, the HPLC of obtained lacquer resins is illustrated in Fig. 2.The ratio of the composition (owing to there being isomer, being thus the total at three peaks) represented with general formula (4) is obtained by the area ratio of this figure.
(embodiment 2)
Phenol 84.6g (0.9 mole), naphthyl alcohol 129.6g (0.9 mole) is added to possessing thermometer, in glass flask that the capacity of the mouth that feeds intake/distillate, water cooler and stirrer is 1000mL, be warming up to till interior temperature is 60 DEG C under nitrogen flowing, make material dissolution thus.Add 4,4 '-bis-(chloromethyl) biphenyl 180.7g (0.7 mole), react 4 hours at interior temperature is 60 DEG C ~ 100 DEG C, and then react 3 hours at 165 DEG C, removed the unreacted component of raw material afterwards by decompression-steam treatment.
The softening temperature of the lacquer resins obtained is 131 DEG C, hydroxyl equivalent is 256g/eq, the ratio [unit of the unit/general formula (3) of general formula (2)] of the unit of the general formula (2) recorded by HPLC and the unit of general formula (3) is 20/80, and the ratio of the composition represented with general formula (4) is for 18%.The deliquescent evaluation of this lacquer resins is judged to be zero.
In addition, the HPLC of the unreacting material of this reaction is illustrated in Fig. 3.The ratio being calculated phenol in unreacting material and aphthols by this figure is 76% and 24%.Use this ratio, according to described method of calculation, calculate the ratio [unit of the unit/general formula (3) of general formula (2)] of the unit of general formula (2) and the unit of general formula (3).
In addition, the HPLC of obtained lacquer resins is illustrated in Fig. 4.The ratio of the composition (owing to there being isomer, being thus the total at three peaks) represented with general formula (4) is obtained by the area ratio of this figure.
(embodiment 3)
Phenol 94.0g (1.0 moles), naphthyl alcohol 144.0g (1.0 moles) is added to possessing thermometer, in glass flask that the capacity of the mouth that feeds intake/distillate, water cooler and stirrer is 1000mL, be warming up to till interior temperature is 60 DEG C under nitrogen flowing, make material dissolution thus.Add 4,4 '-bis-(chloromethyl) biphenyl 161.9g (0.7 mole), react 4 hours at interior temperature is 60 DEG C ~ 100 DEG C, and then react 3 hours at 165 DEG C, removed the unreacted component of raw material afterwards by decompression-steam treatment.
The softening temperature of the lacquer resins obtained is 117 DEG C, and hydroxyl equivalent is 247g/eq, and the ratio of the composition represented with general formula (4) recorded by HPLC is for 24%.The deliquescent evaluation of this lacquer resins is judged to be △.
(embodiment 4)
Phenol 188.0g (2.0 moles), naphthyl alcohol 123.4g (1.0 moles) is added to possessing thermometer, in glass flask that the capacity of the mouth that feeds intake/distillate, water cooler and stirrer is 1000mL, be warming up to till interior temperature is 60 DEG C under nitrogen flowing, make material dissolution thus.Add 4,4 '-bis-(chloromethyl) biphenyl 119.5g (0.5 mole), react 4 hours at interior temperature is 60 DEG C ~ 100 DEG C, and then react 3 hours at 165 DEG C, remove unreacted component by decompression-steam treatment afterwards.
The softening temperature of the lacquer resins obtained is 97 DEG C, and hydroxyl equivalent is 238g/eq, and the ratio of the composition represented with general formula (4) recorded by HPLC is for 30%.The deliquescent evaluation of this lacquer resins is judged to be ×.
(embodiment 5)
Phenol 141.0g (1.5 moles), naphthyl alcohol 216.0g (1.5 moles) is added to possessing thermometer, in glass flask that the capacity of the mouth that feeds intake/distillate, water cooler and stirrer is 1000mL, be warming up to till interior temperature is 60 DEG C under nitrogen flowing, make material dissolution thus.Add 4,4 '-bis-(chloromethyl) biphenyl 125.5g (0.5 mole), react 4 hours at interior temperature is 60 DEG C ~ 100 DEG C, and then react 3 hours at 165 DEG C, remove unreacted component by decompression-steam treatment afterwards.
The softening temperature of the lacquer resins obtained is 94 DEG C, and hydroxyl equivalent is 238g/eq, and the ratio of the composition represented with general formula (4) recorded by HPLC is for 49%.The deliquescent evaluation of this lacquer resins is judged to be ×.
The lacquer resins of embodiment 1 ~ 5 is aggregated in table 1.From the deliquescent evaluation result of this table, in order to be dissolved in equably in solvent by the composition epoxy resin employing lacquer resins of the present invention, the ratio of the composition represented with general formula (4) is less than 27%, preferably less than 20% is suitable.
Table 1
[2] composition epoxy resin of the present invention preparation and with the comparing of patent documentation 2
Below, the material used in the example of composition epoxy resin is described.
(1) epoxy resin
Ortho-cresol type epoxy resin " EOCN-1020-70 ": Japanese chemical drug Inc. makes, epoxy equivalent (weight) is 200g/eq, and softening temperature is 70 DEG C
(2) curing catalyst (curing catalysts)
Triphenylphosphine (TPP): northern Xinghua is learned company and manufactured
Below, the evaluation method of composition epoxy resin is described.
(1) thermotolerance (second-order transition temperature (Tg))
Measuring method according to patent documentation 2 carries out.That is, use the test film formed by the cured article being of a size of 4mm × 6mm × 10mm, heat up with the heat-up rate of 5 DEG C/min, measure according to TMA method (ThermalMechanicalAnalysis, thermomechanical analysis) thus.
(embodiment 6)
The lacquer resins, the ortho-cresol type epoxy resin EOCN-1020-70 and curing catalyst TPP that obtain in embodiment 1 is added with the proportioning shown in table 2, make composition epoxy resin, under the condition of 150 DEG C, heating and melting mixing is carried out to it, at the middle casting mold of the mould (thickness is 4mm) of 150 DEG C after having carried out vacuum defoamation, and solidify 5 hours at 150 DEG C, then solidify 8 hours at 180 DEG C further, obtain curing molding body thus.
For this curing molding body, measure second-order transition temperature, result is 175 DEG C.
With regard to this embodiment 6, except the lacquer resins that change uses, utilize the operation same with the embodiment 5 ~ 6 of patent documentation 2 to prepare composition epoxy resin, and for its cured article, profit use the same method and evaluate.The data of the embodiment 7 of the evaluation result of this embodiment 6 and patent documentation 2 are compared, and is shown in table 2.
Table 2
As shown in Table 2, owing to employing lacquer resins of the present invention, the second-order transition temperature of the cured article of composition epoxy resin significantly improves.
[3] preparation of composition epoxy resin of the present invention and the evaluation that utilizes EMC test film to carry out
Below, the material used in the example of composition epoxy resin is described.
(1) epoxy resin
Biphenyl type epoxy resin " YX-4000 ": Mitsubishi Chemical Ind manufactures, and epoxy equivalent (weight) is 187g/eq
(2) curing catalyst (curing catalysts)
Triphenylphosphine (TPP): northern Xinghua is learned company and manufactured
(3) inorganic filler
Silicon-dioxide " MSR-2212 ": Long Sen company manufactures
Below, the evaluation method of composition epoxy resin is described.
(1) incendivity
Measure according to UL-94.
(2) thermotolerance (second-order transition temperature (Tg))
Use is of a size of the EMC test film of 40mm × 12mm × 1mm, and utilizes Measurement of Dynamic Viscoelasticity device (RSA-G2 that TAInstruments company manufactures) to measure with the heat-up rate of 3 DEG C/min.
(3) mechanical characteristics: physical strength measures according to JISK7171.
(embodiment 7)
With the proportioning shown in table 2 add obtain in embodiment 1 lacquer resins, biphenyl type epoxy resin YX-4000, curing catalyst TPP and inorganic filler silicon-dioxide MSR-2212, under the condition of 80 DEG C ~ 100 DEG C, use two roller to carry out mixing to them, pulverize afterwards, obtain composition epoxy resin of the present invention.
Use the composition epoxy resin obtained to make blank (tablet), utilize low pressure Transfer molding machine die temperature be 175 DEG C, injection pressure is 6.8MPa, the dwell time be the condition of 600 seconds under this blank is injected mould, make test film thus, 180 DEG C, the after fixing of 8 hours is carried out further after mould taking-up, obtain EMC (EpoxyMolderingCompound, the epoxy molding compound) test film formed by the cured article of composition epoxy resin.
The result evaluated it is shown in table 3.
(embodiment 8)
Except employing the lacquer resins that obtains in embodiment 2, carry out same operation with embodiment 7, obtain EMC (EpoxyMolderingCompound, the epoxy molding compound) test film formed by the cured article of composition epoxy resin.
The result evaluated it is shown in table 3.
(embodiment 9)
Except employing the lacquer resins that obtains in embodiment 3, carry out same operation with embodiment 7, obtain EMC (EpoxyMolderingCompound, the epoxy molding compound) test film formed by the cured article of composition epoxy resin.
The result evaluated it is shown in table 3.
(embodiment 10)
Except employing the lacquer resins that obtains in embodiment 4, carry out same operation with embodiment 7, obtain EMC (EpoxyMolderingCompound, the epoxy molding compound) test film formed by the cured article of composition epoxy resin.
The result evaluated it is shown in table 3.
Except employing the lacquer resins that obtains in embodiment 5, carry out same operation with embodiment 7, obtain EMC (EpoxyMolderingCompound, the epoxy molding compound) test film formed by the cured article of composition epoxy resin.
The result evaluated it is shown in table 3.
Except employing the lacquer resins that obtains in embodiment 6, carry out same operation with embodiment 7, obtain EMC (EpoxyMolderingCompound, the epoxy molding compound) test film formed by the cured article of composition epoxy resin.
The result evaluated it is shown in table 3.
(reference example 1)
Add phenol 470.0g (5.0 moles) to possessing thermometer, in glass flask that the capacity of the mouth that feeds intake/distillate, water cooler and stirrer is 1000mL, be warming up to till interior temperature is 60 DEG C under nitrogen flowing, make material dissolution thus.Add 4,4 '-dichloride methyl biphenyl 313.8g (1.3 moles), react 4 hours at interior temperature is 60 DEG C ~ 100 DEG C, and then react 3 hours at 165 DEG C, remove unreacted component by decompression-steam treatment afterwards.The softening temperature of the lacquer resins E obtained is 68 DEG C, and hydroxyl equivalent is 202g/eq.
(comparative example 1)
Except employing the lacquer resins that obtains in reference example 1, same operation is carried out with embodiment 6, obtain forming by the cured article of composition epoxy resin EMC (EpoxyMolderingCompound, the epoxy molding compound) test film being of a size of 40mm × 12mm × 1mm.
The result evaluated it is shown in table 3.
Table 3
[4] manufacture and the evaluation of the copper-clad laminated board of composition epoxy resin of the present invention is employed
Below, the material used in the example to the manufacture of copper-clad laminated board is described.
(1) epoxy resin
Bisphenol A type epoxy resin " 828EL ": Mitsubishi Chemical Ind manufactures, and epoxy equivalent (weight) is 186g/eq
(2) curing catalyst (curing catalysts)
2-ethyl-4-methylimidazole (2E4MZ): four countries change into company and manufacture
(3) solvent (methylethylketone): manufacture with light pure pharmaceutical worker's industry company
(4) woven fiber glass (without alkaline purification woven fiber glass) " M7628-105 ": You Ze manufacturing company manufactures
(5) Copper Foil (electrolytic copper foil) " CF-T9B-THE ": Bo Fen industrial of FUKUDA METAL manufactures, and thickness is 35 μm
Below, the evaluation method of copper-clad laminated board is described.
(1) cementability (stripping strength)
Use Measurement of Dynamic Viscoelasticity device (" AG-5000D " that Shimadzu Corporation manufactures), measure 90 ° of peel strength of copper foils with the trial speed of the load of 1kN/100kgf, 50mm/ minute.
(2) thermotolerance
Use Measurement of Dynamic Viscoelasticity device (" RSA-G2 " that TAInstruments company manufactures), with the determination of heating rate second-order transition temperature (Tg) of 3 DEG C/min.
(3) water-intake rate
Measure according to JISC6481.
(embodiment 12)
Add in diluting solvent methylethylketone 231.2 mass parts obtain in embodiment 1 lacquer resins 131 mass parts, bisphenol-type epoxy resin 100 mass parts, curing catalyst 2E4MZ0.1 mass parts and varnish, the resinous principle concentration obtaining uniform dissolution is the lacquer solutions of 50 quality %.
Impregnated glass-fiber cloth M7628-105 in obtained lacquer solutions, carries out drying afterwards, obtains prepreg under the condition of 130 DEG C, 15 minutes.Overlapping eight these prepregs, and at its both sides overlap Copper Foil CF-T9B-THE, at 170 DEG C, 30kg/cm 2condition under use press to suppress 15 minutes.After being taken out from press by copper-clad laminated body, after fixing 5 hours at 200 DEG C, obtains two sides copper-clad laminated board thus further.
The second-order transition temperature of the copper-clad laminated board obtained is 159 DEG C, and stripping strength is 2.0N/mm, and water-intake rate is 0.05 quality %.Show the result in table 4.
(reference example 2)
Add phenol 470.0g (5.0 moles), 92% paraformaldehyde 110.9g (3.4 moles) and oxalic acid 0.3g to possessing thermometer, in glass flask that the capacity of the mouth that feeds intake/distillate, water cooler and stirrer is 1000mL, react 5 hours at 100 DEG C.After reaction terminates, decompression-steam treatment is utilized to remove unreacted component.The softening temperature of the lacquer resins E obtained is 96 DEG C, and hydroxyl equivalent is 107g/eq.
(comparative example 2)
Replace the lacquer resins that obtains in embodiment 1 except using the lacquer resins of the routine of preparation in reference example 2 and make proportioning as shown in table 4 except, operate similarly to Example 9, obtain two sides copper-clad laminated board.
The second-order transition temperature of the copper-clad laminated board obtained is 147 DEG C, and stripping strength is 1.6N/mm, and water-intake rate is 0.09 quality %.Result is shown in table 4.
Table 4
Utilizability in industry
According to the present invention, a kind of composition epoxy resin can be provided and the lacquer resins of this composition epoxy resin can be suitably used for, this composition epoxy resin is for comprising the composition epoxy resin of lacquer resins (being more particularly phenol-naphthol novolac varnish resin) and epoxy resin, and this composition epoxy resin significantly improves thermotolerance and the resistance to flame of obtained cured article.In addition, according to the present invention, a kind of composition epoxy resin can be provided and the lacquer resins of this composition epoxy resin can be suitably used for, this composition epoxy resin due to the solvability of lacquer resins preferably used excellent, thus be easily dissolved in solvent equably, thus the purposes of such as fabrication layer lamination, interlayer dielectic can be suitably used for.

Claims (10)

1. a lacquer resins, it is made up of the chemical structure represented with following general formula (1),
In general formula (1), A represents 1 valency of 1 valency of following general formula (2) or the unit of divalent or general formula (3) or the unit of divalent independently of one another, n is the integer of 0 ~ 20, R1 represents that carbonatoms is the alkyl of 1 ~ 8 independently of one another, p and q is the integer of 0 ~ 2 independently of one another
Wherein, overall as lacquer resins, A is made up of 1 valency of following general formula (2) or both 1 valency of the unit of divalent and following general formula (3) or the unit of divalent,
In general formula (2), R2 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, i is the integer of 1 ~ 3, and j is the integer of 0 ~ 2, and i and j adds up to less than 4,
In general formula (3), R3 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, k is the integer of 1 ~ 3, and l is the integer of 0 ~ 4, and k and l adds up to less than 6,
Form the composition represented with following general formula (4) in whole compositions of lacquer resins and count less than 27% according to area ratio when being measured by HPLC,
In general formula (4), R1 represents that carbonatoms is the alkyl of 1 ~ 8 independently of one another, p and q is the integer of 0 ~ 2 independently of one another, R3 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, k is the integer of 1 ~ 3, l is the integer of 0 ~ 4, and k and l adds up to less than 6.
2. lacquer resins according to claim 1, it is characterized in that, the unit of the molar ratio of the unit of described general formula (2) and the unit of described general formula (3) and the unit/general formula (3) of general formula (2) is in the scope of 10/90 ~ 90/10.
3. the manufacture method of the lacquer resins described in claim 1 or 2, it is characterized in that, make the phenol that represents with following general formula (5) and react with the biphenol compound represented with following general formula (7) with the aphthols that following general formula (6) represents
In general formula (5), R2 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, i is the integer of 1 ~ 3, and j is the integer of 0 ~ 2, and i and j adds up to less than 4,
In general formula (6), R3 represent independently of one another carbonatoms be 1 ~ 8 alkyl or carbonatoms be the alkoxyl group of 1 ~ 8, k is the integer of 1 ~ 3, and l is the integer of 0 ~ 4, and k and l adds up to less than 6,
In general formula (7), R1 represents that carbonatoms is the alkyl of 1 ~ 8 independently of one another, p and q is the integer of 0 ~ 2 independently of one another, and X represents that carbonatoms is alkoxyl group or the halogen atom of 1 ~ 4.
4. a composition epoxy resin, it comprises lacquer resins (A) described in claim 1 or 2 and epoxy resin (B).
5. composition epoxy resin according to claim 4, is characterized in that, the second-order transition temperature utilizing Measurement of Dynamic Viscoelasticity device to measure of the cured article obtained is more than 155 DEG C.
6. composition epoxy resin according to claim 4, is characterized in that, the second-order transition temperature utilizing thermomechanical analysis to measure of the cured article obtained is more than 155 DEG C.
7. the composition epoxy resin according to any one of claim 4 ~ 6, is characterized in that, the flame retardant resistance based on UL-94 of the cured article obtained is V-0.
8. a composition epoxy resin, it is characterized in that, it comprises lacquer resins (A), epoxy resin (B) and solvent (C) described in claim 1 or 2, wherein, lacquer resins (A) and epoxy resin (B) are dissolved in solvent (C) equably.
9. a cured article, it makes epoxy resin composition according to any one of claim 4 ~ 8.
10. a plywood, it uses the composition epoxy resin described in claim 8 to define matrix resin.
CN201280052226.5A 2011-11-29 2012-11-27 Lacquer resins and employ the composition epoxy resin of this lacquer resins Active CN103958561B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2011259761A JP5752574B2 (en) 2011-11-29 2011-11-29 Phenol novolac resin and epoxy resin composition using the same
JP2011-259761 2011-11-29
PCT/JP2012/080536 WO2013080936A1 (en) 2011-11-29 2012-11-27 Phenol novolak resin and epoxy resin composition using same

Publications (2)

Publication Number Publication Date
CN103958561A CN103958561A (en) 2014-07-30
CN103958561B true CN103958561B (en) 2016-04-27

Family

ID=48535391

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280052226.5A Active CN103958561B (en) 2011-11-29 2012-11-27 Lacquer resins and employ the composition epoxy resin of this lacquer resins

Country Status (5)

Country Link
JP (1) JP5752574B2 (en)
KR (1) KR101889442B1 (en)
CN (1) CN103958561B (en)
TW (1) TW201329137A (en)
WO (1) WO2013080936A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6041663B2 (en) * 2012-12-21 2016-12-14 日本化薬株式会社 Phenol resin, epoxy resin, epoxy resin composition, and cured product thereof
JP2015067806A (en) * 2013-09-30 2015-04-13 日本ゼオン株式会社 Curable composition for forming print wiring board and manufacturing method of laminate for forming print wiring board
JP7098881B2 (en) * 2017-03-31 2022-07-12 住友ベークライト株式会社 Thermosetting resin compositions, resin films with carriers, prepregs, printed wiring boards and semiconductor devices

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1160724A (en) * 1995-12-28 1997-10-01 日本化药株式会社 Epoxy resin, epoxy resin composition and hardened product thereof
CN101326213A (en) * 2005-12-13 2008-12-17 日立化成工业株式会社 Epoxy resin composition for encapsulation and electronic component device

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3577437A (en) * 1969-01-06 1971-05-04 Monsanto Co Epoxy resins from alkylated phenol novolac resins
JP2981281B2 (en) * 1990-11-29 1999-11-22 三井化学株式会社 Method for producing phenolic polymer
JP2866747B2 (en) * 1990-12-21 1999-03-08 三井化学株式会社 Method for producing phenolic polymer
JP3122834B2 (en) 1994-09-20 2001-01-09 明和化成株式会社 New phenol novolak condensate
JP3586327B2 (en) * 1995-12-25 2004-11-10 明和化成株式会社 Phenol-naphthol novolak condensate
JPH09268218A (en) * 1996-03-29 1997-10-14 Nippon Kayaku Co Ltd Production of epoxy resin, epoxy resin composition and irs cured material
JP3992181B2 (en) * 2002-03-22 2007-10-17 日本化薬株式会社 Production method of epoxy resin
JP5228328B2 (en) 2007-02-01 2013-07-03 宇部興産株式会社 Low melt viscosity phenol novolac resin, process for producing the same, and cured epoxy resin using the same
JP5135973B2 (en) 2007-09-28 2013-02-06 Ｄｉｃ株式会社 Epoxy resin composition and cured product thereof
JP2011252037A (en) * 2010-05-31 2011-12-15 Meiwa Kasei Kk Epoxy resin composition and semiconductor sealing material and laminated board using the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1160724A (en) * 1995-12-28 1997-10-01 日本化药株式会社 Epoxy resin, epoxy resin composition and hardened product thereof
CN101326213A (en) * 2005-12-13 2008-12-17 日立化成工业株式会社 Epoxy resin composition for encapsulation and electronic component device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
含联苯结构的环氧树脂固化性能的研究;张春玲 等;《高等学校化学学报》;20040915;第25卷(第9期);第1052-1056页 *
苯酚-亚联苯型酚醛树脂的合成与表征;朱其仁 等;《化工学报》;20090415;第60卷(第4期);第1756-1758页 *

Also Published As

Publication number Publication date
WO2013080936A1 (en) 2013-06-06
JP5752574B2 (en) 2015-07-22
KR20140099229A (en) 2014-08-11
JP2013112738A (en) 2013-06-10
KR101889442B1 (en) 2018-08-17
TW201329137A (en) 2013-07-16
TWI560219B (en) 2016-12-01
CN103958561A (en) 2014-07-30

Similar Documents

Publication Publication Date Title
CN101341181B (en) A curable epoxy resin composition and laminates made therefrom
CN102762581B (en) Phosphorus-atom-containing oligomers, process for producing same, curable resin composition, cured product thereof, and printed wiring board
TWI739817B (en) Thermosetting resin composition, prepreg and its cured product
JP6167621B2 (en) Resin composition, resin film for printed wiring board and method for producing the same
CN106471034B (en) Epoxy resin, hardening resin composition, solidfied material, semiconductor-encapsulating material, semiconductor device, prepreg, circuit board
CN101084250A (en) Modified phenolic resin, epoxy resin composition containing the same, and prepreg containing the composition
JP5459869B2 (en) Novel varnish composition with high glass transition temperature applied to glass fiber laminates
CN103724596A (en) Epoxy resin composition and condensate
CN109415484A (en) Active ester composition and its solidfied material
CN103958561B (en) Lacquer resins and employ the composition epoxy resin of this lacquer resins
CN104684954A (en) Epoxy resin, curable resin composition, cured product thereof, and printed circuit board
WO2019078300A1 (en) Curable resin composition, varnish, prepreg, cured product, laminate and copper-clad laminate
CN109476820A (en) Solidification compound and its solidfied material
CN105517984A (en) Compound containing phenolic hydroxyl group, phenolic resin, curable composition, cured product thereof, semiconductor sealing material, and printed circuit board
TW201132700A (en) Compositions having phosphorus-containing compounds
CN106132974B (en) Phosphorus system epoxide and preparation method thereof includes its epoxy composite
CN109415483A (en) Active ester resin and its solidfied material
CN103946263A (en) Insulating material using epoxy resin composition
JP5928703B2 (en) Method for producing novolac type phenolic resin, method for producing epoxy resin composition
JP6766316B2 (en) Benzoxazine compound, benzoxazine resin, method for producing benzoxazine compound, curable resin composition, cured product thereof, FRP material, semiconductor encapsulant material, varnish, circuit board, prepreg, and build-up film.
JP6783121B2 (en) Allyl group-containing resin, its manufacturing method, resin varnish and laminated board manufacturing method
JP3141962B2 (en) Epoxy resin composition and cured product thereof
CN109415485A (en) Active ester resin and its solidfied material
CN104364291A (en) Resin composition and cured product thereof
JP6441216B2 (en) Phenolic resin, epoxy resin composition and cured product using the same, copper-clad laminate, semiconductor encapsulant

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230629

Address after: Yamaguchi Japan

Patentee after: Ube Co.,Ltd.

Address before: Yamaguchi Japan

Patentee before: MEIWA PLASTIC INDUSTRIES, LTD.