CN103958561A - Linear phenol novolak resin and epoxy resin composition using same - Google Patents

Linear phenol novolak resin and epoxy resin composition using same Download PDF

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Publication number
CN103958561A
CN103958561A CN201280052226.5A CN201280052226A CN103958561A CN 103958561 A CN103958561 A CN 103958561A CN 201280052226 A CN201280052226 A CN 201280052226A CN 103958561 A CN103958561 A CN 103958561A
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general formula
epoxy resin
carbonatoms
integer
lacquer resins
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CN201280052226.5A
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CN103958561B (en
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冈本慎司
藤永匡敏
木村绘梨奈
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Ube Corp
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Meiwa Plastic Industries Ltd
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    • 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

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  • 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] To provide an epoxy resin composition containing linear phenol novolak resin (more specifically, a phenol-naphthol novolak resin) and epoxy resin, with which it is possible to markedly improve the heat resistance and combustion resistances of articles obtained by curing the resin composition. Also, to provide a linear phenol novolak resin suitable for use in said epoxy resin composition. [Solution] A linear phenol novolak resin comprising the chemical structure represented by general formula (1) below. [Compound represented by formula 1] (In the formula, A represents, independent of one another, a monovalent or bivalent unit of general formula (2) below, or a monovalent or bivalent unit of general formula (3), n is an integer from 0 to 20, R1 represents, independent of one another, an alkyl group having 1 to 8 carbon atoms, and p and q are independent integers from 0 to 2.)

Description

Lacquer resins and used the composition epoxy resin of this lacquer resins
Technical field
The present invention relates to composition epoxy resin and aptly for the lacquer resins (phenol novolak resin) of this composition epoxy resin.Composition epoxy resin of the present invention has improved thermotolerance and the resistance to flame of the cured article obtaining.In addition, for composition epoxy resin of the present invention, due to the solvability excellence of the lacquer resins preferably using, thereby be easily dissolved in solvent equably, thus can be aptly for for example manufacturing the purposes of plywood.
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, be accompanied by the progress of the technology in the electric and electronic such as semiconductor-encapsulating material, plywood field, composition epoxy resin is required further to improve various characteristics.
For example, owing to adopting unleaded scolding tin, Reflow Soldering temperature becomes higher, therefore the composition epoxy resin using in the semiconductor packages such as plywood, interlayer dielectic, sealing material is required to the thermotolerance higher than currently available products.In addition, as the countermeasure for environmental problem, require to improve resistance to flame (flame retardant resistance) in the case of not using when burning may produce the fire retardant such as halogen and the antimony with carinogenicity under a cloud of dioxin.In addition,, in the time using composition epoxy resin as the body material of plywood or interlayer dielectic, by composition epoxy resin being dissolved in solvent and varnish uses, therefore composition epoxy resin is required to the solubility in solvent.
The composition epoxy resin that discloses a kind of phenol phenolic varnish condensation body in patent documentation 1 and comprised this phenol phenolic varnish condensation body and epoxy resin, described phenol phenolic varnish condensation body makes the mixture of the isomer of two (methoxymethyl) biphenyl react and obtain with oxybenzene compound, and the mixture of the isomer of described pair of (methoxymethyl) biphenyl is that the reaction product by making to be obtained by the halogenating reaction of methoxymethyl benzene is carried out dehalogenation linked reaction and synthetic.For this phenol phenolic varnish condensation body, as epoxy curing agent, its water absorbability, thermotolerance and pliability excellence.But, the concrete disclosed phenol phenolic varnish condensation body in this place has just used the mixture of the isomer of two (methoxymethyl) biphenyl, according to embodiment, the second-order transition temperature of the cured article being formed by the composition epoxy resin that comprises obtained phenol phenolic varnish condensation body and epoxy resin is 140 DEG C of left and right, and it also exists room for improvement aspect thermotolerance.
The composition epoxy resin that discloses a kind of phenol-naphthol novolac varnish condensation body in patent documentation 2 and comprised this phenol-naphthol novolac varnish condensation body and epoxy resin, described phenol-naphthol novolac varnish condensation body is to obtain by the condensation reaction of the biphenol compound of phenol and aphthols and two (methoxymethyl) biphenyl and so on.But this place concrete disclosed phenol-naphthol novolac varnish condensation body has also just used the mixture of isomer of two (methoxymethyl) biphenyl as biphenol compound.Although improved low water absorbable and thermotolerance compared with the phenol phenolic varnish condensation body of this phenol-naphthol novolac varnish condensation body and patent documentation 1, but according to embodiment, the second-order transition temperature of the cured article being formed by the composition epoxy resin that comprises phenol-naphthol novolac varnish condensation body and epoxy resin is 150 DEG C of left and right, and it also exists room for improvement aspect thermotolerance.
The mixture of isomer of preferred use specified proportion is disclosed in patent documentation 1,2 as biphenol compound.But, in patent documentation 1,2 not concrete open and teaching ought use separately 4,4 '-bis-(methoxymethyl) biphenyl such 4, which kind of impact 4 '-body can have to thermotolerance, resistance to flame, solvability etc. during as biphenol compound.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 8-143648 communique
Patent documentation 2: Japanese kokai publication hei 9-176262 communique
Summary of the invention
The problem that invention will solve
The invention provides a kind of composition epoxy resin and can be aptly for the lacquer resins of 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 has improved thermotolerance and the resistance to flame of the cured article obtaining significantly.In addition, the invention provides a kind of composition epoxy resin and can be aptly for the lacquer resins of this composition epoxy resin, this composition epoxy resin is due to the solvability excellence of the lacquer resins preferably using, thereby be easily dissolved in solvent equably, thereby can be aptly for for example manufacturing the purposes of plywood.
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 representing with following general formula (1).
(in formula, A represents 1 valency of following general formula (2) or the unit of divalent or 1 valency of general formula (3) or the unit of divalent independently of one another, n is 0～20 integer, and R1 represents that carbonatoms is 1～8 alkyl independently of one another, and p and q are 0～2 integer independently of one another.)
Wherein, as lacquer resins entirety, A is by 1 valency of following general formula (2) or 1 valency of the unit of divalent and following general formula (3) or these two formation of unit of divalent.
(in formula, R2 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, the integer that i is 1～3, and the integer that j is 0～2, i and j add up to below 4.)
(in formula, R3 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, the integer that k is 1～3, and the integer that l is 0～4, k and l add up to below 6.)
(2) according to the lacquer resins described in above-mentioned 1, it is characterized in that, the ratio [unit of the unit/general formula (3) of general formula (2)] of the unit of the unit of described general formula (2) and described general formula (3) is in 10/90～90/10 scope.
(3) according to the lacquer resins described in above-mentioned 1 or 2, it is characterized in that, form the composition that represents with following general formula (4) in whole compositions of the lacquer resins area ratio when measuring by HPLC and count below 27%.
(in formula, R1 represents that carbonatoms is 1～8 alkyl independently of one another, p and q are 0～2 integer independently of one another, R3 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, k is 1～3 integer, l is 0～4 integer, and k and l add up to below 6.)
(4) a kind of manufacture method of lacquer resins, it is characterized in that, the phenol representing with following general formula (5) and the aphthols representing with following general formula (6) are reacted with the biphenol compound representing with following general formula (7).
(in formula, R2 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, the integer that i is 1～3, and the integer that j is 0～2, i and j add up to below 4.)
(in formula, R3 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, the integer that k is 1～3, and the integer that l is 0～4, k and l add up to below 6.)
(in formula, R1 represents that carbonatoms is 1～8 alkyl independently of one another, and p and q are 0～2 integer independently of one another, and X represents that carbonatoms is 1～4 alkoxyl group or halogen atom.)
(5) composition epoxy resin, it is to comprise lacquer resins (A) and the epoxy resin (B) described in any one in above-mentioned 1～3 to form.
(6) according to the composition epoxy resin described in above-mentioned 5, it is characterized in that, the second-order transition temperature of the cured article obtaining is more than 155 DEG C, is preferably more than 170 DEG C, more preferably more than 180 DEG C.
(7) according to the composition epoxy resin described in above-mentioned 5 or 6, it is characterized in that, the flame retardant resistance based on UL-94 of the cured article obtaining is V-0.
(8) a kind of composition epoxy resin, it is characterized in that, it is to comprise lacquer resins (A), epoxy resin (B) and the solvent (C) described in any one in above-mentioned 1～3 to form, wherein, lacquer resins (A) and epoxy resin (B) are dissolved in solvent (C) equably.
(9) cured article, it is any in above-mentioned 5～8 composition epoxy resin to be solidified form.
(10) plywood, it uses the composition epoxy resin of above-mentioned 8 to form matrix resin.
In addition, " independently of one another " refers to herein: when representing that the symbol of corresponding substituting group or numeral exists when multiple, each symbol of multiple expression substituting groups or numeral can be different substituting group or numerals independently of one another.For example, (R1) in described general formula (1) pin R1 with (R1) qin R1 can be identical alkyl, can be also the different alkyl of carbonatoms; And, as (R1) pin R1 while being multiple, each R1 can be respectively identical alkyl, can be also the different alkyl of carbonatoms.
In addition,, in the present invention, as the measuring method of second-order transition temperature, for the ease of relatively measuring by two kinds of methods, in the situation that contingency can produce difference because of measuring method, preferentially utilize the measuring method of Measurement of Dynamic Viscoelasticity device.
Invention effect
According to the present invention, can provide a kind of composition epoxy resin and can be aptly for the lacquer resins of 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 has significantly improved thermotolerance and the resistance to flame of the cured article obtaining.In addition, according to the present invention, can provide a kind of composition epoxy resin and can be aptly for the lacquer resins of this composition epoxy resin, this composition epoxy resin is due to the solvability excellence of the lacquer resins preferably using, thereby be easily dissolved in solvent equably, thereby can be aptly for for example manufacturing the purposes of plywood, interlayer dielectic.
Brief description of the drawings
Fig. 1 is the HPLC figure that removes the reaction mixture before unreacting material composition in embodiment 1 when reaction terminating.
Fig. 2 is the HPLC figure of the lacquer resins that obtains in embodiment 1.
Fig. 3 is the HPLC figure that removes the reaction mixture before unreacting material composition in embodiment 2 when reaction terminating.
Fig. 4 is the HPLC figure of the lacquer resins that obtains in embodiment 2.
Embodiment
Lacquer resins of the present invention can be reacted with the biphenol compound representing with following general formula (7) and be obtained aptly by the phenol that makes to represent with following general formula (5) and the aphthols representing with following general formula (6).
(in formula, R2 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, the integer that i is 1～3, and the integer that j is 0～2, i and j add up to below 4.)
(in formula, R3 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, the integer that k is 1～3, and the integer that l is 0～4, k and l add up to below 6.)
(in formula, R1 represents that carbonatoms is 1～8 alkyl independently of one another, and p and q are 0～2 integer independently of one another, and X represents that carbonatoms is 1～4 alkoxyl group or halogen atom.)
As the phenol representing with general formula (5), as long as the compound on phenyl ring with more than one hydroxyl just, be not particularly limited, can also there is the substituting group such as alkyl, alkoxyl group.For example, 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, methyl hexylphenol, dipropyl phenol, dibutyl phenol etc., be preferably phenol.These phenol can be one matter, can be also multiple mixture.
As the aphthols representing with general formula (6), as long as the compound on naphthalene nucleus with more than one hydroxyl just, be not particularly limited, can also there is the substituting group such as alkyl, alkoxyl group.For example, 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, methyl hexyl naphthols, dimethyl naphthols, diethyl naphthols, dibutyl naphthols etc., be preferably naphthyl alcohol.These aphthols can be one matter, can be also two or more mixtures.
As the biphenol compound representing with general formula (7), can list aptly 4,4 '-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.It is that 1～8 alkyl is as substituting group that these biphenol compounds can also have carbonatoms.These biphenol compounds can be one matter, can be also two or more mixtures.
In the time that phenol and aphthols are reacted with biphenol compound, can not use catalyzer, but conventionally 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, the biphenol compound that particularly has a halogenated methyl in use during as biphenol compound, also can react aptly under the condition that does not have acid catalyst.
In this reaction, with regard to the biphenol compound as raw material, with regard to the mol ratio [(phenol and aphthols)/biphenol compound] of the phenol of raw material and the total of aphthols, preferably 20～1.5, more preferably 6.0～2.0 scope is suitable.In the time that mol ratio is less than 1.5, the viscosity of resin becomes too high, likely can damage operability; In the time that mol ratio exceedes 20, most product becomes lower molecular weight body, thereby the second-order transition temperature of the cured article obtaining becomes insufficient, or unreacting material is also residual in a large number, thereby unfavorable economically.
In addition, with regard to the mol ratio [phenol/aphthols] of the phenol as raw material and aphthols, preferably 10/90～90/10, more preferably 40/60～90/10 scope is suitable.By making as the phenol of raw material and the mol ratio of aphthols within the scope of this, state as follows brightly, can make the unit of general formula (2) of phenol of resulting from of obtained lacquer resins is preferable range of the present invention with resulting from the ratio of unit of general formula (3) of aphthols.,, if naphthols composition is very few, the unit of the general formula (3) importing in resin reduces, thereby is sometimes difficult to obtain sufficient thermotolerance.In addition, if naphthols composition is too much, the unit of the general formula (3) importing in resin increases, and the represented unit of general formula (4) also increases, thereby can cause solvent solubility impaired.
Reaction conventionally can or exist in the situation that not there is not solvent water and/or organic solvent equal solvent and at 0 DEG C～150 DEG C, carry out about 0.5 hour～10 hours, but in order to regulate ratio and the polymerization degree etc. of composition that forms lacquer resins, the reaction conditions to temperature of reaction, reaction times and so on etc. regulates aptly.
In addition, preferably after reaction terminating, unreacted phenol and aphthols etc. under reduced pressure heated or inject the ripple gas while heat of not living, being distilled thus except going to system.In addition, acid catalyst can wait to clean by washing and remove.
By this reaction, biphenol compound forms crosslinking structure between the multiple unit that formed by phenol and/or aphthols and bonding has generated the lacquer resins being formed by the chemical structure representing with general formula (1).
Therefore, in general formula (1), formed molecular end at the phenol, the aphthols that represent with general formula (5) and general formula (6), the A in general formula (1) becomes 1 valency unit of general formula (2) and general formula (3); Entered by group in intramolecular situation, the A in general formula (1) becomes the divalent unit of general formula (2) and general formula (3).
In addition, in this reaction, the composition that the n that first generates general formula (1) is 0.Then the composition that a part for the composition that the n, generating is 0 is further 0 with biphenol compound or the n that generates reacts.Like this, further generate successively n and be 1 and exceed 1 composition.On the other hand, be 1 and during the reaction that exceedes 1 composition carries out generating n, the reaction of the composition that to generate n be 0 is also continuing, thereby the aggregate of the lacquer resins of the present invention Multiple components that normally the n value of general formula (1) is different.
One of feature of the lacquer resins of the present invention obtaining by this reaction is: make phenol and aphthols and by 4, and 4 of 4 '-bis-(chloromethyl) biphenyl and so on, the biphenol compound that 4 '-body forms is used in combination.And, improved aptly thermotolerance and resistance to flame by the cured article that has used the composition epoxy resin of lacquer resins of the present invention to form.
In the present invention, with regard to the lacquer resins being formed by the chemical structure representing with general formula (1), result from phenol general formula (2) unit with result from the ratio [unit of the unit/general formula (3) of general formula (2)] of unit of general formula (3) of aphthols and be preferably in 10/90～90/10 scope, more preferably in 10/90～60/40 scope, more preferably in 10/90～50/50 scope, be particularly preferably in 10/90～40/60 scope.
By making the ratio of the unit of general formula (2) and the unit of general formula (3) within the scope of this, can improve aptly thermotolerance and the resistance to flame of the cured article being formed by composition epoxy resin of the present invention.
By combining by 4 in resin, the biphenol compound that 4 '-body forms, and import the unit representing with general formula (3), the thermotolerance of the resin obtaining is improved effectively, improves resistance to flame thereby can effectively suppress burning.But in the time that the ratio of the unit of general formula (3) is too high, the viscosity, the softening temperature that cause resin rise, thereby damage sometimes operability, in addition, the unit of the general formula (4) in resin increases, thereby is difficult to control the solvability of resin.
Therefore, in the reaction of preparation lacquer resins of the present invention, preferably so that the mode of the ratio of the unit of the unit of general formula (2) and general formula (3) in described scope the usage ratio of the phenol representing with general formula (5) as raw material and the aphthols that represents with general formula (6) is regulated.Certainly, hope can be improved to the usage ratio of the raw material of the unit of the ratio importing in lacquer resins and improve, but with regard to its ratio, because the reactivity of these phenol, aphthols and biphenol compound is different separately, therefore also to regulate its ratio with reference to the mol ratio of the total of their reactivity size and then biphenol compound and phenol and aphthols [(phenol and aphthols)/biphenol compound] and the reaction conditions adopting etc.To those skilled in the art, its control method is apparent, can find out simply by carrying out preparative experiment if desired.
In the present invention, one of preferred configuration of lacquer resins is: the composition that represents with general formula (4) in whole compositions of the aggregate representing with general formula (1) that the forms lacquer resins area ratio when measuring by HPLC is counted below 27%, be preferably below 20%.If by the Composition Control one-tenth representing with general formula (4), the area ratio when measuring by HPLC is counted below 27% in whole compositions, improving for the solvability of organic solvent, is that 50/50 ratio also can be dissolved equably even if for example make resin/solvent for methylethylketone in mass.
On the other hand, if the area ratio of the composition representing in general formula (4) in whole compositions when measuring by HPLC exceedes 27%, reduce for the solvability of organic solvent, for example, be difficult to dissolve equably in the time making resin/solvent be 50/50 ratio in mass for methylethylketone.
Even if be that the ratio of 50/50 high density also can be dissolved equably in mass if for example use methylethylketone and make resin/solvent, thus easily composition epoxy resin of the present invention is dissolved in to methylethylketone and varnish as body material and the interlayer dielectic of plywood.Cannot dissolve equably, cannot varnish in the situation that, be difficult for body material and interlayer dielectic as plywood.
The adjusting of the amount of the composition representing with general formula (4) in the composition of lacquer resins is carried out as follows: with reference to their reactivity size and the reaction conditions being adopted etc., mol ratio [(phenol and aphthols)/biphenol compound] and the mol ratio [phenol/aphthols] of phenol and aphthols of the total to the biphenol compound using as raw material and phenol and aphthols regulate on one side on one side.
When the mol ratio [(phenol and aphthols)/biphenol compound] of total that makes biphenol compound and phenol and aphthols is during for value (more approaching 1 value) than conventionally less, can make composition polymer quantification on the whole, thereby reduce general formula (4) composition, because of but suitable.In addition, with regard to the mol ratio of phenol and aphthols, because the reactivity of aphthols is higher than phenol, thereby can further advance reaction in the time making the ratio of aphthols relatively high, make composition polymer quantification on the whole, thereby reduce general formula (4) composition, because of but suitable; On the other hand, in the time that the ratio of aphthols is too high, the composition of general formula (4) increases, thereby solvability is had to detrimentally affect.For example, be 100% if make aphthols, be certainly difficult to significantly the amount of the composition that reduces general formula (4), thereby be difficult to improve solubleness.
The adjusting of these ratios will be carried out with reference to their reactivity size and the reaction conditions adopting etc.To those skilled in the art, its control method is apparent, can find out simply by carrying out preparative experiment if desired.
The lacquer resins that chemical structure was formed (A) by representing taking general formula (1) of the present invention preferably softening temperature is 60 DEG C～150 DEG C, more preferably 70 DEG C～140 DEG C.In the time that softening temperature is less than 60 DEG C, easily produce adhesion etc.; If exceed 150 DEG C, operability has problems sometimes.In addition, the weight-average molecular weight of the lacquer resins that chemical structure was formed (A) by representing with general formula (1) of the present invention is preferably 500～10000 scope, more preferably 500～5000, more preferably 500～2000 scope.
Next, composition epoxy resin of the present invention is described.
Composition epoxy resin of the present invention is to comprise by the lacquer resins that chemical structure was formed (A) representing with general formula (1) and epoxy resin (B) to form.
As the epoxy resin using in composition epoxy resin of the present invention (B), for example, can list: in the glycidyl ether type epoxy resin such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aralkyl-type epoxy resin, cresols phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, tris-phenol type epoxy resin, biphenyl type epoxy resin, glycidyl esters type epoxy resin, glycidyl group amine type epoxy resin, halogenated epoxy resin equimolecular, there is the epoxy resin of more than two epoxy group(ing) etc.These epoxy resin can use separately 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, triphenyl methane type epoxy resin, cresols phenolic resin varnish type epoxy resin etc. be suitable especially.
As the adding proportion of the epoxy resin using in composition epoxy resin of the present invention (B), the ratio [hydroxyl equivalent/epoxy equivalent (weight)] of the epoxy equivalent (weight) in hydroxyl equivalent and the epoxy resin of solidifying agent is preferably the scope of 0.5～2.0 left and right, the more preferably scope of 0.8～1.2 left and right.Outside this scope time, because curing reaction does not fully carry out, unreacted solidifying agent and the reason such as epoxy resin is remaining, sometimes cannot bring into play effect of the present invention.
In composition epoxy resin of the present invention, there is the effect of the solidifying agent of epoxy resin by the lacquer resins that chemical structure was formed (A) representing with general formula (1), but in composition epoxy resin of the present invention, also can comprise other solidifying agent except the lacquer resins that chemical structure was formed (A) by representing with general formula (1).
Other solidifying agent except lacquer resins (A) is not particularly limited, can uses various epoxy curing agents according to the application target of composition.For example, can use aptly amine is that solidifying agent, acid amides are the conventional epoxy curing agents such as solidifying agent, acid anhydrides are solidifying agent, resol except the lacquer resins that chemical structure was formed (A) by representing with general formula (1) is solidifying agent.
In addition, in composition epoxy resin of the present invention, the ratio by the lacquer resins that chemical structure was formed (A) representing with general formula (1) in solidifying agent is not particularly limited, but the preferred higher ratio in order to improve the thermotolerance, resistance to flame of cured article, be more than 30 quality %, more than being preferably 50 quality %, more preferably more than 70 quality %, more preferably 90 quality %, are particularly preferably 100 quality %.
Composition epoxy resin of the present invention preferably further contains that solvent (C) forms, 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 to uniform varnish solution with high density, just can be used as aptly body material and the interlayer dielectic of plywood.
Described solvent (C), as long as composition epoxy resin is dissolved, is not particularly limited, organic solvent used preferably can use aptly conventionally by the body material of plywood and interlayer dielectic varnish time.For example, 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 use separately, also can be used in combination of two or more.
When by composition epoxy resin varnish of the present invention, do not limit, the concentration of preferred resin composition is 10 quality %～90 quality % left and right, and soltion viscosity is 1cP～5000cP left and right at 30 DEG C.
In composition epoxy resin of the present invention, can use aptly other composition conventionally using in composition epoxy resin according to its purposes.
For example, can use the curing catalyst in order to make epoxy resin cure by resol.As curing catalyst, can list aptly known organic phosphine compound and boron salt thereof, tertiary amine, quaternary ammonium salt, imidazoles and tetraphenyl boron salt thereof etc.Among them, from the viewpoint of solidified nature, wet fastness, triphenylphosphine.In addition, be required, higher mobility, preferably to manifest the curing catalyst of active latent heat by heat treated at composition epoxy resin, wherein the more preferably tetraphenylphosphonium derivative such as tetraphenylphosphonium tetraphenyl borate.The addition of curing catalyst is identical just with the ratio in known composition epoxy resin.
In addition, can also use aptly the weighting agents such as inorganic filler.As inorganic filler, can use amorphism silicon-dioxide, crystallinity silicon-dioxide, aluminum oxide, Calucium Silicate powder, calcium carbonate, talcum, mica, barium sulfate etc., particularly more preferably amorphism silicon-dioxide, crystallinity silicon-dioxide.Particle diameter as inorganic filler is not particularly limited, if but consider that filling ratio is preferably 0.01 μ m～150 μ m.
The mixed ratio of inorganic filler is not particularly limited, and for 70 % by weight～95 % by weight in composition epoxy resin, is preferably 75 % by weight～90 % by weight, more preferably 80 % by weight～90 % by weight.If the ratio of inorganic filler is outside above-mentioned scope, 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, likely damage mobility.
In addition,, for composition epoxy resin of the present invention, can add as required or react in advance releasing agent, tinting material, coupling agent, fire retardant etc. using.In addition, the mixed ratio of these additives is identical just with the ratio in known composition epoxy resin.In composition epoxy resin of the present invention, can also add aptly as required in addition the phosphorus flame retardants such as the nitrogenated flame retardant such as trimeric cyanamide, isocyanuric acid compound, red phosphorus, phosphate cpd, organo phosphorous compounds as flame retardant.
Composition epoxy resin of the present invention can be manufactured by following manner: use such as mixing tank etc., lacquer resins (A), epoxy resin (B) and the curing catalyst adding as required, inorganic filler, other additive etc. are evenly mixed, utilize the mixing rolls such as warming mill, kneader or forcing machine and carry out mixing, coolingly with molten state, and pulverizing as required.
Such composition epoxy resin is not limited, but can be used as aptly semiconductor-encapsulating material etc.
In addition, for composition epoxy resin of the present invention, in methylethylketone, propylene glycol monomethyl ether or dimethyl formamide equal solvent (C), add by the lacquer resins that chemical structure was formed (A) representing with general formula (1), epoxy resin (B) and other solidifying agent adding as required, curing catalyst, inorganic filler, additive etc., heat as required, stir, can manufacture thus at least lacquer resins (A) and epoxy resin (B) the varnish solution that uniform dissolution forms in solvent (C).
To this varnish epoxy resin (solution) composition do not limit, can be aptly as body material and the interlayer dielectic of plywood.
For composition epoxy resin of the present invention, as required by after solvent seasoning, carry out heat treated, can obtain aptly thus cured article.
Although also depend on the having or not of curing catalysts and curing catalyst, their addition etc. for the heat treated condition that obtains cured article, conventionally 100 DEG C～300 DEG C left and right, preferably heat treated is suitable about 1 minute to 10 hours at the temperature of 120 DEG C～200 DEG C of left and right.
Composition epoxy resin of the present invention can be aptly as the sealing material that semiconductor element is sealed.For example, lead frame that is mounted with this semiconductor element etc. is arranged in metal chamber, utilize afterwards the forming methods such as transfer mould, compressed moulding, injection moulding by composition epoxy resin moulding, to the temperature of 300 DEG C of left and right, by heat treated etc., composition epoxy resin is solidified at 120 DEG C, can obtain aptly thus semiconductor device.
In addition, for composition epoxy resin of the present invention, preferably uniform dissolution is in methylethylketone equal solvent and varnish, and with its varnish solution coat or the dipping porous glass base material such as glass or glass fibre, paper, aramid fiber etc., then carry out heat treated (semicure), can manufacture thus printed base plate prepreg.In addition, by obtained printed base plate, with prepreg, multiple are stacked, pressurize as required while carry out heat treated and make it curing, can manufacture thus plywood.
In addition, for plywood or prepreg, stacked tinsel in one or two sides, pressurizes as required while carries out heat treated (for example under 180 DEG C, the pressure of 4MPa heat treated 60 minutes), can obtain thus metal-clad.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, preferably uniform dissolution is in methylethylketone equal solvent and varnish, and utilize mould to be coated with machine (die coater) etc. its varnish solution is evenly coated to the such as supporting body surface such as PET film or Copper Foil, obtained coated film is carried out to heat drying, form thus the duplexer sheet material with resin layer, it can be used as interlayer dielectic aptly.
Embodiment
Below, the present invention will be described in more detail for example.In addition, the invention is not restricted to these examples.
[1] preparation of lacquer resins
The material using in the example of the preparation to lacquer resins below describes.
(1) phenol: and Guang Chun medicine industrial manufactures
(2) naphthyl alcohol (1-naphthols): and Guang Chun medicine industrial manufactures
(3) 4,4 '-bis-(chloromethyl) biphenyl: and Guang Chun medicine industrial manufactures
The analytical procedure and the evaluation method that in the example of the preparation to lacquer resins below, use describe.
(1) softening temperature: measure and carry out by the ring and ball softening point based on JIS K6910.
(2) hydroxyl equivalent: measure and carry out by the hydroxyl equivalent based on JIS K0070.
(3) mensuration of the ratio of the unit of the unit of general formula (2) and general formula (3) [unit of the unit/general formula (3) of general formula (2)]: in the preparation of lacquer resins, measure the charging capacity of raw material, lacquer resins amount and the amount of by-products generating, gone out the amount of unreacting material by reaction budget analysis.Whole amounts of biphenol compound are reacted, therefore unreacting material by as form general formula (2) unit raw material phenol and form as the aphthols of raw material of the unit that forms general formula (3).With regard to the ratio of the unreacted phenol in reaction mixture and aphthols, measure by the HPLC of the condition by shown below the HPLC figure obtaining 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: STR ODS-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 mixed solution that the volume ratio that uses acetonitrile/5% phosphoric acid solution in the time measuring beginning is 20/60, after mensuration starts, be till 60/40 by ratio to the volume ratio that increases linearly acetonitrile for 10 minutes, be then till 100/0 by ratio to the volume ratio that increases linearly acetonitrile for 5 minutes, under this state, use afterwards acetonitrile to measuring end.
Flow: 1.00mL/ minute
Detect wavelength: 220nm
Mathematical expression 1
Import charging capacity-(the aphthols ratio in unreacting material amount × unreacting material) of aphthols amount=aphthols
Import charging capacity-(the phenol ratio in unreacting material amount × unreacting material) of phenol amount=phenol
(4) ratio of the composition representing with general formula (4): measure by the HPLC of the condition by shown below the HPLC obtaining and scheme, obtain as its area ratio.
The condition determination of HPLC
Machine: the HPLC that company of Shimadzu Seisakusho Ltd. manufactures
Post: STR ODS-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 mixed solution that the volume ratio that uses acetonitrile/5% phosphoric acid solution in the time measuring beginning is 50/50, after mensuration starts, be till 75/25 by ratio to the volume ratio that increases linearly acetonitrile for 20 minutes, be then till 100/0 by ratio to the volume ratio that increases linearly acetonitrile for 20 minutes, under this state, use afterwards acetonitrile to measuring end.
Flow: 1.00mL/ minute
Detect wavelength: 220nm
(5) solvability:
Utilize method shown below, evaluate 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: after dissolving and at normal temperature (23 DEG C), after lower standing 12 hours, observe by range estimation.By resin uniform dissolution and after leaving standstill, also to have kept the average evaluation of uniform solution be 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)
To possessing thermometer, feed intake/distillate mouthful, add phenol 188.0g (2.0 moles), naphthyl alcohol 123.4g (0.9 mole) in glass flask processed that the capacity of water cooler and stirrer is 1000mL, till being warming up to interior temperature being 60 DEG C under nitrogen gas stream, make thus material dissolution.Add 4,4 '-bis-(chloromethyl) biphenyl 179.3g (0.7 mole), be to react 4 hours at 60 DEG C～100 DEG C in interior temperature, and then at 165 DEG C, react 3 hours, remove afterwards the unreacted component of raw material by decompression-steam treatment.
The softening temperature of the lacquer resins obtaining 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) recording by HPLC and the unit of general formula (3) is 30/70, and the ratio of the composition representing taking general formula (4) is as 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 to Fig. 1.Calculate phenol in unreacting material and the ratio of aphthols is 82% and 18% by this figure.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) importing in resin and the unit of general formula (3).
In addition, the HPLC of obtained lacquer resins is illustrated in to Fig. 2.Obtained the ratio of the composition (owing to there being isomer, thereby being the total at three peaks) representing with general formula (4) by the Area Ratio of this figure.
(embodiment 2)
To possessing thermometer, feed intake/distillate mouthful, add phenol 84.6g (0.9 mole), naphthyl alcohol 129.6g (0.9 mole) in glass flask processed that the capacity of water cooler and stirrer is 1000mL, till being warming up to interior temperature being 60 DEG C under nitrogen gas stream, make thus material dissolution.Add 4,4 '-bis-(chloromethyl) biphenyl 180.7g (0.7 mole), be to react 4 hours at 60 DEG C～100 DEG C in interior temperature, and then at 165 DEG C, react 3 hours, remove afterwards the unreacted component of raw material by decompression-steam treatment.
The softening temperature of the lacquer resins obtaining 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) recording by HPLC and the unit of general formula (3) is 20/80, and the ratio of the composition representing taking general formula (4) is as 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 to Fig. 3.Calculate phenol in unreacting material and the ratio of aphthols is 76% and 24% by this figure.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 to Fig. 4.Obtained the ratio of the composition (owing to there being isomer, thereby being the total at three peaks) representing with general formula (4) by the Area Ratio of this figure.
(embodiment 3)
To possessing thermometer, feed intake/distillate mouthful, add phenol 94.0g (1.0 moles), naphthyl alcohol 144.0g (1.0 moles) in glass flask processed that the capacity of water cooler and stirrer is 1000mL, till being warming up to interior temperature being 60 DEG C under nitrogen gas stream, make thus material dissolution.Add 4,4 '-bis-(chloromethyl) biphenyl 161.9g (0.7 mole), be to react 4 hours at 60 DEG C～100 DEG C in interior temperature, and then at 165 DEG C, react 3 hours, remove afterwards the unreacted component of raw material by decompression-steam treatment.
The softening temperature of the lacquer resins obtaining is 117 DEG C, and hydroxyl equivalent is 247g/eq, and the ratio of the composition representing taking general formula (4) recording by HPLC is as 24%.The deliquescent evaluation of this lacquer resins is judged to be △.
(embodiment 4)
To possessing thermometer, feed intake/distillate mouthful, add phenol 188.0g (2.0 moles), naphthyl alcohol 123.4g (1.0 moles) in glass flask processed that the capacity of water cooler and stirrer is 1000mL, till being warming up to interior temperature being 60 DEG C under nitrogen gas stream, make thus material dissolution.Add 4,4 '-bis-(chloromethyl) biphenyl 119.5g (0.5 mole), be to react 4 hours at 60 DEG C～100 DEG C in interior temperature, and then at 165 DEG C, react 3 hours, remove unreacted component by decompression-steam treatment afterwards.
The softening temperature of the lacquer resins obtaining is 97 DEG C, and hydroxyl equivalent is 238g/eq, and the ratio of the composition representing taking general formula (4) recording by HPLC is as 30%.The deliquescent evaluation of this lacquer resins is judged to be ×.
(embodiment 5)
To possessing thermometer, feed intake/distillate mouthful, add phenol 141.0g (1.5 moles), naphthyl alcohol 216.0g (1.5 moles) in glass flask processed that the capacity of water cooler and stirrer is 1000mL, till being warming up to interior temperature being 60 DEG C under nitrogen gas stream, make thus material dissolution.Add 4,4 '-bis-(chloromethyl) biphenyl 125.5g (0.5 mole), be to react 4 hours at 60 DEG C～100 DEG C in interior temperature, and then at 165 DEG C, react 3 hours, remove unreacted component by decompression-steam treatment afterwards.
The softening temperature of the lacquer resins obtaining is 94 DEG C, and hydroxyl equivalent is 238g/eq, and the ratio of the composition representing taking general formula (4) recording by HPLC is as 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, for the composition epoxy resin that has used lacquer resins of the present invention is dissolved in solvent equably, the ratio of the composition representing taking general formula (4) as below 27%, to be preferably below 20% be suitable.
Table 1
[2] preparation of composition epoxy resin of the present invention and with the comparison of patent documentation 2
Below, the material using in the example of composition epoxy resin is described.
(1) epoxy resin
Ortho-cresol type epoxy resin " EOCN-1020-70 ": Japanese chemical drug company manufactures, and epoxy equivalent (weight) is 200g/eq, and softening temperature is 70 DEG C
(2) curing catalyst (curing catalysts)
Triphenylphosphine (TPP): Bei Xing chemical company manufactures
Below, the evaluation method of composition epoxy resin is described.
(1) thermotolerance (second-order transition temperature (Tg))
Carry out according to the measuring method of patent documentation 2.That is, use the test film being formed by the cured article that is of a size of 4mm × 6mm × 10mm, heat up with the heat-up rate of 5 DEG C/min, measure according to TMA method (Thermal Mechanical Analysis, thermomechanical analysis) thus.
(embodiment 6)
Add the lacquer resins, ortho-cresol type epoxy resin EOCN-1020-70 and the curing catalyst TPP that in embodiment 1, obtain with the proportioning shown in table 2, make composition epoxy resin, under the condition of 150 DEG C, it is carried out to heating and melting mixing, carrying out after vacuum defoamation casting mold in the mould (thickness is 4mm) at 150 DEG C, and solidify 5 hours at 150 DEG C, then further at 180 DEG C, solidify 8 hours, obtain thus curing molding body.
For this curing molding body, measure second-order transition temperature, result is 175 DEG C.
With regard to this embodiment 6, except changing the lacquer resins using, 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 be shown in table 2.
Table 2
As shown in Table 2, owing to having used 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 using 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): Bei Xing chemical company manufactures
(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 TA Instruments company manufactures) to measure with the heat-up rate of 3 DEG C/min.
(3) mechanical characteristics: physical strength is measured according to JIS K7171.
(embodiment 7)
Add the lacquer resins, biphenyl type epoxy resin YX-4000, curing catalyst TPP and the inorganic filler silicon-dioxide MSR-2212 that in embodiment 1, obtain with the proportioning shown in table 2, under the condition of 80 DEG C～100 DEG C, use two rollers to carry out mixing to them, pulverize afterwards, obtain composition epoxy resin of the present invention.
Make blank (tablet) with obtained composition epoxy resin, utilizing low pressure Transfer molding machine is that 175 DEG C, injection pressure are, under the condition of 600 seconds, this blank is injected to mould for 6.8MPa, dwell time in die temperature, make thus test film, from taking out, mould further at 180 DEG C, carries out the after fixing of 8 hours, obtain EMC (Epoxy Moldering Compound, the epoxy molding compound) test film being formed by the cured article of composition epoxy resin.
By the table 3 that the results are shown in that it is evaluated.
(embodiment 8)
The lacquer resins having obtained in having used embodiment 2, carry out same operation with embodiment 7, obtain EMC (Epoxy Moldering Compound, the epoxy molding compound) test film being formed by the cured article of composition epoxy resin.
By the table 3 that the results are shown in that it is evaluated.
(embodiment 9)
The lacquer resins having obtained in having used embodiment 3, carry out same operation with embodiment 7, obtain EMC (Epoxy Moldering Compound, the epoxy molding compound) test film being formed by the cured article of composition epoxy resin.
By the table 3 that the results are shown in that it is evaluated.
(embodiment 10)
The lacquer resins having obtained in having used embodiment 4, carry out same operation with embodiment 7, obtain EMC (Epoxy Moldering Compound, the epoxy molding compound) test film being formed by the cured article of composition epoxy resin.
By the table 3 that the results are shown in that it is evaluated.
The lacquer resins having obtained in having used embodiment 5, carry out same operation with embodiment 7, obtain EMC (Epoxy Moldering Compound, the epoxy molding compound) test film being formed by the cured article of composition epoxy resin.
By the table 3 that the results are shown in that it is evaluated.
The lacquer resins having obtained in having used embodiment 6, carry out same operation with embodiment 7, obtain EMC (Epoxy Moldering Compound, the epoxy molding compound) test film being formed by the cured article of composition epoxy resin.
By the table 3 that the results are shown in that it is evaluated.
(reference example 1)
To possessing thermometer, feed intake/distillate mouthful, add phenol 470.0g (5.0 moles) in glass flask processed that the capacity of water cooler and stirrer is 1000mL, till being warming up to interior temperature being 60 DEG C under nitrogen gas stream, make thus material dissolution.Add 4,4 '-dichloride methyl biphenyl 313.8g (1.3 moles), is to react 4 hours at 60 DEG C～100 DEG C in interior temperature, and then at 165 DEG C, reacts 3 hours, removes unreacted component afterwards by decompression-steam treatment.The softening temperature of the lacquer resins E obtaining is 68 DEG C, and hydroxyl equivalent is 202g/eq.
(comparative example 1)
The lacquer resins having obtained in having used reference example 1, carry out same operation with embodiment 6, obtain forming by the cured article of composition epoxy resin EMC (Epoxy Moldering Compound, the epoxy molding compound) test film that is of a size of 40mm × 12mm × 1mm.
By the table 3 that the results are shown in that it is evaluated.
Table 3
[4] manufacture and the evaluation of the copper-clad laminated board of composition epoxy resin of the present invention have been used
Below, the material using in the example of the manufacture to copper-clad laminated board describes.
(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): and Guang Chun medicine industrial manufactures
(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 μ m
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 TA Instruments 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 JIS C6481.
(embodiment 12)
Lacquer resins 131 mass parts that obtain add embodiment 1 in diluting solvent methylethylketone 231.2 mass parts in, bisphenol-type epoxy resin 100 mass parts, curing catalyst 2E4MZ0.1 mass parts and varnish, the resinous principle concentration that obtains uniform dissolution is the varnish solution of 50 quality %.
Impregnated glass-fiber cloth M7628-105 in obtained varnish solution is dried afterwards under the condition of 130 DEG C, 15 minutes, obtains prepreg.Overlapping eight these prepregs, and in its both sides overlapping Copper Foil CF-T9B-THE, at 170 DEG C, 30kg/cm 2condition under use press compacting 15 minutes.After copper-clad laminated body is taken out from press, further after fixing 5 hours at 200 DEG C, obtains two sides copper-clad laminated board thus.
The second-order transition temperature of the copper-clad laminated board obtaining 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)
To possessing thermometer, feed intake/distillate mouthful, add phenol 470.0g (5.0 moles), 92% paraformaldehyde 110.9g (3.4 moles) and oxalic acid 0.3g in glass flask processed that the capacity of water cooler and stirrer is 1000mL, at 100 DEG C, react 5 hours.After reaction finishes, utilize decompression-steam treatment to remove unreacted component.The softening temperature of the lacquer resins E obtaining is 96 DEG C, and hydroxyl equivalent is 107g/eq.
(comparative example 2)
Except use in reference example 2 the conventional lacquer resins of preparation to replace the lacquer resins obtaining in embodiment 1 and make proportioning as shown in table 4, operation, obtains two sides copper-clad laminated board similarly to Example 9.
The second-order transition temperature of the copper-clad laminated board obtaining is 147 DEG C, and stripping strength is 1.6N/mm, and water-intake rate is 0.09 quality %.The results are shown in table 4.
Table 4
Utilizability in industry
According to the present invention, can provide a kind of composition epoxy resin and can be aptly for the lacquer resins of 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 has significantly improved thermotolerance and the resistance to flame of the cured article obtaining.In addition, according to the present invention, can provide a kind of composition epoxy resin and can be aptly for the lacquer resins of this composition epoxy resin, this composition epoxy resin is due to the solvability excellence of the lacquer resins preferably using, thereby be easily dissolved in solvent equably, thereby can be aptly for for example manufacturing the purposes of plywood, interlayer dielectic.

Claims (10)

1. a lacquer resins, it is made up of the chemical structure representing with following general formula (1),
In general formula (1), A represents 1 valency of following general formula (2) or the unit of divalent or 1 valency of general formula (3) or the unit of divalent independently of one another, n is 0～20 integer, R1 represents that carbonatoms is 1～8 alkyl independently of one another, p and q are 0～2 integer independently of one another
Wherein, as lacquer resins entirety, by 1 valency of following general formula (2) or the unit of divalent and 1 valency of following general formula (3) or the unit of divalent, these two forms A,
In general formula (2), R2 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, the integer that i is 1～3, and the integer that j is 0～2, i and j add up to below 4,
In general formula (3), R3 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, the integer that k is 1～3, and the integer that l is 0～4, k and l add up to below 6.
2. lacquer resins according to claim 1, it is characterized in that, the ratio of the unit of the unit of described general formula (2) and described general formula (3) is that the unit of unit/general formula (3) of general formula (2) is in 10/90～90/10 scope.
3. lacquer resins according to claim 1 and 2, is characterized in that, form the composition that represents with following general formula (4) in whole compositions of the lacquer resins area ratio when measuring by HPLC and count below 27%,
In general formula (4), R1 represents that carbonatoms is 1～8 alkyl independently of one another, p and q are 0～2 integer independently of one another, R3 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, k is 1～3 integer, l is 0～4 integer, and k and l add up to below 6.
4. a manufacture method for lacquer resins, is characterized in that, the phenol representing with following general formula (5) and the aphthols representing with following general formula (6) are reacted with the biphenol compound representing with following general formula (7),
In general formula (5), R2 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, the integer that i is 1～3, and the integer that j is 0～2, i and j add up to below 4,
In general formula (6), R3 represents that carbonatoms is the alkoxyl group that 1～8 alkyl or carbonatoms are 1～8 independently of one another, the integer that k is 1～3, and the integer that l is 0～4, k and l add up to below 6,
In general formula (7), R1 represents that carbonatoms is 1～8 alkyl independently of one another, and p and q are 0～2 integer independently of one another, and X represents that carbonatoms is 1～4 alkoxyl group or halogen atom.
5. a composition epoxy resin, it is to comprise the lacquer resins described in any one (A) and epoxy resin (B) in claim 1～3 to form.
6. composition epoxy resin according to claim 5, is characterized in that, the second-order transition temperature of the cured article obtaining is more than 155 DEG C.
7. according to the composition epoxy resin described in claim 5 or 6, it is characterized in that, the flame retardant resistance based on UL-94 of the cured article obtaining is V-0.
8. a composition epoxy resin, it is characterized in that, it is to comprise the lacquer resins described in any one (A) in claim 1～3, epoxy resin (B) and solvent (C) to form, wherein, lacquer resins (A) and epoxy resin (B) are dissolved in solvent (C) equably.
9. a cured article, it is to make in claim 5～8 composition epoxy resin described in any one solidify to form.
10. a plywood, its right to use requires the composition epoxy resin described in 8 to form 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)

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