KR20190054058A - Flame retardant resin composition and resin-attached copper foil - Google Patents

Flame retardant resin composition and resin-attached copper foil Download PDF

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KR20190054058A
KR20190054058A KR1020197004704A KR20197004704A KR20190054058A KR 20190054058 A KR20190054058 A KR 20190054058A KR 1020197004704 A KR1020197004704 A KR 1020197004704A KR 20197004704 A KR20197004704 A KR 20197004704A KR 20190054058 A KR20190054058 A KR 20190054058A
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flame retardant
resin
parts
mass
general formula
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히로아키 우메다
마사노리 미야모토
가즈히로 마쓰다
겐 유카와
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타츠타 전선 주식회사
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • 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
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

(EN) Disclosed is a flame retardant resin composition capable of obtaining a flame retardant resin having both good adhesion, flame retardance, dielectric constant and dielectric tangent in good balance, and a flame retardant resin and a resin - attached copper foil, copper clad laminate and printed wiring board using the flame retardant resin. A resin composition comprising a resin component containing a bismaleimide compound represented by the following general formula (I), a curing agent, a phosphorus flame retardant such as cyclophosphane represented by the following general formula (II), and a fluorine resin filler, 0.5 to 30 parts by mass based on 100 parts by mass of the resin component, the content of the phosphorus-based flame retarder is 5 to 30 parts by mass with respect to 100 parts by mass of the resin component, and the content of the fluororesin filler is 10 To 200 parts by mass of the flame retardant resin composition.

Figure pct00016

Description

Flame retardant resin composition and resin-attached copper foil

The present invention relates to a flame retardant resin composition suitable for producing a printed wiring board and the like, a resin-attached copper foil, a copper clad laminate, and a printed wiring board using the same.

With the spread of information terminals such as smart phones, processors and communication modules capable of high-speed processing have emerged and electric signals flowing through the circuit boards on which they are mounted have been speeded up. Therefore, The demand for a substrate material for a substrate is increasing.

The multilayer board is obtained by laminating a resin-coated copper foil coated with a curing resin of a B-stage on a copper foil on the surface of a core substrate and curing the multilayered board to form a multilayered layer, then etching the copper foil to form a circuit, Forming a via hole, plating and connecting the layers to each other. Here, as means for curing the curable resin, a method in which a heat decomposition agent or a photoinitiator is added to the curable resin and heating or light irradiation is used.

In order to improve the high-speed transfer characteristics of the substrate, it is required to use a resin having a low dielectric constant and dielectric tangent to the resin-coated copper foil used for the substrate. For example, fluororesin and liquid crystal polymer have been put to practical use. However, the fluororesin is inferior in adhesiveness and flexibility, and the liquid crystal polymer is inferior in adhesion and processability. Thus, although the use of a bismaleimide compound has been proposed in Patent Document 1, a substrate using the bismaleimide compound of Patent Document 1 has a problem of being easily burned.

In order to solve this problem, it is possible to consider adding a flame retardant to the bismaleimide compound. However, there is a problem that the dielectric constant and the dielectric tangent of the flame retardant increase due to the addition of the flame retardant, Respectively.

In addition, the bismaleimide compound used in Patent Document 1 has a low melt viscosity and a problem that resin flow occurs at the time of press molding. For this reason, as disclosed in Patent Document 1, there is disclosed a technique of making the B stage type by carrying out ultraviolet ray irradiation (irradiation) prior to pressurization. However, depending on the thickness of the resin layer, there is a problem that the bismaleimide resin can not be uniformly cured due to the unevenness in irradiation with ultraviolet rays, the problem that the flame retardant, the curing agent and the wear resistance added to the bismaleimide resin block ultraviolet rays, A problem that hinders the curing of the bismaleimide resin may occur.

Japanese Patent Application Laid-Open No. 2003-243836

Disclosure of the Invention The present invention addresses the above problems and provides a flame retardant resin composition capable of obtaining a flame retardant resin having good balance of adhesion, flame retardance, dielectric constant and dielectric tangent, and a flame retardant resin thereof and a copper foil, a copper clad laminate, And to provide a wiring board.

In order to solve the above problems, the flame retardant resin composition of the present invention comprises a resin component containing a bismaleimide compound represented by the following general formula (I), a curing agent, a cyclophosphazene flame retardant represented by the following general formula (II) , A phosphate flame retardant represented by the following general formula (III), and a phosphate flame retardant represented by the following general formula (IV), and a fluorine resin filler, Wherein the content of the hardening agent is 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin component and the content of the phosphorus flame retardant is 5 to 30 parts by mass with respect to 100 parts by mass of the resin component, And 10 to 200 parts by mass with respect to 100 parts by mass of the resin component.

Figure pct00001

In the formula (I), X represents a hydrocarbon group having an aliphatic, alicyclic or aromatic hydrocarbon group and having 10 to 30 carbon atoms in the main chain (main chain), and these groups may be substituted with a hetero atom, And Y may be a hetero atom, aliphatic, alicyclic or aromatic hydrocarbon group, and these groups may have a hetero atom, a substituent, a phenyl ether skeleton, a sulfonyl skeleton, or a siloxane skeleton, and n is 1 Represents the number of ranges of.

Figure pct00002

In the formula (II), X represents any one of an alkyl group, an alkoxy group, an aryloxy group, an amino group and a phenoxy group.

Figure pct00003

In the formula (III), n is 1 to 100, X 1 is an ammonia or triazine derivative, and p is a number satisfying 0 <p? N + 2.

Figure pct00004

In the formula (IV), r is 1 to 100, Y 1 represents a diamine, and q represents a number satisfying 0 <r? N + 2.

The resin component may contain an epoxy resin.

The curing agent may be one or more selected from a radical initiator, an imidazole-based curing agent, an azo-based curing agent, and a cationic curing agent.

Further, the flame retardant resin composition may have a complex viscosity at 80 캜 of 5 x 10 3 Pa · s to 5 × 10 5 Pa · s.

The flame-retardant resin composition can be made into a flame-retardant resin by curing.

By having the flame-retardant resin on a part or all of the surface of the copper foil, a resin-attached copper foil can be obtained.

The copper clad laminate can be formed by laminating the flame retardant resin and the copper foil.

The flexible printed wiring board may have a part of the copper clad laminate.

According to the flame retardant resin composition of the present invention, a flame retardant resin having both good adhesion, flame retardance, dielectric constant and dielectric tangent can be obtained. It is possible to further improve the high-speed transfer characteristics by lowering the dielectric constant and the dielectric tangent, and it becomes possible to provide a printed wiring board capable of meeting the demand for high-speed processing, which is increasing year by year.

Hereinafter, embodiments of the present invention will be described more specifically.

The flame retardant resin composition according to the present embodiment contains a resin component containing a bismaleimide compound, a curing agent, a phosphorus flame retardant, and a fluorine resin filler. The &quot; resin component &quot; referred to in the present invention includes, besides the polymer, a monomer or a prepolymer which becomes a polymer after curing. The resin component used in the present invention may contain an epoxy resin in addition to the bismaleimide compound as described later. By curing this flame retardant resin composition, the flame retardant resin of the present invention is obtained.

As the bismaleimide compound, those represented by the following general formula (I) are used.

Figure pct00005

In formula (I), X represents an aliphatic, alicyclic or aromatic hydrocarbon group, and these groups may have a hetero atom, a substituent, or a siloxane skeleton. X is preferably an aliphatic or alicyclic hydrocarbon or an aliphatic hydrocarbon group modified by an alicyclic hydrocarbon group, more preferably an aliphatic hydrocarbon group having 10 to 45 carbon atoms, more preferably 10 to 40 carbon atoms Is more preferable. The hydrocarbon group X preferably has 10 to 30 carbon atoms in the main chain, more preferably 10 to 20 carbon atoms.

Y represents an aliphatic, alicyclic or aromatic hydrocarbon group, and these groups may have a hetero atom, a substituent, a phenyl ether skeleton, a sulfonyl skeleton, or a siloxane skeleton. Y is preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 5 to 30 carbon atoms.

n is the number of repeating units and represents a number in the range of 1 to 20; When n is 1 or more, a flame-retardant resin which is a cured product of the flame retardant resin composition having excellent dielectric properties is obtained. When n is 20 or less, a flame retardant resin having excellent strength can be obtained. The bismaleimide compound may be used singly or as a mixture of two or more of those having n of 1 to 20, more preferably a mixture of 1 to 10 of n.

The method for producing the bismaleimide compound is not particularly limited and can be produced by a known method, for example, condensation reaction of an acid anhydride and a diamine followed by dehydration and cyclization (imidization).

Examples of the acid anhydrides usable in the preparation include polybutadiene-graft-maleic anhydride; Polyethylene-graft-maleic anhydride; Polyethylene-maleic anhydride alternating copolymers; Poly-maleic anhydride-1-octadecene alternating copolymer; Polypropylene-graft-maleic anhydride; Poly (styrene-maleic anhydride) copolymer; Pyromellitic anhydride; Maleic anhydride, succinic anhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic dianhydride; Bicyclo (2.2.2) octo-7-ene-2,3,5,6-tetracarboxylic dianhydride; Diethylene triamine pentaacetic acid dianhydride; Ethylenediaminetetraacetic acid dianhydride; 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride; 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride; 4,4'-oxydiphthalic anhydride; 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride; 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride; 4,4'-bisphenol A diphthalic anhydride; 5- (2,5-dioxytetrahydro) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; Ethylene glycol bis (trimellitic anhydride); Hydroquinone diphthalic anhydride; Allyl nadic anhydride; 2-octen-1-yl succinic anhydride; Phthalic anhydride; 1,2,3,6-tetrahydrophthalic anhydride; 3,4,5,6-tetrahydrophthalic anhydride; 1,8-naphthalic anhydride; Glutaric anhydride; Dodecenylsuccinic anhydride; Hexadecenylsuccinic anhydride; Hexahydrophthalic anhydride; Methylhexahydrophthalic anhydride; Tetradecenylsuccinic anhydride and the like.

Examples of diamines usable for the production include 1,10-diaminodecane; 1,12-diaminododecane; Dimer diamine; 1,2-diamino-2-methylpropane; 1,2-diaminocyclohexane; 1,2-diaminopropane; 1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane; 1,7-diaminoheptane; 1,8-diaminomethane; 1,8-diaminooctane; 1,9-diaminononane; 3,3'-diamino-N-methyldipropylamine;Diaminomalonitrile;1,3-diaminopentane;9,10-diaminophenanthrene;4,4'-diaminooctafluorobiphenyl; 3,5-diaminobenzoic acid; 3,7-diamino-2-methoxyfluorene; 4,4'-diaminobenzophenone;3,4-diaminobenzophenone;3,4-diaminotoluene;2,6-diaminoanthraquinone;2,6-diaminotoluene;2,3-diaminotoluene;1,8-diaminonaphthalene;2,4-diaminotoluene;2,5-diaminotoluene;1,4-diaminoanthraquinone;1,5-diaminoanthraquinone;1,5-diaminonaphthalene;1,2-diaminoanthraquinone; 2,4-cumene diamine; 1,3-bisaminomethylbenzene; 1,3-bisaminomethylcyclohexane; 2-chloro-1,4-diaminobenzene; 1,4-diamino-2,5-dichlorobenzene; 1,4-diamino-2,5-dimethylbenzene; 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl; Bis (amino-3-chlorophenyl) ethane; Bis (4-amino-3,5-dimethylphenyl) methane; Bis (4-amino-3,5-diethylphenyl) methane; Bis (4-amino-3-ethyldiaminofluorene, diaminobenzoic acid, 2,3-diaminonaphthalene, 2,3-diaminophenol, -5-methylphenyl) methane; Bis (4-amino-3-methylphenyl) methane; Bis (4-amino-3-ethylphenyl) methane; 4,4'-diaminophenyl sulfone; 3,3'-diaminophenyl sulfone; 2,2-bis (4- (4-aminophenoxy) phenyl) sulfone; 2,2-bis (4- (3-aminophenoxy) phenyl) sulfone; 4,4'-oxydianiline;4,4'-diaminodiphenylsulfide;3,4'-oxydianiline; 2,2-bis (4- (4-aminophenoxy) phenyl) propane; 1,3-bis (4-aminophenoxy) benzene; 4,4'-bis (4-aminophenoxy) biphenyl; 4,4'-diamino-3,3'-dihydroxybiphenyl;4,4'-diamino-3,3'-dimethylbiphenyl;4,4'-diamino-3,3'-dimethoxybiphenyl; Bisaniline M; Bisaniline P; 9,9-bis (4-aminophenyl) fluorene; o-tolidinesulfone; Methylene bis (anthranilic acid); 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane; 1,3-bis (4-aminophenoxy) propane; 1,4-bis (4-aminophenoxy) butane; 1,5-bis (4-aminophenoxy) butane; 2,3,5,6-tetramethyl-1,4-phenylenediamine; 3,3 ', 5,5'-tetramethylbenzidine;4,4'-diaminobenzanilide; 2,2-bis (4-aminophenyl) hexafluoropropane; Polyoxyalkylene diamines (e.g., Jeffamine D-230, D400, D-2000 and D-4000 from Huntsman); 1,3-cyclohexane bis (methylamine); m-xylylenediamine; p-xylylene diamine; Bis (4-amino-3-methylcyclohexyl) methane; 1,2-bis (2-aminoethoxy) ethane; (Aminomethyl) tricyclo (5.2.1.0 2,6 ) decane, 1,2-bis (aminooctyl) -3-octyl-4-hexyl-cyclohexane, . Among these, from the viewpoint of obtaining a flame retardant resin exhibiting excellent dielectric properties and strength, a diamine having 10 to 30 carbon atoms in the main chain of the alkyl chain is preferable, and a diamine having 10 to 20 carbon atoms in the main chain of the alkyl chain is more preferable Do.

Examples of the bismaleimide compound include commercially available compounds such as BMI-3000 (synthesized from dimer diamine, pyromellitic acid dianhydride and maleic anhydride) manufactured by DESIGNER MOLECURES Inc., BMI-1500, BMI-2550, BMI-1400, BMI-2310 and BMI-3005 can be preferably used.

Among them, the structural formula of the bismaleimide compound of BMI-3000 manufactured by DESIGNER MOLECURES Inc., which is a bismaleimide compound preferably used, is expressed as follows.

Figure pct00006

To the flame retardant resin composition, an epoxy resin can be blended to the extent that the dielectric constant or dielectric tangent is not adversely affected in order to improve the adhesion.

The epoxy resin is not particularly limited as long as it contains an epoxy group in the molecule, and specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl amine type epoxy resin, glycidyl ether type epoxy resin, And a cis-ester-based epoxy resin. These may be used singly or in combination of two or more.

When the epoxy resin is used, the content of the epoxy resin (the total amount when two or more kinds are used together) is not particularly limited, but it is preferably 1 to 25 parts by mass, more preferably 2 to 20 parts by mass in 100 parts by mass of the resin component And more preferably 2 to 15 parts by mass.

The curing agent is not particularly limited, and one kind selected from a radical initiator, an imidazole curing agent, an azo curing agent, and a cationic curing agent may be used singly or in combination of two or more.

Examples of the radical type hardening agent (polymerization initiator) include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetate peroxide, 1,1-bis (tert-hexylperoxy) Trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, (Tert-butylperoxy) -2-methylcyclohexane, 1,1-bis (tert-butylperoxy) -cyclohexane, 1,1- (4,4-di-tert-butylperoxycyclohexyl) propane, p-menthol hydroperoxide, diisopropylbenzene hydroperoxide, Tertiary butyl hydroperoxide, tertiary butyl hydroperoxide, alpha, alpha '-bis (tert-butyl) oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, tert-butylcumylperoxide, di-tert-butylperoxide, 2,5- Dimethyl-2,5-bis (tert-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, Di-n-propyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-n-propyl peroxydicarbonate, m-toluoyl benzoyl peroxide, benzoyl peroxide, Di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-sec-butylperoxydicarbonate, di (3-methyl- Butyl) peroxydicarbonate,?,? '- bis (neodecanoylperoxy) diisopropylbenzene, cumyl peroxyneodec Octyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl- Peroxyneodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5- 2-ethylhexanoate, 2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxyisobutyrate, tert-butylperoxydmate, tert- Butyl peroxy isopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxyacetate, tert-butyl peroxyacetate, Tert-butyl peroxybenzoate, tert-butyl peroxybenzoate, bis (tert-butylperoxy) isophthalate, 2,5-dimethyl- Butyl peroxyallyl monocarbonate, tert-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetrahexyl peroxybenzoate, 2,5-dimethyl- , 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, and 2,3-dimethyl-2,3-diphenylbutane.

Examples of the imidazole-based curing agent include imidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- Triazine, and the like.

Examples of the azo type curing agent include 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1 - [(1-cyano- 1- methylethyl) azo] formamide, Bis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis Azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, Azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydride chloride, 2,2'-azobis [N- Azobis [2-methyl-N- (2-propylphenyl) propionamidine] dihydrochloride, 2,2'-azobis Phenyl) propionamidine] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionimino ] Dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) Diazepin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro- Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- Dihydrochloride, 2,2'-azobis [2- [1- (2-hydroxyethyl) -2- 2-yl] propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin- Bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2'-azobis [2-methyl- N- [1,1- ] Propionamide], 2,2'-azobis [2-methyl-N- (2- Ethyl) propionamide], 2,2'-azobis (2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane, 2,2'-azobis Azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis [2- (hydroxymethyl) (2-methyl-1-methylethyl) azo) formamide (2- (carbamoyl azo) isobutyronitrile), 2,2'-azobis N- (2- (1-hydroxybutyl)) propionamide), and the like.

Examples of the cationic curing agent include amine salts of boron trifluoride, P-methoxybenzene diazonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, triphenylsulfonium, tetra-n-butylphosphonium tetraphenylborate , Tetra-n-butylphosphonium-o, o-diethylphosphorothioate, and the like.

Of these, azo based curing agents are preferred, and more specifically, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2 ' Azo compounds such as azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 1- (1-cyano- Azo) isobutyronitrile), and more preferably 1,1'-azobis (cyclohexane-1-carbonitrile).

The content of the curing agent (the total amount when two or more kinds are used together) is not particularly limited, but is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the resin component Mass part is more preferable. If the amount is 0.5 parts by mass or more, sufficient curing is obtained to obtain adhesion, and if it is 30 parts by mass or less, a hot life can be ensured within a range that does not impair workability.

As the phosphorus flame retardant, a phosphorus-based flame retardant composed of at least one kind selected from the group consisting of a cyclophosphazene flame retardant and a phosphate flame retardant is used.

As the cyclophosphazene-based flame retardant, those represented by the following general formula (II) are used.

Figure pct00007

In the formula (II), X represents any one of an alkyl group, an alkoxy group, an aryloxy group, an amino group and a phenoxy group, and among these, a phenoxy group is preferable. Each X is independently selected.

Specific examples of the cyclophosphazene-based flame retardant include, but are not limited to, propoxyphosphazene, phenoxyphospazene, aminophosphazene, fluoroalkylphosphazene, and the like. Of these, phenoxyphospazene is preferred from the viewpoint of compatibility between flame retardance, low dielectric constant and low dielectric loss tangent. Examples of such cyclophosphazene-based flame retardants include "SPB-100", which is commercially available from Otsuka Chemical Co., Ltd., and the like. As the cyclophosphazene-based flame retardant, the above-mentioned compounds may be used singly or in combination of two or more.

The content of the cyclophosphazene flame retardant (the total amount when two or more flame retardants are used together) is preferably 5 to 30 parts by mass, more preferably 7 to 25 parts by mass relative to 100 parts by mass of the resin component from the viewpoint of both the flame retardancy and the low dielectric constant More preferably 10 to 20 parts by mass.

As the phosphate flame retardant, a phosphate flame retardant A containing a salt of ammonia and a polyphosphoric acid or a triazine derivative and a salt of polyphosphoric acid, a phosphate flame retardant B containing a salt of a diamine and a polyphosphoric acid, Or two or more of them may be used in combination.

The polyphosphate in the phosphate flame retardant A can be represented by the following formula (III).

Figure pct00008

In the formula (III), n is from 1 to 100, and preferably from 1 to 30, more preferably from 1 to 10, and most preferably from 1 to 10, from the viewpoint of compatibility with the bismaleimide- = 2 is particularly preferable. X 1 represents an ammonia or triazine derivative, and p represents a number satisfying 0 <p? N + 2.

Specific examples of the triazine derivatives in the phosphate flame retardant A include melamine, acetoguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4 Diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino- Triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy- 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine, , 6-dimercapto-1,3,5-triazine, and the like. Of these, melamine is preferable from the viewpoint of flame retardancy.

The polyphosphate in the phosphate flame retardant B can be represented by the following formula (IV).

Figure pct00009

In the formula (IV), r is 1 to 100, preferably 1 to 30, more preferably 1 to 10, and r = 2 from the viewpoint of compatibility with the bismaleimide resin and flame retardancy Particularly preferred. Y 1 represents a diamine, and q represents a number satisfying 0 <r? N + 2.

Examples of the diamine in the phosphate flame retardant B include N, N, N ', N'-tetramethyldiaminomethane, ethylenediamine, N, N'-dimethylethylenediamine, N, , N, N'-dimethylethylenediamine, N, N-diethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, Diamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, 1,6-dimethylpiperazine, Rajin and others. Of these, piperazine is preferable from the viewpoint of flame retardancy.

The content of the phosphate flame retardant (the total amount when two or more of them are used together) is not particularly limited, but is preferably 5 to 30 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the resin component , And more preferably 10 to 25 parts by mass. When the amount is 5 parts by mass or more, the flame retardancy is sufficiently obtained. When the amount is 30 parts by mass or less, the flame retardancy is improved without greatly deteriorating the physical properties such as adhesion, bulk strength and shear strength, dielectric constant and dielectric tangent .

The ratio of the phosphate flame retardant A to the phosphate flame retardant B is preferably 20/80 to 50/50, more preferably 30/70 to 50/50, in terms of the mass ratio, from the viewpoint of flame retardancy , And more preferably 35/65 to 45/55.

The content of the phosphorus flame retardant (the total amount of the cyclophosphazene flame retardant and the phosphate flame retardant) is not particularly limited, but is preferably 5 to 30 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the resin component , More preferably 10 to 25 parts by mass. When the amount is not less than 5 parts by mass, the flame retardancy is sufficiently obtained. When the amount is not more than 30 parts by mass, the flame retardancy can be improved without greatly impairing the properties such as adhesion, bulk strength and shear strength, dielectric constant and dielectric tangent.

Examples of the fluororesin filler include, but are not particularly limited to, perfluoroalkoxy fluororesin, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, and ethylene chlorotrifluoroethylene copolymer. These may be used singly or in combination of two or more.

The content of the fluororesin filler (the total amount when two or more kinds are used together) is preferably 10 to 200 parts by mass, more preferably 20 to 200 parts by mass with respect to 100 parts by mass of the resin component from the viewpoints of both the flame retardance and the adhesiveness Do.

The particle diameter of the fluororesin filler is not particularly limited, but it is preferable that the average particle diameter is 0.2 to 30 占 퐉. Here, in the present specification, the average particle diameter refers to the median diameter (D50) measured by the laser diffraction method.

The flame retardant resin composition of the present invention is obtained by blending a predetermined amount of each of the above-mentioned components and sufficiently mixing together with a solvent to be used as required.

The solvent is not particularly limited, but an organic solvent is preferably used. Specific examples thereof include methyl ethyl ketone, toluene, methanol, tetralin, and the like. These solvents may be used singly or in combination of two or more kinds.

The content of the solvent is not particularly limited, but is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass, and still more preferably 30 to 100 parts by mass with respect to 100 parts by mass of the resin component.

The flame-retardant resin composition may contain an additive that has been added to the flame-retardant resin composition of the prior art within the range not deviating from the object of the present invention.

The complex viscosity of the flame retardant resin composition at 80 캜 in the absence of a solvent is not particularly limited, but is preferably 5 × 10 3 Pa · s to 5 × 10 5 Pa · s, more preferably 1 × 10 4 that the Pa · s~5 × 10 5 Pa · s is more preferable, and 5 × 10 4 Pa · s~5 × 10 5 Pa · s is more preferred.

If the complex viscosity at 80 캜 is 5 × 10 3 Pa · s or more, the flow of the flame retardant resin composition during press molding is not easily generated even when the ultraviolet ray is not cured, and molding is easy. When the complex viscosity at 80 캜 is 5 × 10 5 Pa · s or less, the flowability of the flame-retardant resin composition is appropriate, and the step difference of the pattern copper or the like can be compensated at the time of forming the multilayer substrate . When the complex viscosity at 80 캜 is less than 5 × 10 3 Pa · s, the viscosity may be adjusted by adding an additive such as silica if necessary.

The flame retardant resin composition of the present invention may contain not only the above cyclophosphazene flame retardant or the above phosphate flame retardant but also other flame retardants within a range that does not impair the effect of the present invention and is not particularly limited, A phosphorus flame retardant and the like are preferably used. Flame retardancy can be imparted without greatly impairing the dielectric constant and dielectric tangent.

The phosphorus-based flame retardant other than the cyclophosphazene-based flame retardant and the phosphate-based flame retardant is not particularly limited, but phosphate ester, phosphoric acid condensate ester, linear phosphazene compound and the like can be used. These may be used singly or in combination of two or more.

Examples of the phosphoric ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricilylenyl phosphate, 2-ethylhexyldiphenyl phosphate, tris (2,6-dimethylphenyl) phosphate, resorcinediphenyl phosphate, and the like can be used.

Examples of phosphoric acid condensation esters include ammonium polyphosphate, polyphosphoric acid amide, red phosphorus, guanidine phosphate, and dialkylhydroxymethylphosphonate.

Examples of the linear phosphazene compounds include polyarylphosphazenes such as polydiphenylphosphazene, polydiaryloxiphosphazenes such as polydiphenoxaphosphazenes, polydiaminophosphazenes, polydifluoroalkylphosphazenes and the like. .

The flame retardant resin composition can be used for resin-coated copper foil. Here, in the present invention, the resin-coated copper foil refers to a composite material obtained by applying a semi-curable (so-called B-stage) flame retardant resin composition to be a base material on a copper foil.

The flame retardant resin of the present invention is a cured product of the flame retardant resin composition and may be a copper clad laminate in which a flame retardant resin and a copper foil are laminated. Herein, the copper clad laminate in the present invention refers to a copper clad laminated with resin and cured. Further, a flame-retardant resin or a fiber substrate such as a glass cloth is impregnated with the flame-retardant resin composition, and a copper foil is bonded to the fiber substrate.

The flexible printed wiring board is formed by laminating copper foils on one side or both sides of a copper clad laminate, and a film (polyimide or the like) made of a flexible insulator is bonded to a conductive (conductive) metal such as a copper foil And a substrate on which an electric circuit is formed.

The method for producing the resin-coated copper foil of the present invention is not particularly limited. For example, the flame-retardant resin composition is applied to polyethylene terephthalate (PET) having a uniform thickness so that the thickness thereof becomes uniform, Drying it to prepare a film, attaching a copper foil thereon, and hot pressing. The press condition at this time is not particularly limited, but the first stage press is performed while heating for 5 to 10 minutes under the conditions of 80 to 130 캜 and a surface pressure of 5 to 20 kg / cm 2 , It is preferable to carry out the second-step pressing while heating for 15 to 60 minutes under the condition of -40 kg / cm &lt; 2 &gt;.

The method for producing the copper clad laminate is not particularly limited, and for example, a copper clad laminate according to the present invention can be manufactured by laminating a plurality of resin-attached copper foils according to the present invention and molding the same by pressing while heating. Press conditions are also not particularly limited, and under the conditions of a heating temperature is 160~200 ℃, surface pressure 15~40kg / cm 2, and preferably 30-120 minutes press, the heating temperature is 160~180 ℃, It is more preferable to press for 30 to 90 minutes under the condition that the surface pressure is 20 to 30 kg / cm 2 . Further, a resin substrate, a polyimide film, a fiber substrate, or the like may be sandwiched between the resin-coated copper foils and pressed while heating. The strength of the copper clad laminate is improved by interposing a fluororesin substrate, a polyimide film, a fiber substrate, or the like.

The manufacturing method of the flexible printed wiring board is not particularly limited. For example, a flexible printed wiring board can be obtained by forming a circuit by pattern-etching the copper clad laminate by a conventional method and thermally bonding the coverlay. The pressing conditions at this time are not particularly limited, but it is preferable that the pressing is performed for 30 to 120 minutes under the conditions of a heating temperature of 160 to 200 캜 and a surface pressure of 15 to 40 kg / cm 2 , It is more preferable to press for 30 to 90 minutes under the condition that the surface pressure is 20 to 30 kg / cm &lt; 2 &gt;.

The completed flexible printed wiring board can satisfy the UL-VT04 standard of the UL standard for determining the combustibility in the double-sided copper clad state.

[Example]

Examples of the present invention will be described below, but the present invention is not limited to the following examples. In the following, the mixing ratio and the like are based on mass unless otherwise specified.

A flame-retardant resin composition was obtained by mixing the bismaleimide compound, the epoxy resin, the curing agent, the flame retardant, the silica, and the fluorine resin filler according to the blend shown in Tables 1 and 2 below.

Details of the compounds listed in the table are as follows.

· Bismaleimide compound: "BMI-3000" (manufactured by DESIGNER MOLECULES INC.)

Epoxy resin: "VG3101L, 50 mass% methyl ethyl ketone solution" (manufactured by PRINTEC Co., Ltd.)

· Curing agent 1: Radical curing agent "Dicumyl peroxide"

Curing agent 2: An imidazole-based curing agent "2E4MZ (2-ethyl-4-methylimidazole)" (manufactured by Shikoku Kasei Kogyo Co., Ltd.)

Curing agent 3: Cationic curing agent &quot; tetra-n-butylphosphonium tetraphenylborate &quot;

· Curing agent 4: Azo base curing agent "1,1'-azobis (cyclohexane-1-carbonitrile)"

Flame Retardant 1: Cyclophosphazene flame retardant "SPB-100" (manufactured by Otsuka Chemical Co., Ltd.)

Flame retarding agent 2: Phosphate flame retardant A (n = 2, X = melamine, p = 1) represented by the general formula (III) and phosphate flame retardant B (r = 2, Y = Piperazine, q = 1) (A / B = 15/20)

Flame retardant 3: Antimony trioxide "PATOX-SUF" (manufactured by Nippon Seiko Co., Ltd.)

Silica: &quot; WG1000 &quot; (manufactured by Toyo Seisakusho Co., Ltd.)

Fluorine resin filler: "KTL-500F" (manufactured by Kitamura Co., Ltd., average particle diameter: 0.6 μm)

The obtained flame retardant resin composition was evaluated for its complex viscosity, dielectric constant and dielectric tangent, shear strength, flow of the resin composition, step-fillability of resin-coated copper foil, and flame retardancy. The evaluation method is as follows.

For the complex viscosity and shear strength, the obtained flame retardant resin composition was applied by using a coater so as to have a thickness of about 25 占 퐉 by using the PET obtained by the release treatment, and the solvent was dried (at 40 占 폚 for one minute, Then dried at 50 ° C for 1 minute, and then dried at 80 ° C for 1 minute) to prepare a film made of a flame retardant resin composition, and measurement and evaluation were carried out.

With respect gender flow of the resin composition, and the step embedded in the resin coated copper foil, and presses the film made of the obtained flame-retardant resin composition, the surface pressure at 80 ℃ 10 bungan, 15kg / cm 2 using a pressing machine, conditioning (粗, Followed by bonding a copper foil having a thickness of 10 mu m to both surfaces of the PTFE (polytetrafluoroethylene) having a thickness of 100 mu m and then bonding the copper foil to both surfaces thereof at 170 DEG C for 60 minutes at 30 kg / cm 2 to obtain a resin-attached copper foil, and measurement and evaluation were carried out. The press machine was a high-temperature vacuum press (KVHC-II type manufactured by Kitagawa Precision Machinery Co., Ltd.).

· Complex viscosity: 30 sheets of the film made of the above-mentioned flame retardant resin composition were superposed and used as a measurement sample. The complex viscosity was measured in the following apparatus and measuring conditions, and the complex viscosity at 80 캜 was obtained.

Device name: MCR302 (Modular Compact Rheometer) manufactured by Anton Paar Co.,

Swing angle: 0.1%

Frequency: 1Hz

Measuring range: 25 ~ 200 ℃

Temperature rise speed: 5 ° C / min

The obtained flame retardant resin composition was poured into a mold having a depth of 0.7 mm, a length of 120 mm and a width of 70 mm, and the surface was flattened with a metal spatula, and then allowed to stand at room temperature for 24 hours. And the solvent was dried. Insert the resulting resin sheets, 0.5mm in thickness, 110mm vertical, 70mm horizontal type of the fluororesin, the sandwiched by the top and bottom with a fluorine resin sheet, at 180 ℃ 60 minutes and pressed under a surface pressure 10kg / cm 2, the molded article &Lt; / RTI &gt;

The obtained molded article was cut into a width of about 2 mm in the longitudinal direction to prepare a sample. The permittivity and dielectric loss tangent were measured for three samples by the cavity resonator perturbation method (cavity resonator perception method), and an average value was obtained. The network analyzer used was E8361A manufactured by Agilent Technologies, and the cavity resonator was CP531 (10GHz) manufactured by Kanto Electronics Application Development Co., Ltd.

The value of the dielectric constant is preferably 2.5 or less. The value of the dielectric loss tangent is preferably 0.004 or less.

Shear Strength: The obtained flame retardant resin composition was applied to a copper plate and shear strength was measured in accordance with JIS K 6850. In the solder dipping test, the test piece was floated in a solder bath at 260 캜 for 30 seconds, and the shear strength after cooling at room temperature was measured.

The value of the shearing strength is preferably 3 MPa or more, more preferably 4 MPa or more.

Flow of Resin Composition: When a resin-coated copper foil was produced, whether or not a flow of the flame retardant resin composition was formed was observed with an optical microscope (x 80), and when no flow occurred, &Quot; x &quot; was obtained.

Stepped filling property: The above-mentioned resin film was applied to a flexible printed circuit board on which a pattern of a copper foil having a thickness of 18 占 퐉 and a line and space of 100 占 퐉 / 100 占 퐉 was formed at 170 占 폚 for 60 minutes, cm &lt; 2 & gt ;. The cross section of the sample was observed with an optical microscope (x 80), and the samples in which the steps were filled with the composition were evaluated as &quot;&quot;, and those in which the steps were not filled with the composition were evaluated as &quot;

Further, the flame retardancy of the double-sided copper clad flexible printed wiring board using the resin-attached copper foil was evaluated.

Flame Retardancy: The above flame retardant resin composition was applied to polyethylene terephthalate (PET) subjected to release treatment so as to have a uniform thickness, and the flame retardant resin composition was dried and cured to prepare a film made of a flame retardant resin composition. a thickness of the surface conditioning 100㎛ ETFE (ethylene-tetrafluoro ethylene copolymer) substrate, or, in 100㎛ of stretching (延伸) on both sides of the porous PTFE thickness, 10 minutes at 80 ℃, 15kg / cm 2 in surface pressure Then, a copper foil was bonded thereon, pressed at 170 캜 for 60 minutes under a surface pressure of 30 kg / cm 2 , and finally cured to obtain a flame retardant sample. As the bonding film, PTFE having a thickness of 25 占 퐉 was used and stretched porous PTFE was used having a thickness of 50 占 퐉.

The obtained flame-retardant sample was evaluated for flame retardancy in accordance with UL94-V0 standard of UL standard.

The results showed that all of the samples with the melting time of 10 seconds or less in the test of N = 5, the double-sided copper clad flexible printed wiring board satisfying the UL94-V0 standard were evaluated as &quot; "

[Table 1]

Figure pct00010

[Table 2]

Figure pct00011

The results are shown in Tables 1 and 2. In Examples 1 to 11, all of them had a low dielectric constant of 2.5 or less, a dielectric loss tangent of 0.004 or less, a shear strength of 4 mPa or more, and excellent adhesion. In addition, the flame retardancy satisfied the UL94-V0 standard. Also, in any of the embodiments, the complex viscosity at 80 캜 is in the range of 5 × 10 3 Pa · s to 5 × 10 5 Pa · s, so that the step difference filling property is excellent and no flow of the resin composition occurs.

On the other hand, in Comparative Example 1 in which the content of the predetermined phosphorus flame retardant was less than 5 parts by mass and the content of the fluororesin filler was less than 10 parts by mass, sufficient flame retardancy was not obtained. Further, the complex viscosity at 80 캜 was low, and a flow of the resin composition was obtained.

In Comparative Example 2 in which the content of the predetermined phosphorylated flame retardant was more than 30 parts by mass and the content of the fluorine resin filler was more than 200 parts by mass, sufficient shear strength was not obtained and the adhesion was not excellent. Also, the composition had a high complex viscosity at 80 占 폚, and was not excellent in step-gap filling property.

Comparative Example 3 in which the flame retardant was not a predetermined phosphorylated flame retardant did not have excellent dielectric constant, dielectric tangent, and flame retardancy.

Comparative Example 4 in which the content of the curing agent was less than 0.5 parts by mass and the fluororesin filler was not contained, was not excellent in dielectric constant, dielectric tangent, shear strength and flame retardancy. Further, the complex viscosity at 80 캜 was low, and a flow of the resin composition was obtained.

In Comparative Example 5 in which the content of the curing agent was more than 30 parts by mass, dielectric loss tangent was not excellent. Also, the composition had a high complex viscosity at 80 占 폚, and was not excellent in step-gap filling property.

In Comparative Example 6 in which the content of the fluororesin filler was less than 10 parts by mass, sufficient flame retardancy was not obtained. Further, the complex viscosity at 80 캜 was low, and a flow of the resin composition was obtained.

In Comparative Example 7 in which the content of the fluororesin filler was more than 200 parts by mass, sufficient shear strength was not obtained and the adhesion was not excellent. In addition, the complex viscosity at 80 캜 was high and the step difference filling property was not excellent.

In Comparative Example 8 in which the content of the phosphate flame retardant agent was less than 5 parts by mass and the content of the fluorine resin filler was less than 10 parts by mass, sufficient flame retardancy was not obtained. Further, the complex viscosity at 80 캜 was low, and a flow of the resin composition was obtained.

In Comparative Example 9 in which the content of the phosphate flame retardant was less than 5 parts by mass, sufficient flame retardancy was not obtained.

Claims (8)

A resin component containing a bismaleimide compound represented by the following general formula (I)
Hardener,
At least one selected from the group consisting of a cyclophosphazene flame retardant represented by the following general formula (II), a phosphate flame retardant represented by the following general formula (III), and a phosphate flame retardant represented by the following general formula (IV) A phosphorus-containing flame retardant, and
Containing fluorine resin filler,
The content of the curing agent is 0.5 to 30 parts by mass based on 100 parts by mass of the resin component,
The phosphorus flame retardant is contained in an amount of 5 to 30 parts by mass based on 100 parts by mass of the resin component,
Wherein the content of the fluororesin filler is 10 to 200 parts by mass based on 100 parts by mass of the resin component.
Figure pct00012

In the general formula (I), X represents a hydrocarbon group having an aliphatic, alicyclic or aromatic hydrocarbon group and having 10 to 30 carbon atoms in the main chain (main chain), and these groups may be substituted with a hetero atom, , Or a siloxane skeleton, and Y represents an aliphatic, alicyclic or aromatic hydrocarbon group, and these groups may have a hetero atom, a substituent, a phenyl ether skeleton, a sulfonyl skeleton, or a siloxane skeleton, and n Represents a range number of 1 to 20,
Figure pct00013

In the general formula (II), X represents any one of an alkyl group, an alkoxy group, an aryloxy group, an amino group and a phenoxy group.
Figure pct00014

In the general formula (III), n is 1 to 100, X 1 is an ammonia or triazine derivative, p is a number satisfying 0 < p < = n +
Figure pct00015

In the general formula (IV), r is 1 to 100, Y 1 is a diamine, and q is a number satisfying 0 <r? N + 2. The method according to claim 1,
Wherein the resin component further contains an epoxy resin. 3. The method according to claim 1 or 2,
Wherein the curing agent is one or more selected from a radical initiator, an imidazole-based curing agent, an azo-based curing agent, and a cationic curing agent. 4. The method according to any one of claims 1 to 3,
And has a complex viscosity at 80 캜 of 5 x 10 3 Pa · s to 5 × 10 5 Pa · s. A flame-retardant resin which is a cured product of the flame retardant resin composition according to any one of claims 1 to 4. A resin-coated copper foil having the flame-retardant resin according to claim 5 on at least a part of the surface of the copper foil. A copper clad laminate comprising the flame retardant resin according to claim 6 and a copper foil laminated thereon. A flexible printed wiring board having a copper clad laminate according to any one of claims 7 to 10.
KR1020197004704A 2016-09-14 2017-08-17 Flame retardant resin composition and resin-attached copper foil KR20190054058A (en)

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PCT/JP2017/029544 WO2018051715A1 (en) 2016-09-14 2017-08-17 Flame-retardant resin composition and resin-coated copper foil

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