JP2003026939A - Material for insulating substrate, printed wiring board, laminate, copper foil with resin, copper-clad laminate, polyimide film, film for tab, and prepreg - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material for an insulating substrate which is excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc., and can exhibit an excellent flame-retardant effect due to the shape retention effect on burning; and a printed wiring board, a copper foil with a resin, a copper-clad laminate, a polyimide film, a film for TAB, and a prepreg prepared by using the material for an insulating substrate. SOLUTION: This material for an insulating substrate contains 100 pts.wt. resin component comprising a thermoplastic resin or a mixture of a thermoplastic resin with a thermosetting resin and 0.1-100 pts.wt. layered silicate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a material for an insulating substrate which is excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy and the like, and in particular exhibits an excellent flame retardant effect by a shape retaining effect during combustion, The present invention relates to a printed board, a laminated board, a resin-coated copper foil, a copper-clad laminated board, a polyimide film, a TAB film and a prepreg.

[0002]

2. Description of the Related Art Generally, a multilayer printed circuit board used in electronic equipment is composed of a plurality of layers of insulating boards.
As this interlayer insulating substrate, a thermosetting resin prepreg in which glass cloth is impregnated with a thermosetting resin, or a film made of a thermosetting resin or a photocurable resin is used.

In recent years, it has been desired to make the layers extremely thin as the density and the thickness of the multilayer printed circuit board are reduced.
There is a need for an interlayer insulating substrate that uses a thin glass cloth or no glass cloth at all. As such an interlayer insulating substrate, for example, rubber (elastomer)
It is known to be composed of a thermosetting resin material modified with an acrylic resin or the like, a thermoplastic resin material containing a large amount of an inorganic filler, and the like.

For example, Japanese Patent Application Laid-Open No. 2000-183539 discloses "High molecular weight epoxy polymer having an average molecular weight of 50,000 or more obtained by polymerizing a bifunctional epoxy resin and a bifunctional phenol, a polyfunctional epoxy resin, and a curing agent. An epoxy adhesive film obtained by blending a non-fibrous inorganic filler having an average particle size of 0.8 to 5 μm with a varnish containing an agent and a cross-linking agent as main components and applying the non-fibrous inorganic filler to one or both sides of a support A method for producing a multilayer insulating substrate used as an insulating layer "is disclosed.

However, in the multilayer insulating substrate produced by the above manufacturing method, the interfacial area between the inorganic filler and the high molecular weight epoxy polymer or polyfunctional epoxy resin necessary for improving mechanical properties such as mechanical strength is limited. Therefore, there is a problem that it is necessary to mix a large amount of inorganic filler, it is difficult to thin the layers, and problems such as an increase in the number of steps occur during processing.

Further, an interlayer insulating substrate using a thin glass cloth or no glass cloth at all has a problem that heat resistance and dimensional stability are insufficient, and is fragile and easily cracked. There have been problems such as breakage often occurring during the manufacturing process.

On the other hand, in recent years, polymeric materials used for industrial applications have been required to be environmentally friendly materials due to the problems of waste plastic processing and environmental hormones.
Conversion to environmentally friendly materials is desired. In particular,
For example, conversion from halogen-containing flame retardants to non-halogen flame retardants is being studied in order to deal with problems such as dioxin generation during combustion. In addition, halogen-containing flame retardants are highly flame retardant and have relatively little deterioration in moldability and mechanical properties of molded products, but when used, a large amount is used during molding and combustion. The halogen-containing gas may be generated, and the generated halogen-based gas may corrode the equipment or have an unfavorable effect on the human body.Therefore, in terms of safety, so-called halogen-free flame retardants are not used. It is strongly desired to establish flame retardant treatment technology and treatment method.

Therefore, in recent years, with respect to materials for insulating substrates, materials using non-halogen type flame retardants have been developed in order to switch to environmentally compatible materials. But,
In the case of non-halogen type flame retardants, it is necessary to add a large amount of flame retardants in order to develop the required flame retardancy, so in terms of heat resistance, dimensional stability, etc., conventional halogen-containing flame retardants have been used. There was a problem that it was not as good as the material for the insulating substrate.

That is, the problem with these insulating substrate materials is that, for example, when a thin insulating substrate is used, it is difficult to maintain heat resistance, dimensional stability, and mechanical properties.
In order to develop the required flame retardancy with a non-halogen flame retardant, it is necessary to add a large amount of flame retardant, so it is difficult to obtain the mechanical properties and heat resistance required during the manufacturing process. Etc.

[0010]

In view of the above situation, the present invention has excellent mechanical properties, dimensional stability, heat resistance, flame retardancy, etc. Material for insulating substrate, printed board, laminated board, copper foil with resin, copper clad laminated board, polyimide film, TAB
The purpose is to provide a film for use and a prepreg.

[0011]

The present invention 1 is a material used for an insulating substrate, which is 100 parts by weight of a thermoplastic resin or a mixture of a thermoplastic resin and a thermosetting resin, and a layered silicate. The material for an insulating substrate contains 1 to 100 parts by weight.

The present invention 2 is a material used for an insulating substrate, which is a phenol resin, a urea resin, an unsaturated polyester resin, an allyl resin, a thermosetting polyimide resin, a bismaleimide triazine resin, a thermosetting modified polyphenylene ether resin. An insulating substrate material containing 100 parts by weight of at least one thermosetting resin selected from the group consisting of a silicon resin and a benzoxazine-based resin, and 0.1 to 100 parts by weight of a layered silicate.

The present invention 3 is a material used for an insulating substrate, which is a flame retardant containing 0.1 to 100 parts by weight of a layered silicate and substantially no halogen composition with respect to 100 parts by weight of an epoxy resin. It is an insulating substrate material containing 0.1 to 100 parts by weight. The present invention is described in detail below.

The insulating substrate material of the present invention comprises a thermoplastic resin and / or a thermosetting resin. The thermoplastic resin is not particularly limited, and examples thereof include polyolefin resin, polystyrene resin, polyphenylene ether resin, functional group-modified polyphenylene ether resin; polyphenylene ether resin or functional group-modified polyphenylene ether resin. And a thermoplastic resin compatible with a polyphenylene ether resin such as a polystyrene resin or a functional group-modified polyphenylene ether resin; alicyclic hydrocarbon resin, thermoplastic polyimide resin, polyamideimide resin , Polyester imide resin, polyester resin, polyether ether ketone (PEEK) resin, polyether sulfone resin, polyamide resin, polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl acetate resin, Li (meth) acrylate resin, polyoxymethylene resins. Among them, polyphenylene ether-based resin, functional group-modified polyphenylene ether-based resin, polyphenylene ether-based resin or a mixture of functional group-modified polyphenylene ether-based resin and polystyrene-based resin, alicyclic hydrocarbon-based resin and thermoplastic polyimide Resins and the like are preferably used. These thermoplastic resins may be used alone or 2
More than one kind may be used in combination. In addition, in this specification, "(meth) acryl" means "acryl" or "methacryl."

The polyphenylene ether resin is
It is a polyphenylene ether homopolymer or a polyphenylene ether copolymer comprising a repeating unit represented by the following general formula (1).

[0016]

[Chemical 1]

In the formula, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or an alkoxyl group. Each of these alkyl group, aralkyl group, aryl group and alkoxyl group may be substituted with a functional group.

The polyphenylene ether homopolymer is not particularly limited, and examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,4-phenylene). Ether, poly (2,6-diethyl-1,4-phenylene) ether,
Poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-
1,4-phenylene) ether, poly (2-ethyl-6)
-N-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, etc. Is mentioned.

The polyphenylene ether copolymer is not particularly limited, and examples thereof include a copolymer partially containing alkyl trisubstituted phenol such as 2,3,6-trimethylphenol in the polyphenylene ether repeating unit, Examples of the polyphenylene ether copolymer further include a copolymer obtained by graft-copolymerizing one kind or two or more kinds of styrene-based monomers such as styrene, α-methylstyrene and vinyltoluene. These polyphenylene ether resins may be used alone or in combination of two or more having different compositions, components or molecular weights.

The functional group-modified polyphenylene ether-based resin is not particularly limited. For example, the polyphenylene ether-based resin may be one of functional groups such as maleic anhydride group, glycidyl group, amino group, allyl group or the like.
Examples include those modified with more than one type. These functional group-modified polyphenylene ether resins may be used alone or in combination of two or more.

When the above-mentioned functional group-modified polyphenylene ether resin is used as the thermoplastic resin, the insulating substrate material can undergo a cross-linking reaction, further improving mechanical properties, heat resistance, dimensional stability and the like. be able to.

The mixture of the polyphenylene ether resin or the functional group-modified polyphenylene ether resin and the polystyrene resin is not particularly limited. For example, the polyphenylene ether resin or the functional group-modified polyphenylene ether resin is used. And a styrene homopolymer; a copolymer of styrene and one or more kinds of styrene-based monomers such as α-methylstyrene, ethylstyrene, t-butylstyrene and vinyltoluene;
Examples thereof include a mixture with a polystyrene resin such as a styrene elastomer. The polystyrene resins may be used alone or in combination of two or more. A mixture of these polyphenylene ether-based resins or functional group-modified polyphenylene ether-based resins and polystyrene-based resins may be used alone, or 2
More than one kind may be used in combination.

The alicyclic hydrocarbon resin is not particularly limited as long as it is a hydrocarbon resin having a cyclic hydrocarbon group in the polymer chain. For example, a cyclic olefin homopolymer or copolymer. Etc. These alicyclic hydrocarbon resins may be used alone or in combination of two or more kinds.

The above-mentioned cyclic olefin is a norbornene-based monomer, and examples thereof include norbornene, methanooctahydronaphthalene, dimethanooctahydronaphthalene, dimethanodecahydroanthracene, dimethanodecahydroanthracene, trimetanodecahydroanthracene and dimethanodecahydroanthracene. Cyclopentadiene, 2,3-dihydrocyclopentadiene, methanooctahydrobenzoindene, dimethanooctahydrobenzoindene, methanodecahydrobenzoindene, dimethanodecahydrobenzoindene,
Examples thereof include methanooctahydrofluorene, dimethanooctahydrofluorene and the like, and substitution products thereof. These cyclic olefins may be used alone or in combination of two or more kinds.

The substituent in the above-mentioned norbornene and the like is not particularly limited, and examples thereof include known hydrocarbon groups such as alkyl group, alkylidene group, aryl group, cyano group, alkoxycarbonyl group, pyridyl group and halogen atom. Examples include polar groups. These substituents may be used alone or in combination of two or more.

The substitution product of norbornene and the like is not particularly limited, and examples thereof include 5-methyl-2-norbornene and
5,5-dimethyl-2-norbornene, 5-ethyl-2
-Norbornene, 5-butyl-2-norbornene, 5-
Ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5- Methyl-2-norbornene and the like can be mentioned. These substitution products such as norbornene may be used alone or in combination of two or more kinds.

Among the above alicyclic hydrocarbon resins, those commercially available include, for example, JS (JS).
R) product name "Arton" series manufactured by Nippon Zeon Co., Ltd., product name "Zeonor" series and the like.

The thermoplastic polyimide resin is not particularly limited, and examples thereof include a polyetherimide resin having an imide bond and an ether bond in the molecular main chain, and a polyamide having an imide bond and an amide bond in the molecular main chain. Examples thereof include imide resins and polyesterimide resins having an imide bond and an ester bond in the main chain of the molecule. These thermoplastic polyimide resins may be used alone or in combination of two or more kinds.

The above polyether ether ketone resin is not particularly limited, and examples thereof include those obtained by polycondensing dihalogenobenzophenone and hydroquinone.

The above-mentioned thermosetting resin is a resin raw material made of a relatively low molecular weight substance such as liquid, semi-solid or solid at room temperature, and shows fluidity at room temperature or under heating, but a curing agent, catalyst or It is a resin that becomes insoluble and infusible by causing a chemical reaction such as a curing reaction or a crosslinking reaction by the action of heat to form a network-like three-dimensional structure with an increase in the molecular weight.

The thermosetting resin is not particularly limited, and examples thereof include phenolic resin, epoxy resin, unsaturated polyester resin, alkyd resin, furan resin, urea resin, melamine resin, polyurethane resin. , Aniline resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, allyl resin,
Examples thereof include bismaleimide triazine resin, silicon resin, and benzoxazine-based resin. Among them, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, allyl resin, thermosetting polyimide resin, bismaleimide triazine resin, thermosetting modified polyphenylene ether resin, silicon resin, benzoxazine resin are suitable. Used. These thermosetting resins may be used alone or in combination of two or more.

The epoxy resin is an organic compound having at least one oxirane ring (epoxy group). The number of epoxy groups in the epoxy resin is preferably 1 or more per molecule, and more preferably 2 or more per molecule. Here, the number of epoxy groups per molecule is obtained by dividing the total number of epoxy groups in the epoxy resin by the total number of molecules in the epoxy resin.

The above-mentioned epoxy resin is not particularly limited, and various conventionally known epoxy resins can be used, and examples thereof include the epoxy resins (1) to (11) shown below. These epoxy resins may be used alone or in combination of two or more kinds. The epoxy resin (1) is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, a bisphenol S type epoxy resin or other bisphenol type epoxy resin; a phenol novolac type epoxy resin, a cresol novolac type epoxy resin or the like. Novolak type epoxy resins; aromatic epoxy resins such as trisphenolmethane triglycidyl ether, and hydrogenated products and brominated products thereof.

The epoxy resin (2) includes 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-2-methylcyclohexylmethyl 3,4-epoxy-2-methylcyclohexanecarboxylate. , Bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl- 5,5-
Spiro-3,4-epoxy) cyclohexanone-meta-
Dioxane, bis (2,3-epoxycyclopentyl)
It is an alicyclic epoxy resin such as ether. Examples of commercially available epoxy resin (2) include, for example, trade name “EHPE-3150” (softening temperature 71 ° C.,
Manufactured by Daicel Chemical Industries, Ltd.).

The epoxy resin (3) includes diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, and diglycol of polyethylene glycol. Glycidyl ether, diglycidyl ether of polypropylene glycol, polyglycidyl ether of long-chain polyol containing polyoxyalkylene glycol containing 2 to 9 (preferably 2 to 4) alkylene groups and polytetramethylene ether glycol, etc. And other aliphatic epoxy resins.

Epoxy resin (4) includes phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, salicylic acid glycidyl ether-glycidyl ester, dimer acid glycidyl ester. Glycidyl ester type epoxy resins such as esters and hydrogenated products thereof.

The epoxy resin (5) includes triglycidyl isocyanurate, N, N'-diglycidyl derivative of cyclic alkylene urea, and N, N, O- of p-aminophenol.
Triglycidyl derivative, N of m-aminophenol,
Glycidyl amine type epoxy resins such as N, O-triglycidyl derivatives and hydrogenated products thereof.

The epoxy resin (6) includes glycidyl (meth) acrylate, ethylene, vinyl acetate and (meth).
It is a copolymer with a radically polymerizable monomer such as an acrylic ester.

The epoxy resin (7) is obtained by epoxidizing the unsaturated carbon double bond of a polymer mainly composed of a conjugated diene compound such as epoxidized polybutadiene or a polymer of a partially hydrogenated product thereof.

The epoxy resin (8) is an epoxidized SBS.
Such as “a polymer block mainly composed of a vinyl aromatic compound” and a “polymer block mainly composed of a conjugated diene compound or a polymer block of a partially hydrogenated product thereof” in the same molecule. It is a polymer obtained by epoxidizing a double bond of unsaturated carbon of a conjugated diene compound.

The epoxy resin (9) is a polyester resin having one or more, preferably two or more epoxy groups per molecule.

The epoxy resin (10) is a urethane-modified epoxy resin or polycaprolactone-modified epoxy resin in which a urethane bond or a polycaprolactone bond is introduced into the structure of each of the above various epoxy resins.

The epoxy resin (11) is a rubber-modified epoxy resin in which a rubber component such as NBR, CTBN, polybutadiene or acrylic rubber is added to the above various epoxy resins.

The curing agent used for the epoxy resin is not particularly limited, and conventionally known curing agents for various epoxy resins can be used. For example, compounds such as amine compounds and polyaminoamide compounds synthesized from amine compounds can be used. Examples include tertiary amine compounds, imidazole compounds, hydrazide compounds, dicyanamide and its derivatives, melamine compounds, acid anhydrides, phenol compounds, thermal latent cationic polymerization catalysts, and optical latent cationic polymerization initiators. These curing agents may be used alone or 2
More than one kind may be used in combination.

Examples of the amine compound include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine and polyoxypropylenetriamine, and derivatives thereof; mensendiamine,
Isophorone diamine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8 , 10-Tetraoxaspiro (5,5)
Cycloaliphatic amines such as undecane and derivatives thereof; m-
Aromatic amines such as xylenediamine, α- (m / p aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, α, α-bis (4-aminophenyl) -p-diisopropylbenzene, and derivatives thereof. Etc.

Examples of compounds such as polyaminoamide compounds synthesized from the above amine compounds include the above various amine compounds, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadioic acid, isophthalic acid, terephthalic acid, and the like. Polyaminoamide compounds and their derivatives synthesized from carboxylic acid compounds such as dihydroisophthalic acid, tetrahydroisophthalic acid and hexahydroisophthalic acid; polyamino compounds synthesized from the above various amine compounds and maleimide compounds such as diaminodiphenylmethane bismaleimide An imide compound and its derivative; a ketimine compound synthesized from the above various amine compounds and a ketone compound and its derivative;
Epoxy compound, urea, thiourea, aldehyde compound,
Examples thereof include polyamino compounds synthesized from compounds such as phenol compounds and acrylic compounds and their derivatives.

Examples of the tertiary amine compound include:
N, N-dimethylpiperazine, pyridine, picoline, benzyldimethylamine, 2- (dimethylaminomethyl)
Phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabiscyclo (5,4,4
0) Undecene-1 and its derivatives and the like.

Examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole and derivatives thereof.

Examples of the hydrazide compound include:
1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadiene-
1,18-dicarbohydrazide, eicosane diacid dihydrazide, adipic acid dihydrazide and derivatives thereof and the like can be mentioned. Examples of the melamine compound include 2,
4-diamino-6-vinyl-1,3,5-triazine and derivatives thereof and the like can be mentioned.

Examples of the above-mentioned acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrihydrate. Melitate, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5- (2,5 -Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, polyazelaic anhydride, polydodecane dianhydride Acid anhydride, Rend anhydride and derivatives thereof.

Examples of the above-mentioned phenol compound include:
Phenol novolac, o-cresol novolac, p
-Cresol novolac, t-butylphenol novolac, dicyclopentadiene cresol and derivatives thereof and the like.

As the above-mentioned thermal latent cationic polymerization catalyst,
For example, an ionic thermal latent cationic polymerization catalyst such as benzylsulfonium salt, benzylammonium salt, benzylpyridinium salt, benzylphosphonium salt, etc., in which antimony hexafluoride, phosphorus hexafluoride, boron tetrafluoride and the like are used as counter anions; N -Nonionic thermal latent cationic polymerization catalysts such as benzyl phthalimide and aromatic sulfonic acid esters.

Examples of the photolatent cationic polymerization initiator include aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts with counter anions such as antimony hexafluoride, phosphorus hexafluoride, and boron tetrafluoride. Ionic photolatent cationic polymerization initiators such as onium salts such as salts, iron-allene complexes, titanocene complexes, and organometallic complexes such as arylsilanol-aluminum complexes; nitrobenzyl esters, sulfonic acid derivatives, phosphate esters, phenols Sulfonate, diazonaphthoquinone, N-
Examples thereof include nonionic photolatent cationic polymerization initiators such as hydroxyimide sulfonate.

The thermosetting modified polyphenylene ether resin is not particularly limited, and is obtained, for example, by modifying the polyphenylene ether resin with a thermosetting functional group such as a glycidyl group, an isocyanate group or an amino group. Resin etc. are mentioned. These thermosetting modified polyphenylene ether resins may be used alone or in combination of two or more kinds.

The thermosetting polyimide resin is a resin having an imide bond in the molecular main chain, and its specific example is not particularly limited. For example, condensation of aromatic diamine and aromatic tetracarboxylic acid. Polymer, bismaleimide resin which is addition polymer of aromatic diamine and bismaleimide, polyamino bismaleimide resin which is addition polymer of aminobenzoic acid hydrazide and bismaleimide, bismaleimide consisting of dicyanate compound and bismaleimide resin Triazine resin etc. are mentioned. Among them, bismaleimide triazine resin is preferably used. These thermosetting polyimide-based resins may be used alone or in combination of two or more kinds.

The urea resin is not particularly limited as long as it is a thermosetting resin obtained by the addition condensation reaction of urea and formaldehyde. The curing agent used in the curing reaction of the urea resin is not particularly limited, and examples thereof include an inorganic acid, an organic acid, an explicit curing agent composed of an acid salt such as sodium acid sulfate; a carboxylic acid ester, an acid anhydride, and a chloride. Latent curing agents such as salts of ammonium, ammonium phosphate and the like can be mentioned. Of these, a latent curing agent is preferable in terms of shelf life.

The allyl resin is not particularly limited as long as it is obtained by the polymerization and curing reaction of the diallyl phthalate monomer. Examples of the diallyl phthalate monomer include an ortho body, an iso body, and a tele body. Further, as a curing catalyst at the time of curing, for example, t-butyl perbenzoate and di-t-butyl peroxide are used together.

The above-mentioned silicon resin has a silicon-silicon bond, a silicon-carbon bond, a siloxane bond, and a silicon-nitrogen bond in the molecular chain, and examples thereof include polysiloxane, polycarbosilane, and polysilazane.

The benzoxazine resin is obtained by ring-opening polymerization of the oxazine ring of the benzoxazine monomer. The benzoxazine monomer is not particularly limited, and examples thereof include those having a functional group such as a phenyl group, a methyl group or a cyclohexyl group bonded to the nitrogen of the oxazine ring.

The above-mentioned thermoplastic resin and / or thermosetting resin may contain thermoplastic elastomers, cross-linked rubbers, in order to modify the properties of the resin, if necessary, within a range not hindering the achievement of the object of the present invention. Oligomers and the like may be blended.
Also, these may be used alone or in combination.

The thermoplastic elastomers are not particularly limited, and examples thereof include styrene elastomer, olefin elastomer, urethane elastomer, polyester elastomer and the like. These thermoplastic elastomers may be used alone or in combination of two or more.

The crosslinked rubber is not particularly limited, and examples thereof include isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, silicone rubber and urethane rubber. To be In order to improve the compatibility with the resin, it is preferable to use a functional group-modified one of these crosslinked rubbers. These crosslinked rubbers may be used alone or in combination of two or more.

The above-mentioned oligomers are not particularly limited, and examples thereof include maleic anhydride-modified polyethylene oligomers. These oligomers may be used alone or in combination of two or more kinds.

Further, the above-mentioned thermoplastic resin and / or thermosetting resin may contain crystals for refining crystals as an auxiliary means for homogenizing physical properties, if necessary, within a range not hindering achievement of the object of the present invention. Nucleating agents that can serve as nuclei, antioxidants (aging inhibitors), heat stabilizers, light stabilizers, UV absorbers,
One of various additives such as lubricants, flame retardants, antistatic agents, anti-fog agents, etc.
One kind or two or more kinds may be mixed.

The insulating substrate material of the present invention contains a thermoplastic resin and / or a thermosetting resin, and a layered silicate. The layered silicate means a silicate mineral having an exchangeable metal cation between layers. The layered silicate is not particularly limited, and examples thereof include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, and swelling mica. Among them, montmorillonite and / or swelling mica and / or hectorite are preferably used. The layered silicate may be a natural product or a synthetic product. Further, these layered silicates may be used alone or in combination of two or more kinds.

As the layered silicate, it is preferable to use a smectite clay mineral or a swelling mica having a large shape anisotropy effect defined by the following formula (2). By using the layered silicate having a large shape anisotropy effect, the insulating substrate material of the present invention has more excellent mechanical properties. Shape anisotropy effect = area of crystal surface (A) / area of crystal surface (B) In the formula (2), the crystal surface (A) means a layer surface, and the crystal surface (B) means a layer side surface. .

The shape of the layered silicate is not particularly limited, but the preferable lower limit of the average length is 0.0
1 μm, the upper limit is 3 μm, and the preferable lower limit of the thickness is 0.00
1 μm, upper limit is 1 μm, preferred lower limit of aspect ratio is 20, upper limit is 500, more preferred lower limit of average length is 0.05 μm, upper limit is 2 μm, more preferred lower limit of thickness is 0.01 μm, upper limit is 0 The preferable lower limit of the aspect ratio is 0.5 μm, and the upper limit is 200.

The exchangeable metal cations existing between the layers of the layered silicate are metal ions such as sodium and calcium existing on the crystal surface of the layered silicate, and these metal ions are cationic substances. Since it has a cation exchangeability with, it is possible to insert (intercalate) various substances having a cationic property between the crystal layers of the layered silicate.

The cation exchange capacity of the layered silicate is not particularly limited, but the preferred lower limit is 50 milliequivalents / 100g and the upper limit is 200 milliequivalents / 100g. Cation exchange capacity of layered silicate is 50 milliequivalent / 1
If the amount is less than 00 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate due to cation exchange is small, so that the crystal layers may not be sufficiently depolarized (hydrophobicized). If it exceeds the milliequivalent / 100 g, the bonding force between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may be difficult to peel off.

In the present invention, when a low-polarity resin such as polyphenylene ether resin is used as the thermoplastic resin and / or the thermosetting resin, the layers of the layered silicate are cation-exchanged with a cationic surfactant in advance. Therefore, it is preferable to make it hydrophobic. By making the layers of the layered silicate hydrophobic in advance, the affinity between the layered silicate and the low-polarity thermoplastic resin or the thermosetting resin is increased, and the layered silicate is formed in the low-polarity thermoplastic resin and / or It can be finely dispersed more uniformly in the thermosetting resin.

The cationic surfactant is not particularly limited, and examples thereof include a quaternary ammonium salt and a quaternary phosphonium salt. Among them, a quaternary ammonium salt having an alkyl chain having 6 or more carbon atoms (alkylammonium salt having 6 or more carbon atoms) is suitable because it can sufficiently depolarize (hydrophobicize) the crystal layers of the layered silicate. Used.

The quaternary ammonium salt is not particularly limited, and examples thereof include trimethylalkyl ammonium salt,
Triethylalkylammonium salt, tributylalkylammonium salt, dimethyldialkylammonium salt, dibutyldialkylammonium salt, methylbenzyldialkylammonium salt, dibenzyldialkylammonium salt, trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt, A quaternary ammonium salt having an aromatic ring,
Quaternary ammonium salts derived from aromatic amines such as trimethylphenylammonium, dialkyl quaternary ammonium salts having two polyethylene glycol chains, dialkyl quaternary ammonium salts having two polypropylene glycol chains, trialkyls having one polyethylene glycol chain Examples thereof include quaternary ammonium salts and trialkyl quaternary ammonium salts having one polypropylene glycol chain. Among them, especially lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-hardened tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl-N , N-dimethylammonium salt and the like are preferable. These quaternary ammonium salts may be used alone or in combination of two or more kinds.

The quaternary phosphonium salt is not particularly limited, and examples thereof include dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylphosphonium salt, distearyldimethylphosphonium salt, Examples thereof include distearyl dibenzylphosphonium salt. These quaternary phosphonium salts may be used alone or in combination of two or more kinds.

The layered silicate used in the present invention can be improved in dispersibility in the thermoplastic resin and / or the thermosetting resin by the chemical treatment as described above. The above chemical treatment is not limited to the cation exchange method using a cationic surfactant (hereinafter, also referred to as the chemical modification (1) method), and for example, the following chemical modification (2) to chemical modification (6). It can also be carried out by various chemical treatment methods of the method. These chemical modification methods may be used alone or in combination of two or more. In addition, a layered silicate whose dispersibility in a thermoplastic resin and / or a thermosetting resin is improved by various chemical treatment methods shown below including the chemical modification (1) method is referred to as “organized layered material”. Silicate "
Also called.

In the chemical modification (2) method, the hydroxyl group existing on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method is a functional group capable of chemically bonding with the hydroxyl group, or a chemical bond is It is a method of chemically treating with a compound having at least one functional group having a large chemical affinity at the end of the molecule even if it does not.

The chemical modification (3) method comprises a functional group capable of chemically bonding a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method or a chemical bond. It is a method of chemically treating with a compound having one or more functional groups and reactive functional groups having a large chemical affinity even if they are not.

The chemical modification (4) is a method in which the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) is chemically treated with a compound having anionic surface activity.

The chemical modification (5) is a chemical modification (4) in which a compound having one or more reactive functional groups in addition to the anion site in the molecular chain of the compound having anionic surface activity is chemically treated. Is.

The chemical modification (6) method is the same as the above chemical modification (1).
Method to the chemical modification (5), a functional group capable of reacting with a layered silicate such as a maleic anhydride-modified polyphenylene ether resin is further added to the organically modified layered silicate chemically treated. It is a method using a composition to which the resin is added.

In the above-mentioned chemical modification (2) method, the functional group capable of chemically bonding with a hydroxyl group or the functional group having a large chemical affinity without chemical bonding is not particularly limited, and examples thereof include an alkoxy group and glycidyl. Examples thereof include functional groups such as groups, carboxyl groups (including dibasic acid anhydrides), hydroxyl groups, isocyanate groups, aldehyde groups, and other functional groups having high chemical affinity with hydroxyl groups. The compound having a functional group capable of chemically bonding to the hydroxyl group, or a functional group having a large chemical affinity even if not chemically bonded, is not particularly limited, for example, the functional groups exemplified above. Examples thereof include a silane compound having a group, a titanate compound, a glycidyl compound, carboxylic acids and alcohols. These compounds may be used alone or in combination of two or more kinds.

The silane compound is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy).
Silane, γ-aminopropyltrimethoxysilane, γ-
Aminopropylmethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxy Silane, hexyltrimethoxysilane, hexyltriethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane,
N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane , Γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane and the like. These silane compounds may be used alone or 2
More than one kind may be used in combination.

In the chemical modification (4) method and the chemical modification (5) method, a compound having anionic surface activity, having anionic surface activity and having at least one reactive functional group other than the anion site in the molecular chain. The compound is not particularly limited as long as the layered silicate can be chemically treated by ionic interaction, and examples thereof include sodium laurate, sodium stearate, sodium oleate, higher alcohol sulfate ester salt, and secondary higher alcohol sulfate. Examples thereof include ester salts and unsaturated alcohol sulfate ester salts.
These compounds may be used alone or in combination of two or more kinds.

The layered silicate has an average inter-layer distance of 3 nm or more on the (001) plane measured by the wide-angle X-ray diffraction measurement method, and a part or all of the layered silicate is dispersed in 5 layers or less. Is more preferable, and more preferably, it is a layered silicate in which the average interlayer distance is 3 nm or more and 5 nm or less, and part or all of which is dispersed in 5 layers or less. In the present specification, the average interlaminar distance of the layered silicate means the average interlaminar distance when the fine flaky crystals of the layered silicate are formed into a layer, and the X-ray diffraction peak and the transmission electron microscope photograph, that is, , Can be calculated by wide-angle X-ray diffractometry.

The fact that the average interlayer distance of the layered silicate is 3 nm or more means that the layers of the layered silicate are split to 3 nm or more, and part or all of the layered silicate is cleaved. Dispersed in 5 layers or less means that part or all of the layered silicate laminate is dispersed. Each of these means that the interaction between the layers of the layered silicate is weakened.

When the average interlayer distance of the layered silicate is 3 nm or more and a part or the whole is dispersed in 5 layers or less, the layered silicate is blended in the thermoplastic resin and / or the thermosetting resin. The material for an insulating substrate of the present invention obtained by dispersing the above compound exhibits excellent properties such as flame retardancy, mechanical properties, heat resistance, and dimensional stability. Average interlayer distance is 3 nm
If it is less than the above range, the effect due to the dispersion of the layered silicate on the nanometer scale cannot be sufficiently obtained, and the improvement of mechanical properties and flame retardancy remains within the same range as when the ordinary inorganic filler is compounded. A more preferable lower limit of the average interlayer distance is 3 nm, and an upper limit thereof is 5 nm. If the average interlayer distance exceeds 5 nm, the crystal flakes of the layered silicate are separated into layers, and the interaction of the layered silicate weakens to a negligible level, so the film formation rate during combustion is slowed and flame retardancy is improved. May not be obtained sufficiently.

The fact that a part or all of the layered silicate is dispersed in 5 layers or less means that, specifically, one of the layered silicates is
It means that 0% or more is preferably dispersed in 5 layers or less, and more preferably 20% of the layered silicate.
% Or more is dispersed in 5 layers or less. In addition, the dispersed state of the layered silicate is observed in a transmission electron microscope at a magnification of 50,000 to 100,000 times, and out of the total number (X) of the layered aggregates of the layered silicate that can be observed in a certain area. The number of layers (Y) of the laminated assembly dispersed with 5 layers or less can be measured and calculated by the following formula (3). Proportion (%) of layered silicate dispersed in 5 layers or less = (Y / X) × 100
(3)

The number of laminated layered silicates is preferably divided into 5 layers or less, whereby the above effect can be obtained, but more preferably 3 or less layers are divided. It is particularly preferable that the thin film is formed into a single layer.

In the insulating substrate material of the present invention, the layered silicate has an average interlayer distance of 3 nm or more, and a part or all of the layered silicate is dispersed in 5 layers or less, that is, thermoplasticity. If the layered silicate is highly dispersed in the resin and / or thermosetting resin, the thermoplastic resin and / or
Or the interfacial area between the thermosetting resin and the layered silicate increases,
The average distance between the crystal flakes of the layered silicate becomes smaller.

When the interface area between the thermoplastic resin and / or thermosetting resin and the layered silicate increases, the degree of restraint of the thermoplastic resin and / or thermosetting resin on the surface of the layered silicate increases, and the elastic modulus increases. Mechanical properties such as are improved. Further, when the degree of restraint of the thermoplastic resin and / or the thermosetting resin on the surface of the layered silicate increases, the melt viscosity increases and the moldability also improves. Furthermore, since gas molecules are much more likely to diffuse in a polymer than in an inorganic substance, when a gas molecule diffuses in a thermoplastic resin and / or a thermosetting resin, it diffuses while bypassing the inorganic substance. Therefore, the gas barrier property can be exhibited.

On the other hand, when the average distance between the crystal flakes of the layered silicate is small, it becomes easy to form a sintered body by the movement of the crystal flakes of the layered silicate during combustion. That is, the insulating substrate material in which the crystal flakes of the layered silicate are dispersed so that the average interlayer distance is 3 nm or more facilitates the formation of a sintered body that can be a flame retardant coating. Since this sintered body is formed at an early stage of combustion, not only the supply of oxygen from the outside can be cut off, but also the combustible gas generated by the combustion can be cut off. Exhibits excellent flame retardancy.

The insulating substrate material of the present invention 1 is based on 100 parts by weight of the above-mentioned thermoplastic resin or a mixture of the above-mentioned thermoplastic resin and the above-mentioned thermosetting resin, and 0.1% of the above-mentioned layered silicate.
To 100 parts by weight. The insulating substrate material of the present invention 2 contains 0.1 to 100 parts by weight of the layered silicate with respect to 100 parts by weight of the thermosetting resin. The insulating substrate material according to the third aspect of the present invention contains the layered silicate of 0.1 to 1 with respect to 100 parts by weight of the epoxy resin.
It contains 100 parts by weight.

Thermoplastic resin and / or thermosetting resin 10
If the content of the layered silicate is less than 0.1 parts by weight relative to 0 parts by weight, the effect of improving flame retardancy and mechanical properties becomes small, and if it exceeds 100 parts by weight, the density (specific gravity) of the insulating substrate material is increased. Becomes higher and the mechanical strength also lowers, resulting in poor practicability. The preferable lower limit of the content is 1 part by weight and the upper limit is 50 parts by weight. If the amount is less than 1 part by weight, a sufficient flame retarding effect may not be obtained when the insulating substrate material of the present invention is thinly formed, and if it exceeds 50 parts by weight, moldability may be deteriorated. A more preferable lower limit of the content is 5 parts by weight and an upper limit thereof is 20 parts by weight. When the amount is 5 to 20 parts by weight, there is no problem in mechanical properties and process suitability, and a sufficient flame retardant effect can be obtained.

The method for dispersing the layered silicate in the thermoplastic resin and / or the thermosetting resin is not particularly limited,
For example, a method using the above-mentioned organically modified layered silicate; a method in which a thermoplastic resin and / or a thermosetting resin and a layered silicate are mixed by a conventional method and then foamed; a method using a dispersant and the like can be mentioned. By using these dispersion methods,
The layered silicate can be more uniformly and finely dispersed in the thermoplastic resin and / or the thermosetting resin.

The above-mentioned thermoplastic resin and / or thermosetting resin and the layered silicate are mixed by a conventional method, and then foaming is carried out by foaming the thermoplastic resin and / or thermosetting resin using a foaming agent. Then, the foaming energy is converted into the dispersion energy of the layered silicate. The foaming agent is not particularly limited, and examples thereof include a gaseous foaming agent, an easily volatile liquid foaming agent, and a heat decomposable solid foaming agent.
These foaming agents may be used alone or in combination of two or more kinds.

In the presence of the layered silicate, the thermoplastic resin and / or
Alternatively, the specific method for dispersing the layered silicate in the thermoplastic resin and / or the thermosetting resin by foaming the thermosetting resin is not particularly limited, and examples thereof include the thermoplastic resin and / or the thermosetting resin. A resin composition consisting of 100 parts by weight of a resin and 0.1 to 100 parts by weight of a layered silicate is impregnated with a gaseous foaming agent under high pressure, and then the gaseous foaming agent is vaporized in the resin composition. A method of forming a foam by forming a foam; a method of preliminarily containing a heat-decomposable foaming agent between the layers of the layered silicate and decomposing the heat-decomposable foaming agent by heating to form a foam. Etc.

The insulating substrate material of the present invention preferably contains a flame retardant containing substantially no halogen-based composition. The phrase "substantially free of halogen-based composition" means that a slight amount of halogen may be mixed in due to reasons such as the manufacturing process of the flame retardant.

The above flame retardant is not particularly limited, and examples thereof include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, dihydrate gypsum and calcium hydroxide; metal oxides; red phosphorus. And phosphorus compounds such as ammonium polyphosphate; melamine,
Nitrogen-based compounds such as melamine cyanurate, melamine isocyanurate, melamine phosphate and melamine derivatives such as those obtained by subjecting these to surface treatment, layered double hydrates such as fluororesins, silicone oils and hydrotalcites; silicone- Acrylic composite rubber and the like can be mentioned. Among them, metal hydroxides and melamine derivatives are preferably used. Among the above metal hydroxides, magnesium hydroxide and aluminum hydroxide are particularly preferable, and these may be those which have been surface-treated with various surface-treating agents. The surface treatment agent is not particularly limited, and examples thereof include a silane coupling agent, a titanate coupling agent, a PVA surface treatment agent, and an epoxy surface treatment agent. These flame retardants may be used alone or in combination of two or more.

When the flame retardant is a metal hydroxide, it is preferable that the content of the thermoplastic resin or the mixture of the thermoplastic resin and the thermosetting resin is 100 parts by weight in the insulating substrate material of the present invention 1. The lower limit is 0.1 parts by weight and the upper limit is 100 parts by weight. In the insulating substrate material of the present invention 2, the preferred lower limit of the content is 0.1 parts by weight and the upper limit is 100 parts by weight with respect to 100 parts by weight of the thermosetting resin. Is a department
In the insulating substrate material of the present invention 3, the epoxy resin 1
The lower limit of the content of the flame retardant with respect to 00 parts by weight is 0.1.
The upper limit is 100 parts by weight. If it is less than 0.1 part by weight, the flame retarding effect due to the inclusion of these may not be sufficiently obtained, and if it exceeds 100 parts by weight,
The density (specific gravity) of the insulating substrate material may become too high, resulting in poor practicability, or extremely low flexibility and elongation. A more preferable lower limit of the content is 5 parts by weight and an upper limit thereof is 80 parts by weight, and a further preferable lower limit of the content is 10 parts by weight.
Parts by weight, the upper limit is 70 parts by weight. If it is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained if the insulating substrate is made thin, and if it exceeds 80 parts by weight, the defective rate due to swelling during the process at high temperature may increase. is there. 10-7
When it is in the range of 0 parts by weight, there is no problem in mechanical properties, electrical properties and process suitability, and sufficient flame retardancy is exhibited, which is preferable.

When the flame retardant is a melamine derivative,
In the insulating substrate material of the present invention 1, the lower limit of the content is preferably 0.1 parts by weight and the upper limit is 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin or the mixture of the thermoplastic resin and the thermosetting resin. In the insulating substrate material of the present invention 2, the preferable lower limit of the content is 100 parts by weight and the upper limit thereof is 100 parts by weight with respect to 100 parts by weight of the thermosetting resin.
In the insulating substrate material of the present invention 3, the epoxy resin 1
The lower limit of the content of the flame retardant with respect to 00 parts by weight is 0.1.
The upper limit is 100 parts by weight. If it is less than 0.1 part by weight, the flame retarding effect due to the inclusion of these may not be sufficiently obtained, and if it exceeds 100 parts by weight,
Mechanical properties such as flexibility and elongation may be extremely reduced.
A more preferable lower limit of the content is 5 parts by weight and an upper limit thereof is 70 parts by weight, and a further preferable lower limit of the content is 10 parts by weight and an upper limit thereof is 50 parts by weight. If the amount is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained if the insulating substrate is made thin, and if it exceeds 70 parts by weight, mechanical properties such as flexibility and elongation may be extremely deteriorated. . When the amount is in the range of 10 to 70 parts by weight, there is no problem in mechanical properties, electrical properties and process suitability, and sufficient flame retardancy is exhibited, which is preferable.

The insulating substrate material of the present invention contains, if necessary, a filler, a softening agent, a plasticizer, a lubricant, an antistatic agent, an antifogging agent, a colorant, etc. within a range not hindering the achievement of the object of the present invention. One kind or two or more kinds of various additives such as an antioxidant (antiaging agent), a heat stabilizer, a light stabilizer and an ultraviolet absorber may be blended.

The method for producing the insulating substrate material of the present invention is not particularly limited. For example, each predetermined amount of a thermoplastic resin and / or a thermosetting resin and a layered silicate, and various additives to be blended as necessary. A method of directly blending and kneading one kind or two or more kinds of respective predetermined amounts of the agent at room temperature or under heating (hereinafter, also referred to as direct kneading method) or after mixing in a solvent,
There is a method of removing the solvent. In addition, a master batch prepared by previously mixing a thermoplastic resin and / or a thermosetting resin with a predetermined amount or more of a layered silicate and kneading the master batch and the thermoplastic resin and / or the thermosetting resin is prepared. A method of kneading a predetermined amount of the balance (remaining amount) and one or more predetermined amounts of various additives to be blended as needed at room temperature or under heating, or in a solvent (master) Batch method) and the like.

The concentration of the layered silicate in the above masterbatch is not particularly limited, but the preferable lower limit is 1 part by weight and the upper limit is 500 parts by weight with respect to 100 parts by weight of the thermoplastic resin and / or the thermosetting resin. Parts, more preferably the lower limit is 5 parts by weight and the upper limit is 300 parts by weight. If it is less than 1 part by weight, the convenience as a masterbatch that can be diluted to an arbitrary concentration may be lost, and if it exceeds 500 parts by weight, the dispersibility of the masterbatch itself, especially the thermoplastic resin and / or The dispersibility of the layered silicate when diluted with a thermosetting resin to a predetermined amount may deteriorate.

Further, in the above masterbatch method,
A resin composition (A) (masterbatch) in which a layered silicate is mixed with a thermoplastic resin and / or a thermosetting resin, and a thermoplastic resin used when the masterbatch is diluted to a predetermined layered silicate concentration, and The resin composition (B) made of a thermosetting resin may have the same composition or different compositions. As the resin composition (A), at least one resin selected from the group consisting of a polyamide resin, a polyphenylene ether resin, a polyether sulfone resin, and a polyester resin in which the layered silicate can be easily dispersed. The resin composition (B) is preferably contained, and it is preferable that the resin composition (B) contains an epoxy resin which is inexpensive and has excellent electric characteristics and high-temperature physical properties.
The insulating substrate material produced by such a masterbatch method is also one aspect of the present invention.

When a thermoplastic resin is used as the resin, for example, a layered silicate containing a polymerization catalyst (polymerization initiator) such as transition metal complexes is used to prepare a monomer that constitutes the thermoplastic resin. It is also possible to employ a method in which the thermoplastic resin and the insulating substrate material are simultaneously produced at the same time by kneading the layered silicate and polymerizing the monomer.

Furthermore, when a thermosetting resin is used as the resin, for example, a layered silicate containing a curing agent (crosslinking agent) such as amines is used as a resin raw material for the thermosetting resin. A method may be adopted in which the thermosetting resin is cured (crosslinked) and the insulating substrate material is manufactured simultaneously by kneading the layered silicate and curing (crosslinking) the resin raw material. .

The method of kneading the mixture in the method for producing a material for an insulating substrate of the present invention by the above-mentioned direct kneading method or masterbatch method is not particularly limited, and for example, kneading with an extruder, two rolls, Banbury mixer, etc. Examples of the method include kneading using a machine.

The insulating substrate material of the present invention thus obtained was subjected to a combustion test according to ASTM E 1354, and the combustion residue obtained by burning it for 30 minutes under the radiant heating condition of 50 kW / m ² had a rate of 0. 1 cm / s
It is preferable that the stress at yield point when compressed by 4.9 kPa or more. If it is less than 4.9 kPa, the combustion residue is likely to be collapsed by a small force, and the flame retardancy may be insufficient. That is, in order for the sintered body of the insulating substrate material and the laminated plate of the present invention to sufficiently exhibit the function as a flame-retardant coating, it is preferable that the sintered body retains its shape until the end of combustion. More preferably, it is 15.0 kPa or more.

The insulating substrate material of the present invention is preferably used for forming an insulating substrate by molding, or as a varnish for impregnation and coating by dissolving in an appropriate solvent. Further, it is preferably used for a laminated board, a printed board, a core layer or a build-up layer of a multilayer board, a resin-coated copper foil, a copper-clad laminated board, a polyimide film, a TAB film, a prepreg used for these, or the like. The use of the insulating substrate material is not limited to these.

The method of molding the material for an insulating substrate of the present invention is not particularly limited. For example, a method of melt-kneading with an extruder, then extruding, and molding into a film using a T die, a circular die or the like (extrusion) Molding method); a method of dissolving or dispersing in a solvent such as an organic solvent and then casting to form a film (casting molding method); a varnish obtained by dissolving or dispersing in a solvent such as an organic solvent, glass Examples of the method include a method of dipping a cloth-shaped or non-woven cloth-shaped substrate made of an inorganic material or an organic polymer into a film shape (dipping molding method). Among them, the extrusion molding method and the casting molding method are preferable in order to reduce the thickness of the multilayer substrate. Further, the substrate used in the dipping molding method is not particularly limited,
Examples thereof include glass cloth, aramid fiber, polyparaphenylene benzoxazole fiber and the like.

Since the insulating substrate material of the present invention contains a thermoplastic resin and / or a thermosetting resin, and a layered silicate, it has excellent mechanical properties and transparency. In addition, layered silicate can be used as a thin insulating substrate because it can provide excellent mechanical properties without adding a large amount like ordinary inorganic fillers. It is possible to correspond to. Further, the insulating substrate material of the present invention has a glass transition temperature due to the restraint of molecular chains,
Improvements in heat resistance due to an increase in heat distortion temperature, reduction in coefficient of linear thermal expansion, and improvement in dimensional stability based on the nucleating agent effect of the layered silicate during crystal formation are also attempted. Furthermore, the insulating substrate material of the present invention absorbs water by addition of the layered silicate,
It has the function of preventing moisture absorption and the accompanying reduction in dimensional stability such as expansion.

The material for the insulating substrate of the present invention forms a sintered body of layered silicate during combustion, and retains the shape of combustion residue. As a result, shape collapse does not occur even after combustion, and fire spread can be prevented. Therefore, the insulating substrate material of the present invention exhibits excellent flame retardancy. Further, by combining with a non-halogen flame retardant such as a metal hydroxide or a melamine derivative, it is possible to achieve both high mechanical properties and high flame retardancy while considering the environment.

[0112]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

(Example 1) 92.3 parts by weight of a modified polyphenylene ether resin (made by Asahi Kasei Corporation, Zylon (PKL) X9102) as a thermoplastic resin in a small extruder (made by Japan Steel Works, TEX30), 7.7 parts by weight of swellable fluorinated mica (Somasif MAE-100 manufactured by Coop Chemical Co., Ltd.) that has been organically treated with distearyl dimethyl quaternary ammonium salt as a layered silicate is fed and melt-kneaded at a set temperature of 280 ° C It was then extruded into a strand, and the extruded strand was pelletized by a pelletizer to obtain a material for an insulating substrate. Then
The obtained pellets of the insulating substrate material were pressed by a hot press whose temperature was adjusted to 280 ° C. at each of the upper and lower sides and rolled to produce a plate-shaped molded body having a thickness of 2 mm and 100 μm.

Example 2 In the same manner as in Example 1 except that 20 parts by weight of magnesium hydroxide (manufactured by Kyowa Chemical Industry Co., Ltd., Kisuma 5J) was added as a flame retardant, pellets of an insulating substrate material, and , Thickness 2 mm and 100 μm
The plate-shaped molded body of was produced.

Example 3 An alicyclic hydrocarbon resin (norbornene resin, manufactured by Nippon Zeon Co., Ltd.) as a thermoplastic resin,
ZEONOR 1600R) 70 parts by weight, 20 parts by weight of swellable fluorine mica (Somasif MAE-100 manufactured by Coop Chemical Co., Ltd.) which has been organically treated with a distearyl dimethyl quaternary ammonium salt as a layered silicate, and cyclohexane (Wako Pure Chemical) Made by Kogyo Co., Ltd.) with a resin concentration of 30% by weight
It was charged so that it became, and mixed by stirring to dissolve. To this solution, 85 parts by weight of synthetic silica (manufactured by Mitsubishi Materials Corp., Elsil (spherical product)) and 30 parts by weight of trimellitic acid triallyl ester (Sankyo Co., Ltd., TRIAM705) were added, and the mixture was stirred to obtain a solution. An insulating substrate material was obtained by drying and removing the solvent. Then, the obtained insulating substrate material was pressed by a hot press whose temperature was adjusted to 280 ° C. at each of the upper and lower sides and rolled to produce a plate-shaped molded body having a thickness of 2 mm and 100 μm.

Example 4 In a small extruder (TEX30 manufactured by Japan Steel Works, Ltd.), 92.3 parts by weight of a polyetherimide resin as a thermoplastic resin and a distearyl dimethyl quaternary ammonium salt as a layered silicate were used as organic materials. 7.7 parts by weight of swellable fluorine mica (Somasif MAE-100 manufactured by Cope Chemical Co., Ltd.) and magnesium hydroxide (Kisuma 5J manufactured by Kyowa Chemical Industry Co., Ltd.) as a flame retardant 20
Part by weight was fed, melt-kneaded, extruded into a strand shape, and the extruded strand was pelletized by a pelletizer to obtain a pellet of a material for an insulating substrate.
Then, the pellets of the obtained insulating substrate material are respectively placed on the upper and lower sides by 3
The thickness is 2 by pressing and rolling with a hot press controlled to 50 ℃.
mm and 100 μm plate-shaped compacts were produced.

Example 5 Bisphenol F type epoxy resin (Epiclon 830L, manufactured by Dainippon Ink and Chemicals, Inc.)
VP) 57.7 parts by weight, BT resin (manufactured by Mitsubishi Gas Chemical Co., Inc., BT2100B) 15.7 parts by weight, neopentyl glycol diglycidyl ether 15.7 parts by weight, γ-glycidoxypropyltrimethoxysilane as a coupling agent. An epoxy resin composition 92. 2.1 parts by weight (manufactured by Nippon Unicar Co., Ltd.) and 1.1 parts by weight of iron acetylacetone (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a curing catalyst.
3 parts by weight, a swelling fluorine mica organically treated with distearyl dimethyl quaternary ammonium salt as a layered silicate (Somasif MAE-100 manufactured by Corp Chemical)
After 7.7 parts by weight and 20 parts by weight of magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5J) as a flame retardant were kneaded with a stirring and kneading machine for 1 hour, degassing was performed to obtain a liquid insulating resin composition. It was Then, the obtained liquid insulating resin composition
After heating at 0 ° C for 3 hours, it is further heated at 160 ° C for 3 hours to be cured to obtain a material for an insulating substrate, and a thickness of 2 m.
m and 100 μm plate-shaped molded bodies were produced.

(Examples 6 to 11) 90 parts by weight of a solid epoxy resin (made by Yuka Shell Epoxy Co., Epicoat 1007) in a small extruder (made by Japan Steel Works, TEX30),
As a layered silicate, 10 parts by weight of natural montmorillonite (New S-Ben D, manufactured by Toyojun Yoko Co., Ltd.) that has been organically treated with distearyldimethyl quaternary ammonium salt, and magnesium hydroxide as a flame retardant (Kyowa Chemical Industry Co., Ltd. Kisuma 5J) 0.1, 5, 10, 70, 80, 10
0 parts by weight was fed, melt-kneaded at 100 ° C., extruded into a strand, and the extruded strand was pelletized by a pelletizer.

The pellets were dissolved in methyl ethyl ketone, and dicyandiamide (CG-1200 manufactured by BITI Japan Co., Ltd.) as a curing agent was added as a solid epoxy component 9
3 parts by weight relative to 0 parts by weight, curing catalyst (manufactured by Shikoku Kasei Co.,
Curesol 2E4HZ) was added to this solution in an amount of 3 parts by weight based on 90 parts by weight of the solid epoxy content, and the mixture was sufficiently stirred and then defoamed to prepare an insulating resin composition solution. Then, after removing the solvent in a state where the obtained insulating resin composition solution was placed in a mold or applied on a sheet of polyethylene terephthalate, it was heated at 110 ° C. for 3 hours, and further heated at 160 ° C.
Heat for 3 hours to cure and obtain a material for insulating substrate, thickness 2
mm and 100 μm plate-shaped compacts were produced.

(Examples 12 to 17) 90 parts by weight of a solid epoxy resin (manufactured by Yuka Shell Epoxy Co., Epicoat 1007) in a small extruder (TEX30 manufactured by Japan Steel Works) and an epoxy-modified butadiene rubber as a rubber component. (Denalex R-45 EPT, manufactured by Nagase Chemtex) 1
0 parts by weight, magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5J) 30 parts by weight as a flame retardant, and synthetic mica (Corp Chemical Co., ME-10) as a layered silicate.
0) 0.1, 1, 5, 20, 50, 100 parts by weight was fed, melt-kneaded at 100 ° C. and extruded into a strand, and the extruded strand was pelletized by a pelletizer.

The pellets were dissolved in methyl ethyl ketone, and dicyandiamide (CG-1200 manufactured by BITI Japan Co., Ltd.) as a curing agent was added as a solid epoxy component 9
3 parts by weight relative to 0 parts by weight, curing catalyst (manufactured by Shikoku Kasei Co.,
Curesol 2E4HZ) was added to this solution in an amount of 3 parts by weight based on 90 parts by weight of the solid epoxy content, and the mixture was sufficiently stirred and then defoamed to prepare an insulating resin composition solution. Then, after removing the solvent in a state where the obtained insulating resin composition solution was placed in a mold or applied on a sheet of polyethylene terephthalate, it was heated at 110 ° C. for 3 hours, and further heated at 160 ° C.
Heat for 3 hours to cure and obtain a material for insulating substrate, thickness 2
mm and 100 μm plate-shaped compacts were produced.

(Example 18) A polyphenylene ether resin (made by Asahi Kasei Corp., Zylon X9102) as a thermoplastic resin in a small extruder (made by Japan Steel Works, TEX30).
40 parts by weight, epoxy-modified butadiene rubber as a rubber component (Denarex R-45E manufactured by Nagase Chemtex Corp.)
PT) 10 parts by weight, and synthetic mica (Somasif MAE-100 manufactured by Coop Chemical Co., Ltd.) that has been organically treated with distearyldimethyl quaternary ammonium salt as a layered silicate.
10 parts by weight and 50 parts by weight of a melamine derivative melamine cyanurate (manufactured by Nissan Kagaku Co.) as a flame retardant are fed,
The mixture was melt-kneaded at 280 ° C. and extruded into a strand, and the extruded strand was pelletized by a pelletizer.

The pellets were dissolved in toluene, and the liquid bisphenol A type epoxy resin (D.E.R. 331L, manufactured by Dow Chemical Japan Co., Ltd.) was added to the solution in an amount of 60 parts by weight based on 40 parts by weight of the polyphenylene ether resin. In addition, as a curing agent, dicyandiamide
2 parts by weight of CG-1200 manufactured by TI Japan Co., Ltd. with respect to 60 parts by weight of solid epoxy, and 2 parts by weight of curing catalyst (Curesol 2E4HZ manufactured by Shikoku Kasei) with respect to 60 parts by weight of solid epoxy. After adding to this solution and stirring thoroughly, it was defoamed to prepare an insulating resin composition solution. Then, after removing the solvent in a state where the obtained insulating resin composition solution was put in a mold or applied on a polyethylene terephthalate sheet, it was heated at 110 ° C. for 3 hours and further heated at 160 ° C. for 3 hours. The material for an insulating substrate was obtained by curing and a plate-shaped molded body having a thickness of 2 mm and 100 μm was produced.

(Example 19) 30 parts by weight of 6-nylon resin (T-850 manufactured by Toyobo Co., Ltd.) as a thermoplastic resin and natural as a layered silicate in a small extruder (TEX30 manufactured by Japan Steel Works). Montmorillonite (Toyojun Yoko, B
Engel A) 10 parts by weight and magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5J) 40 parts by weight as a flame retardant are melt-kneaded at 250 ° C. and extruded into a strand, and the extruded strand is pelletized by a pelletizer. Turned into

This pellet was dissolved in o-chlorophenol, and 6 parts of liquid bisphenol A type epoxy resin (D.E.R. 331L, manufactured by Dow Chemical Japan Co.) was added to this solution.
-Adding 70 parts by weight to 30 parts by weight of nylon resin, and further adding dicyandiamide (CG-1200 manufactured by BITI Japan Co., Ltd.) as a curing agent to 2 parts based on 70 parts by weight of solid epoxy content. 2.3 parts by weight of curing catalyst (Curesol 2E4HZ, manufactured by Shikoku Kasei Co., Ltd.) was added to this solution in an amount of 2.3 parts by weight based on 90 parts by weight of solid epoxy content, and the mixture was sufficiently stirred and then defoamed to obtain an insulating resin composition A solution was made. Then, after removing the solvent in a state where the obtained insulating resin composition solution was put in a mold or applied on a polyethylene terephthalate sheet, it was heated at 110 ° C. for 3 hours and further heated at 160 ° C. for 3 hours. The material for an insulating substrate was obtained by curing and a plate-shaped molded body having a thickness of 2 mm and 100 μm was produced.

(Example 20) A polyetheretherketone resin (manufactured by Victorex Co., 450G) was used as a thermoplastic resin in a small extruder (TEX30 manufactured by Japan Steel Works, Ltd.).
2) 90 parts by weight, natural montmorillonite (Toyojun Yoko Corp., New S-Ben, organically treated with distearyldimethyl quaternary ammonium salt as a layered silicate)
D) 10 parts by weight, 10 parts by weight of a melamine derivative melamine cyanurate (manufactured by Nissan Chemical Co., Ltd.) as a flame retardant are fed, melt-kneaded at 370 ° C. and extruded into a strand, and the extruded strand is pelletized by a pelletizer. Thus, a pellet of the insulating substrate material was obtained. Then, the pellets of the obtained insulating substrate material are placed on the upper and lower sides 370, respectively.
2mm thick by pressing and rolling with a hot press controlled to ℃
And a plate-shaped molded body of 100 μm were produced.

(Example 21) 90 parts by weight of a thermosetting polyimide resin (SKYBOND703, manufactured by IST) were treated with a synthetic mica as a layered silicate with distearyldimethyl quaternary ammonium salt. 10 parts by weight (Somasif MAE-100 manufactured by Coop Chemical Co., Ltd.) was added and stirred to obtain a varnish. Then, the obtained varnish was applied onto a polyethylene terephthalate film and the obtained sheet was heated at 120 ° C. for 60 hours to give a thickness of 100 μm.
A sheet having a thickness of 2 mm and a sheet having a thickness of 2 mm were produced by laminating the sheet of m.

(Comparative Example 1) Calcium carbonate having an average particle diameter of 50 μm was used in place of 7.7 parts by weight of swelling fluorine mica (Somasif MAE-100 manufactured by Coop Chemical Co.).
In the same manner as in Example 1 except that 7 parts by weight was used, an insulating substrate material and a plate-shaped molded body having a thickness of 2 mm and 100 μm were produced.

(Comparative Example 2) An insulating substrate material and a thickness of 2 mm were prepared in the same manner as in Example 2 except that the swellable fluorine mica (Somasif MAE-100 manufactured by Coop Chemical Co., Ltd.) was not added. A 100 μm plate-shaped molded body was produced.

(Comparative Example 3) An insulating substrate material and a thickness of 2 mm were prepared in the same manner as in Example 3 except that the swellable fluorine mica (Somasif MAE-100 manufactured by Coop Chemical Co., Ltd.) was not added. A 100 μm plate-shaped molded body was produced.

Comparative Example 4 An insulating substrate material and a thickness of 2 mm were prepared in the same manner as in Example 4 except that the swelling fluorine mica (Somasif MAE-100 manufactured by Coop Chemical Co., Ltd.) was not added. A 100 μm plate-shaped molded body was produced.

(Comparative Example 5) An insulating substrate material and a thickness of 2 mm were prepared in the same manner as in Example 5 except that the swellable fluorine mica (Somasif MAE-100 manufactured by Coop Chemical Co., Ltd.) was not added. A 100 μm plate-shaped molded body was produced.

Comparative Example 6 For insulating substrates in the same manner as in Examples 6 to 11 except that the amount of magnesium hydroxide added was 0.05 parts by weight and the amount of natural montmorillonite added was 0.05 parts by weight. Material and thickness 2 mm and 10
A 0 μm plate-shaped molded body was produced.

Comparative Example 7 An insulating substrate material and thicknesses of 2 mm and 100 were prepared in the same manner as in Examples 6 to 11 except that the amount of magnesium hydroxide added was 120 parts by weight.
A plate-shaped molded body of μm was produced.

(Comparative Example 8) The amount of synthetic mica added was 0.0
A material for an insulating substrate and a thickness of 2 mm and 100 μm in the same manner as in Examples 12 to 17 except that the amount was 5 parts by weight.
The plate-shaped molded body of was produced.

(Comparative Example 9) The addition amount of synthetic mica was set to 130.
A material for an insulating substrate and a plate-shaped molded product having a thickness of 2 mm and 100 μm were produced in the same manner as in Examples 12 to 17 except that the weight part was used.

(Comparative Example 10) An insulating substrate material and an insulating substrate material were prepared in the same manner as in Example 18 except that the melamine derivative was added in an amount of 0.05 parts by weight and the synthetic mica was added in an amount of 0.05 parts by weight. A plate-shaped molded body having a thickness of 2 mm and a thickness of 100 μm was produced.

(Comparative Example 11) A material for an insulating substrate and a plate-shaped molded product having a thickness of 2 mm and 100 µm were produced in the same manner as in Example 18 except that the addition amount of the melamine derivative was 120 parts by weight.

<Evaluation> Examples 1 to 21 and Comparative Example 1
Performance of the plate-shaped molded product obtained in any one of (1) to (11) (average interlayer distance of layered silicate, ratio of layered silicate dispersed in 5 layers or less,
Via processability, shape retention during combustion, film strength of combustion residue)
Was evaluated by the following method. The results are shown in Tables 1 to 6.

(1) Average interlaminar distance of layered silicate Obtained by diffraction of layered surface of layered silicate in a plate-shaped compact having a thickness of 2 mm using an X-ray diffractometer (RINT1100 manufactured by Rigaku Corporation). The 2θ of the diffraction peak is measured, and the (0) of the layered silicate is calculated by the black diffraction formula (4) below.
01) Interplanar spacing (d) was calculated, and the obtained d was defined as the average interlayer distance (nm). λ = 2d sin θ (4) In the formula, λ is 1.54, d represents the interplanar spacing of the layered silicate, and θ represents the diffraction angle.

(2) Ratio of layered silicate dispersed in 5 layers or less Observed at 50,000 to 100,000 times with a transmission electron microscope,
Of the total number (X) of layered silicate laminates that can be observed in a given area, the number of layered silicate layers (Y) dispersed in 5 or less layers was measured, and 5 was calculated by the following formula (3). The ratio (%) of the layered silicate dispersed below the layer was calculated. Ratio (%) of layered silicate dispersed in 5 layers or less = (Y / X) × 100 (3)

(3) Via Workability Using a high peak short pulse oscillation type carbon dioxide gas laser processing machine (ML605GTX-5100U, manufactured by Mitsubishi Electric Corporation),
Micro vias were formed in a plate-shaped molded body having a thickness of 100 μm. Then, the via surface was observed using a scanning electron microscope (SEM), and the via processability was evaluated according to the following criteria. ◯: Carbide generation was small, and the difference in via shape and via opening diameter was small. X: Carbide was generated frequently, and the difference in via shape and via opening diameter was large.

(4) Shape retention during burning ASTM E 1354 "Testing method for flammability of building materials"
According to the standard, thickness 2 cut into 100 mm x 100 mm
5 mm with a cone calorimeter
It was burned by irradiating it with a heat ray of 0 kW / m ² . At this time, the change in shape of the plate-shaped molded product before and after combustion was visually observed, and the shape retention during combustion was evaluated according to the following criteria. ◯: The change in shape was slight. X: The shape change was severe.

(5) Maximum heat release rate and film strength of combustion residue ASTM E 1354 "Test method for flammability of building materials"
According to the standard, thickness 2 cut into 100 mm x 100 mm
5 mm with a cone calorimeter
It was burned by irradiating it with a heat ray of 0 kW / m ² . The maximum heat generation rate (kW / m ² ) at this time was measured. Further, the combustion residue was compressed at a speed of 0.1 cm / s using a strength measuring device, and the coating strength (kPa) of the combustion residue was measured.

[0145]

[Table 1]

[0146]

[Table 2]

[0147]

[Table 3]

[0148]

[Table 4]

[0149]

[Table 5]

[0150]

[Table 6]

From the table, it can be seen that in the plate-shaped moldings produced using the materials for insulating substrates obtained in Examples 1 to 21, the average interlayer distance of the layered silicate was 3 nm or more, and
Since the proportion of the layered silicate dispersed in 5 layers or less was 10% or more, the shape retention during combustion and the via processability were excellent. In addition, the maximum heat generation rate was slow and the film strength of the combustion residue was 4.9 kPa or more because a sintered body that could be a flame-retardant film was easily formed.

On the other hand, calcium carbonate was dispersed in a layered manner in the plate-shaped molded product made of the material for insulating substrate obtained in Comparative Example 1 in which calcium carbonate was used instead of the swelling fluoromica (layered silicate). Since the shape retention during combustion and via workability are both poor, and it is difficult to form a sintered body that can form a flame-retardant coating, the maximum heat generation rate is fairly fast, and the coating strength of combustion residues is extremely low. It was

Comparative Example 2 in which no layered silicate was added
The plate-shaped molded body made of the insulating substrate material obtained in
In many cases, the shape retention during combustion and via processability were poor, and the combustion residue did not form a film, or the film strength of the combustion residue was extremely low.

Further, the plate-like molded body made of the material for an insulating substrate obtained in Comparative Example 8 containing a small amount of the layered silicate was poor in shape retention during combustion and via workability, and the film strength of combustion residue was low. In the plate-like molded body made of the material for insulating substrate obtained in Comparative Example 9 containing a large amount of the layered silicate, the proportion of the layered silicate dispersed in 5 layers or less was 4%, and the via processability was It was bad.

Further, the plate-shaped compacts made of the materials for insulating substrates obtained in Comparative Examples 6 and 10 in which the amounts of the layered silicate and the flame retardant were small were poor in shape retention during combustion, and the maximum heat generation rate was high. Furthermore, the film strength of the combustion residue was extremely low. The plate-shaped molded bodies made of the insulating substrate material obtained in Comparative Examples 7 and 11 containing a large amount of the flame retardant had problems such as poor via processability.

[0156]

INDUSTRIAL APPLICABILITY According to the present invention, a material for an insulating substrate which is excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy and the like, and particularly exhibits an excellent flame retardant effect by a shape retaining effect during combustion,
It is possible to provide a printed board, a laminate, a resin-coated copper foil, a copper-clad laminate, a polyimide film, a TAB film, and a prepreg.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/00 C08L 63/00 C H01B 17/56 H01B 17/56 A 17/62 17/62 H05K 1 / 03 610 H05K 1/03 610N // C08L 79:08 C08L 79:08 (31) Priority claim number Japanese Patent Application 2001-141888 (P2001-141888) (32) Priority date May 11, 2001 (2001.5) 11) (33) Country of priority claim Japan (JP) (72) Inventor Katsuo Fushimi 2-1 Hyakusanyama, Honcho, Shimamoto-cho, Mishima-gun, Osaka Prefecture (72) Inside Sekisui Chemical Co., Ltd. (72) Hideyuki Takahashi, Mishima-gun Island, Osaka Prefecture Honcho Hyakuzan 2-1 Sekisui Chemical Co., Ltd. (72) Inventor Koji Taniguchi Shimamoto-cho, Mishima-gun, Osaka Prefecture 2-1 Sekisui Chemical Co., Ltd. (72) Inventor Motohiro Yagi Shimamoto-cho, Mishima-gun Osaka Hyakusan 2-1 Sekisui F-Term (Reference) within Chemical Industry Co., Ltd. BK001 CB001 CC032 CC182 CD002 CF001 CF212 CH071 CH072 CH091 CK012 CK022 CL001 CM041 CM042 CN031 CP002 CP033 DE077 DE087 DE147 DE187 DH007 DH027 DJ006 EU187 GF00 GQ01 GQ05 5G333 AA05 AB05 BA01 CB08 DA03 DA04 DA02 DA02 DA02 DA02 DA02 DA02 DA02

Claims (20)

[Claims] 1. A material used for an insulating substrate, which contains 100 parts by weight of a thermoplastic resin or a mixture of a thermoplastic resin and a thermosetting resin, and 0.1 to 100 parts by weight of a layered silicate. An insulating substrate material characterized by the above. 2. The thermoplastic resin is a polyphenylene ether resin, a functional group-modified polyphenylene ether resin, a polyphenylene ether resin or a mixture of a functional group-modified polyphenylene ether resin and polystyrene resin, and a resin. At least one selected from the group consisting of a cyclic hydrocarbon resin, a thermoplastic polyimide resin, a polyether ether ketone resin, a polyether sulfone resin, a polyamideimide resin and a polyesterimide resin. Item 2. An insulating substrate material according to item 1. 3. A material used for an insulating substrate, which is a phenol resin, a urea resin, an unsaturated polyester resin, an allyl resin, a thermosetting polyimide resin, a bismaleimide triazine resin, a thermosetting modified polyphenylene ether resin, or a silicon resin. And 100 parts by weight of at least one thermosetting resin selected from the group consisting of benzoxazine-based resins, and 0.1 to 100 parts by weight of layered silicate, a material for an insulating substrate. 4. The material for an insulating substrate according to claim 1, comprising 0.1 to 100 parts by weight of a flame retardant containing substantially no halogen-based composition. 5. A layered silicate of 0.1 to 1 relative to 100 parts by weight of an epoxy resin, which is a material used for an insulating substrate.
A material for an insulating substrate, containing 100 parts by weight of a flame retardant which does not substantially contain a halogen-based composition. 6. A resin composition (A) containing 100 parts by weight of a resin composed of at least one or more thermoplastic resins and / or thermosetting resins and 1 to 500 parts by weight of a layered silicate.
And a resin composition (B) having the same or different composition as the resin composition (A) and containing at least one or more thermoplastic resins and / or thermosetting resins. An insulating substrate material characterized by the above. 7. The resin composition (A) contains at least one resin selected from the group consisting of a polyamide resin, a polyphenylene ether resin and a polyester resin, and the resin composition (B) is an epoxy resin. The insulating substrate material according to claim 6, further comprising a resin. 8. The insulating substrate material according to claim 4, wherein the flame retardant is a metal hydroxide. 9. The insulating substrate material according to claim 4, wherein the flame retardant is a melamine derivative. 10. The layered silicate is at least one selected from the group consisting of montmorillonite, swelling mica, and hectorite.
The material for an insulating substrate according to 2, 3, 4, 5, 6, 7, 8 or 9. 11. The insulation according to claim 1, wherein the layered silicate contains an alkylammonium ion having 6 or more carbon atoms. Substrate material. 12. The layered silicate has an average inter-layer distance of 3 nm or more on the (001) plane measured by a wide-angle X-ray diffractometry and a part or all of which is dispersed in 5 layers or less. Claims 1, 2, 3, 4, 5, 6, 7, characterized in that
The material for an insulating substrate according to 8, 9, 10 or 11. 13. In a combustion test according to ASTM E 1354, 3 under a radiant heating condition of 50 kW / m ^2.
The yield point stress was 4.9 kP when the combustion residue burned by heating for 0 minutes was compressed at a speed of 0.1 cm / s.
a or more, Claims 1, 2, 3, 4,
The material for an insulating substrate according to 5, 6, 7, 8, 9, 10, 11 or 12. 14. Claims 1, 2, 3, 4, 5, 6, 7,
A laminated board comprising the insulating substrate material described in 8, 9, 10, 11, 12 or 13. 15. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A printed circuit board, which is made of the material for an insulating substrate according to 8, 9, 10, 11, 12 or 13. 16. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A resin-coated copper foil comprising the insulating substrate material according to 8, 9, 10, 11, 12 or 13. 17. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A copper-clad laminate comprising the insulating substrate material described in 8, 9, 10, 11, 12 or 13. 18. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A polyimide film comprising the insulating substrate material described in 8, 9, 10, 11, 12 or 13. 19. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A film for TAB, which is made of the material for an insulating substrate according to 8, 9, 10, 11, 12 or 13. 20. Claims 1, 2, 3, 4, 5, 6, 7,
A prepreg characterized by using the material for an insulating substrate according to 8, 9, 10, 11, 12 or 13.