JP2003292803A - Material for insulated-substrate, printed board, laminated board, copper foil with resin, copper-clad laminated board, polyimide film and film for tab and pre-preg - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material for an insulated-substrate, a printed board, a laminated board, a copper foil with a resin, a copper-clad laminated board, a polyimide film, a film for a TAB and a pre-preg, which is excellent in mechanical properties, dimensional stability, heat resistance, fire retardancy and so on and particularly can show excellent fire retardant effect by its form retention effect upon burning. <P>SOLUTION: The material for an insulated-substrate comprises 100 pt.wt. of at least one thermoplastic resin mixture and/or thermosetting resin mixture, 0.1-100 pt.wt. of a layered silicate, 0.1-100 pt.wt. of a fire retardant containing substantially no halogen composition and 0.1-50 pt.wt. of a fire retardant auxiliary. <P>COPYRIGHT: (C)2004,JPO

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.

[0004] For example, in Patent Document 1, "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, a curing agent and a cross-linking 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 as a main component and applying the non-fibrous inorganic filler on one side or both sides of the support as an insulating layer. A method of manufacturing a multi-layer insulating substrate "is disclosed.

However, in the multi-layer insulating substrate produced by this manufacturing method, the interfacial area between the inorganic filler and the high molecular weight epoxy polymer or polyfunctional epoxy resin required 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 the inorganic filler, which makes it difficult to thin the layers and causes a problem such as an increase in the number of steps 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.

The multilayer printed circuit board is manufactured by a build-up method for obtaining a multilayer board by repeating circuit formation and stacking on layers, or a batch stacking method for stacking circuit-formed layers at once. It includes processes that require solvent resistance, water resistance, heat resistance, and dimensional stability at high temperatures, such as processes, curing processes, and solder reflow processes. Further, since the number of steps is large, the quality of the material has a great influence on the yield.

Therefore, the qualities required for these materials are resistance to acids, alkalis and organic solvents, low hygroscopicity that also affects electrical characteristics, and high temperature that affects highly accurate circuit connection between upper and lower layers. In addition, dimensional stability after heating, heat resistance at 260 ° C. corresponding to lead-free solder, low migration property of copper that affects connection reliability, and the like are included.

In Patent Document 1, an attempt is made to improve high temperature physical properties by using an epoxy resin having high heat resistance and by using an inorganic compound together, but the physical properties below the glass transition point are improved, but the effect is Is small. Furthermore, there is almost no improvement effect above the glass transition point. Further, the effect of improving hygroscopicity and solvent resistance cannot be expected.

On the other hand, in recent years, polymeric materials used for industrial purposes have been required to be environmentally friendly materials due to the problems of processing waste plastics 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.

For this reason, in recent years, materials for insulating substrates have also been developed using non-halogen flame retardants 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.

From the above, the problem with the conventional insulating substrate material is that it is difficult to maintain heat resistance, dimensional stability and mechanical properties when a thin insulating substrate is used, and non-halogen type flame retardant causes Since a large amount of flame retardant must be blended in order to develop the required flame retardancy, it is difficult to obtain the mechanical properties and heat resistance required during the manufacturing process.

[0013]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-183539

[0014]

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.

[0015]

The present invention relates to a material used for an insulating substrate, which is 100 parts by weight of a mixture of at least one or more thermoplastic resins and / or thermosetting resins, and a layered silicate. It is an insulating substrate material containing 100 parts by weight, 0.1 to 100 parts by weight of a flame retardant containing substantially no halogen-based composition, and 0.1 to 50 parts by weight of a flame retardant aid. The present invention is described in detail below.

The insulating substrate material of the present invention comprises at least 1
It contains a mixture of one or more thermoplastic resins and / or thermosetting resins. 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 type resin, thermoplastic polyimide type resin, polyamideimide type resin, polyesterimide type resin, polyester type resin, polyether ether ketone (PE
EK) type resin, polyether sulfone resin, polyamide type resin, polyvinyl acetal type resin, polyvinyl alcohol type resin, polyvinyl acetate type resin, poly (meth)
Examples thereof include acrylic acid ester-based resins and polyoxymethylene-based resins. Among them, polyphenylene ether resin, functional group-modified polyphenylene ether resin,
A polyphenylene ether resin, a mixture of a functional group-modified polyphenylene ether resin and a polystyrene resin, an alicyclic hydrocarbon resin, a thermoplastic polyimide resin, or the like is preferably used. These thermoplastic resins may be used alone or in combination of two or more kinds. 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).

[0018]

[Chemical 1]

In the formula, R1, R2, R3 and R4 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 above polyphenylene ether copolymer is not particularly limited, and for example, a copolymer partially containing alkyl trisubstituted phenol such as 2,3,6-trimethylphenol in the above 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 or two of functional groups such as maleic anhydride group, glycidyl group, amino group and allyl group.
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 to further improve 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-based resin is not particularly limited as long as it is a hydrocarbon-based resin having a cyclic hydrocarbon group in the polymer chain, and examples thereof include homopolymers or copolymers of cyclic olefins. 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, trimethanodecahydroanthracene 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 an alkyl group, an alkylidene group, an aryl group, a cyano group, an alkoxycarbonyl group, a pyridyl group and a 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 polyether ether ketone resin is not particularly limited, and examples thereof include those obtained by polycondensing dihalogenobenzophenone and hydroquinone.

The thermosetting resin is a resin raw material composed 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 it may be hardener, 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 phenol 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 means 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 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.

Examples of the epoxy resin (1) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; phenol novolac type epoxy resin, cresol. Examples thereof include novolac type epoxy resins such as novolac type epoxy resins; aromatic epoxy resins such as trisphenolmethane triglycidyl ether and hydrogenated products and bromides thereof.

As the epoxy resin (2), for example,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 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- Examples thereof include alicyclic epoxy resins such as epoxy) cyclohexanone-meta-dioxane and bis (2,3-epoxycyclopentyl) ether. Examples of commercially available epoxy resin (2) include, for example, trade name "EHPE-3".
150 "(softening temperature 71 ° C, manufactured by Daicel Chemical Industries, Ltd.).

As the epoxy resin (3), for example,
Diglycidyl ether of 1,4-butanediol, 1,
6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, carbon number 2-9 (preferably 2-4) Aliphatic epoxy resins such as polyglycidyl ethers of long chain polyols containing polyoxyalkylene glycols containing a number of alkylene groups, polytetramethylene ether glycols, and the like.

As the epoxy resin (4), for example, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, salicylic acid glycidyl ether-glycidyl ester, Examples thereof include glycidyl ester type epoxy resins such as dimer acid glycidyl ester and hydrogenated products thereof.

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

Examples of the epoxy resin (6) include a copolymer of glycidyl (meth) acrylate and a radical polymerizable monomer such as ethylene, vinyl acetate and (meth) acrylic acid ester.

As the epoxy resin (7), for example, a polymer having a conjugated diene compound such as epoxidized polybutadiene as a main component or a polymer of a partially hydrogenated product thereof in which an unsaturated carbon double bond is epoxidized, etc. Is mentioned.

Examples of the epoxy resin (8) include "a polymer block mainly containing a vinyl aromatic compound" and "a polymer block mainly containing a conjugated diene compound or a partial water thereof, such as epoxidized SBS. Examples thereof include block copolymers having an “polymer block of an additive” in the same molecule, in which a double bond of unsaturated carbon of a conjugated diene compound is epoxidized.

As the epoxy resin (9), for example, 1
Examples thereof include polyester resins having one or more, and preferably two or more epoxy groups per molecule.

As the epoxy resin (10), for example,
Examples thereof include a urethane-modified epoxy resin and a polycaprolactone-modified epoxy resin in which a urethane bond or a polycaprolactone bond is introduced into the structures of the above various epoxy resins.

As the epoxy resin (11), for example,
Examples thereof include rubber-modified epoxy resins in which a rubber component such as NBR, CTBN, polybutadiene, and acrylic rubber is contained in the 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 above-mentioned amine compound include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, 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 and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadioic acid, isophthalic acid, terephthalic acid, 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 acid anhydride include phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydrotrimellitate, and 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 initiators include aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts having 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 silicon resin contains 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 above-mentioned 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 characteristics 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 elastomers, olefin elastomers, urethane elastomers, polyester elastomers and the like. In order to improve compatibility with the resin, functional groups modified from these thermoplastic elastomers can also be used. 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.

Examples of the crosslinked rubber modified with a functional group include epoxy modified butadiene rubber and epoxy modified nitrile rubber.

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

Furthermore, the above-mentioned thermoplastic resin and / or thermosetting resin may contain crystals for refining the crystals as an auxiliary means for homogenizing the physical properties, if necessary, within a range not hindering the 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) (2) In the formula, crystal surface (A) means a layer surface, and 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 a polyphenylene ether resin is used as the thermoplastic resin and / or the thermosetting resin, the layers of the layered silicate are previously cation-exchanged with a cationic surfactant. 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, trioctylmethylphosphonium salt, Examples thereof include distearyl dimethylphosphonium salt and 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.

The chemical modification (2) method is 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 at least one functional group having a large chemical affinity at the end of the molecule even if it does not.

In the chemical modification (3) method, the hydroxyl group present 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 one or more functional groups and reactive functional groups having a large chemical affinity even if they are not.

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

The chemical modification (5) method is the chemical modification (4) method in which the compound having one or more reactive functional groups other than 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 and 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 above-mentioned layered silicate is a layered silicate having an average interlayer distance of (001) plane of 3 nm or more measured by a wide-angle X-ray diffraction measurement method, and part or all of which 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 cleaved 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, high temperature properties, heat resistance, and dimensional stability. If the average inter-layer distance is less than 3 nm, the effect due to the dispersion of the layered silicate on the nanometer scale cannot be sufficiently obtained, and the mechanical properties,
The improvement of flame retardancy remains in the same range as when the usual inorganic filler is compounded. A more preferable lower limit of the average interlayer distance is 3n
m, the upper limit 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). Ratio (%) 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 effects 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.

More specifically, when the degree of restraint of the thermoplastic resin and / or the thermosetting resin on the surface of the layered silicate is increased, the mechanical properties are improved in a wide temperature range from normal temperature to high temperature. Surprisingly, the glass transition point of the resin,
Mechanical properties can be maintained even in a high temperature region above the melting point. As a result, the coefficient of linear expansion at high temperature can be suppressed to a low level. Although the reason for this is not clear, it is considered that even in the region above the glass transition point or the melting point, the finely dispersed layered silicate acts as one kind of pseudo-crosslinking point to exhibit these physical properties. .

Regarding the gas barrier property, not only the solvent resistance, hygroscopicity and water absorption are improved, but also the barrier property of substances other than gas molecules is exhibited. In a multilayer printed wiring board, migration of copper from a copper circuit may become a problem, but this is also suppressed. Further, in these materials, even a trace amount of additive added to the material may cause defects such as defective plating due to bleeding out on the surface, but bleedout of the additive does not easily occur.

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 due to 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.

In the insulating substrate material of the present invention, the lower limit of the amount of the layered silicate compounded is 100 parts by weight, and the upper limit thereof is 100 parts by weight, based on 100 parts by weight of the mixture with the thermoplastic resin and / or the thermosetting resin. It is a department. If it is less than 0.1 part by weight, the effect of improving flame retardancy and mechanical properties becomes small, and 1
If it exceeds 00 parts by weight, the density (specific gravity) of the insulating substrate material
Becomes higher and the mechanical strength also lowers, resulting in poor practicability. The preferred lower limit is 1 part by weight and the upper limit is 50.
Parts by weight. When it is less than 1 part by weight, sufficient flame retardant effect may not be obtained when the insulating substrate material is thinly molded, and when it exceeds 50 parts by weight, moldability may be deteriorated. A more preferred lower limit is 5 parts by weight and an upper limit is 20 parts by weight. Within this range, 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 a thermoplastic resin and / or a thermosetting resin is not particularly limited, and examples thereof include a method using the organically modified layered silicate; a thermoplastic resin and / or a thermosetting resin. A method of mixing the organic resin and the layered silicate by a conventional method and then foaming the mixture; 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 method of foaming after mixing the thermoplastic resin and / or thermosetting resin and the layered silicate by a conventional method is to foam the thermoplastic resin and / or thermosetting resin using a foaming agent. , A method of converting the foaming energy into the dispersion energy of the layered silicate.

The foaming agent is not particularly limited, and examples thereof include a gaseous foaming agent, a 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 contains a flame retardant containing substantially no halogen 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 flame retardant is not particularly limited, and examples thereof include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminide, gypsum dihydrate and calcium hydroxide; red phosphorus and ammonium polyphosphate. Phosphorus compounds such as; melamine, melamine cyanurate, melamine isocyanurate, melamine phosphate, nitrogen compounds such as melamine derivatives such as those surface-treated, layered double hydrates such as hydrotalcite, etc. Is mentioned. Among them, metal hydroxides and melamine derivatives are preferably used.

Of the above metal hydroxides, magnesium hydroxide and aluminum hydroxide are particularly preferable, and these may be surface-treated with various surface treatment 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.

The lower limit of the content of the flame retardant with respect to 100 parts by weight of the thermoplastic resin and / or the thermosetting resin is 0.1 parts by weight, and the upper limit thereof is 100 parts by weight. If it is less than 0.1 parts by weight, the flame retarding effect due to the inclusion of these cannot be sufficiently obtained, and if it exceeds 100 parts by weight, the density (specific gravity) of the insulating substrate material becomes too high, Practicality is poor, and flexibility and elongation are extremely reduced. The preferred lower limit is 5 parts by weight and the upper limit is 80 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 80 parts by weight,
The defect rate may increase due to swelling during the process at high temperature. A more preferred lower limit is 10 parts by weight and an upper limit is 70 parts by weight. Within this range, there are no regions in which mechanical properties, electrical properties and process suitability are problematic, and sufficient flame retardancy is exhibited, which is preferable.

The insulating substrate material of the present invention contains a flame retardant aid. The flame retardant aid is added together with the flame retardant to improve the flame retardancy of the material. Although the flame retardant aid is not particularly limited, for example, silicone oil; metal oxides such as alumina and copper oxide; silicon compounds such as silicon oxide, fluororesin and silicone-acryl composite rubber; carbon black and the like are preferable.

The above flame retardant aid may be one which has been surface-treated with various surface treatment agents. The surface treatment agent is not particularly limited, and examples thereof include silane coupling agents, titanate coupling agents, PVA.
Examples of the surface treatment agent, epoxy surface treatment agent and the like.
These flame retardant aids may be used alone or in combination of two or more.

The lower limit of the content of the flame retardant aid with respect to 100 parts by weight of the thermoplastic resin and / or the thermosetting resin is 0.1.
Parts by weight, the upper limit is 50 parts by weight. If it is less than 0.1 part by weight, the flame retardant effect is not remarkable, and if it exceeds 50 parts by weight, mechanical properties and moldability are impaired, and high specific gravity is not practical. The preferred lower limit is 0.5 parts by weight and the upper limit is 45.
Parts by weight.

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 coloring agent, as long as the object of the present invention is not hindered. 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 material for an insulating substrate 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 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 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.

In the 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.

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.

Further, 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 in a combustion test by heating it for 30 minutes under a radiant heating condition of 50 kW / m ² . 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 suitably used for forming an insulating substrate, or for forming a varnish for impregnation or 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 for molding the material for an insulating substrate of the present invention is not particularly limited, and 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. Since the quality of the material is improved as described above, the yield of the multilayer printed wiring board manufactured through multiple steps can be significantly improved.

The material for the insulating substrate of the present invention forms a sintered body of the layered silicate during combustion, and retains the shape of the 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.

[0121]

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) 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 distearyldimethyl quaternary as a layered silicate. 10 parts by weight of swellable fluorine mica (Somasif MAE-100 manufactured by Coop Chemical Co., Ltd.) that has been subjected to an organic treatment with an ammonium salt, 45 parts by weight of synthetic silica (Elsil (spherical product) manufactured by Mitsubishi Materials) as a flame retardant aid. Part, and 70 parts by weight of magnesium hydroxide (Kisuma 5J, manufactured by Kyowa Chemical Industry Co., Ltd.) as a flame retardant were melt-kneaded at 100 ° C. and extruded into a strand, and the extruded strand was pelletized by a pelletizer.

This pellet was 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.
By heating for 3 hours and curing, a plate-like molded body made of a material for an insulating substrate and having a thickness of 2 mm and 100 μm was produced.

Example 2 80 parts by weight of a solid epoxy resin (Okaka Shell Epoxy Co., Epicoat 1007) in a small extruder (TEX30 manufactured by Japan Steel Works) and an epoxy-modified butadiene rubber (Nagase) as a rubber component. 10 parts by weight of Dentalex R-45 EPT manufactured by Chemtex Co., Ltd., 10 parts by weight of natural montmorillonite (New S-Ben D manufactured by Toyosyun Yoko Co., Ltd.) that has been organically treated with distearyl dimethyl quaternary ammonium salt as a layered silicate. Part, synthetic silica (made by Mitsubishi Materials Corporation,
40 parts by weight of Elsil (spherical product) and magnesium hydroxide as a flame retardant (manufactured by Kyowa Chemical Industry Co., Ltd., Kisuma 5J)
70 parts by weight were 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.
By heating for 3 hours and curing, a plate-like molded body made of a material for an insulating substrate and having a thickness of 2 mm and 100 μm was produced.

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

(Comparative Example 2) A thickness of 2 mm and 100 μm made of an insulating substrate material was obtained in the same manner as in Example 2 except that natural montmorillonite (Toyojun Yoko Corp., New S-Ben D) was not added. The plate-shaped molded body of was produced.

(Comparative Example 3) A plate-like molded body made of a material for an insulating substrate and having a thickness of 2 mm and 100 µm was prepared in the same manner as in Example 1 except that the amount of magnesium hydroxide added was 0.05 part by weight. did.

(Comparative Example 4) A plate-shaped molded body made of a material for an insulating substrate and having a thickness of 2 mm and 100 µm was prepared in the same manner as in Example 2 except that the amount of magnesium hydroxide added was 120 parts by weight.

<Evaluation> Examples 1 and 2 and Comparative Examples 1 to 1
Performance of plate-shaped molded product obtained in No. 4 (average interlayer distance of layered silicate, ratio of layered silicate dispersed in 5 layers or less, via workability, shape retention during combustion, yield point stress of combustion residue) (Coating strength)) was evaluated by the following method. The results are shown in Table 1.

(1) Average interlaminar distance of layered silicate Obtained by diffraction of laminated 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 was measured, and the (0
01) Interplanar spacing (d) was calculated, and the obtained d was defined as the average interlayer distance (nm). λ = 2 dsin θ (4) In the formula, λ is 0.154, 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 combustion ASTM E 1354 "Testing method for combustibility 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 Yield Point Stress of Combustion Residue (Film Strength) ASTM E 1354 "Test Method for Combustibility 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. The combustion residue was compressed at a speed of 0.1 cm / s using a strength measuring device, and the yield point stress (coating strength) (kPa) of the combustion residue was measured.

[0136]

[Table 1]

From Table 1, it can be seen that in the plate-shaped moldings made of the materials for insulating substrates obtained in Examples 1 and 2, the average interlayer distance of the layered silicate was 3 nm or more and the number of layers was 5 or less. Since the ratio of the dispersed layered silicate 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 yield point stress (coating strength) of the combustion residue was 4.9 kPa or more because a sintered body that could be a flame-retardant coating was easily formed.

On the other hand, in the plate-shaped molded body 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), calcium carbonate was dispersed in layers. However, since the shape retention during combustion is 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 yield residue stress (coating strength) of the combustion residue is extremely low. It was

Comparative Example 2 in which no layered silicate was added
The plate-shaped compact made of the insulating substrate material obtained in step 1 has poor shape retention during combustion, and it is difficult to form a sintered body that can form a flame-retardant coating. The point stress (coating strength) was extremely low.

Further, the plate-shaped molded body made of the insulating substrate material obtained in Comparative Example 3 containing a small amount of the flame retardant had a high maximum heat generation rate. The plate-shaped molded body made of the insulating substrate material obtained in Comparative Example 4 containing a large amount of the flame retardant had a problem of poor via processability.

[0141]

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 laminated board, a resin-coated copper foil, a copper-clad laminated board, a polyimide film, a TAB film and a prepreg.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 1/03 610 H05K 1/03 610S (72) Inventor Kazunori Ako 2-Momoyama, Shimamoto-cho, Mishima-gun, Osaka 2- 1 Sekisui Chemical Co., Ltd. (72) Inventor Kazutaka Shiranase 2-2, Kamitowaue Tonkocho-cho, Minami-ku, Kyoto-shi, Kyoto Prefecture F-Term (reference) 4F072 AA07 AA08 AD02 AD03 AD07 AD11 AD13 AD20 AD23 AD38 AD42 AD45 AD46 AD47 AE07 AF04 AF06 AF28 AG03 AL12 AL13 AL14 4F100 AA03A AA17A AA17H AA20H AB17B AB33B AC05A AH03A AH03H AK01A AK02A AK13A AK17H AK25A AK25H AK25J AK33A AK36A AK44A AK49A AK50A AK52A AK52H AK52J AK53A AK54A AK55A AK56A AL01A AL05A AL06A AN02A AN02H BA02 CA08A GB43 JB13A JB16A JJ03 JJ07 JK01 JL04 YY00A YY00H 4J002 AA011 AA021 BD122 BG022 CD001 CD181 CP032 DA036 DA05 6 DE076 DE086 DE096 DE146 DE186 DE286 DG056 DH026 DJ006 DJ016 DJ056 EU186 EU196 FD132 FD136 GF00 GQ01

Claims (16)

[Claims] 1. A material used for an insulating substrate, which is 100 parts by weight of a mixture of at least one thermoplastic resin and / or thermosetting resin, 0.1 to 100 parts by weight of layered silicate, and substantially halogen. Flame retardant containing no system composition
1 to 100 parts by weight, and 0.1 to 50 parts by weight of a flame retardant aid, a material for an insulating substrate. 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 polyamide imide resin, and a polyester imide resin. Item 2. An insulating substrate material according to item 1. 3. The thermosetting resin is epoxy resin, phenol resin, urea resin, unsaturated polyester resin, allyl resin, thermosetting polyimide resin, bismaleimide triazine resin, thermosetting modified polyphenylene ether resin, silicon resin. 2. The insulating substrate material according to claim 1, which is at least one selected from the group consisting of and a benzoxazine-based resin. 4. The flame retardant is a metal hydroxide and / or a melamine derivative, wherein the flame retardant is a metal hydroxide and / or a melamine derivative.
The insulating substrate material described. 5. The flame retardant aid is at least one selected from the group consisting of silicone oil, metal oxides, silicon oxide, fluororesins, and silicone-acrylic composite rubbers. The material for an insulating substrate according to 3 or 4. 6. 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 3, 4, or 5. 7. The insulating substrate material according to claim 1, wherein the layered silicate contains an alkylammonium ion having 6 or more carbon atoms. 8. 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. Claim 1, 2, 3, 4, 5, 6, or 7 characterized.
The insulating substrate material described. 9. In a combustion test according to ASTM E 1354, 30 under a radiant heating condition of 50 kW / m ^2.
The rate of combustion residue of the combustion residue burned by heating for 0.
Yield point stress when compressed at 1 cm / s is 4.9 kPa or more, Claims 1, 2, 3, 4, 5,
The material for an insulating substrate according to 6, 7, or 8. 10. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A laminated board comprising the insulating substrate material described in 8 or 9. 11. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A printed circuit board comprising the insulating substrate material described in 8 or 9. 12. 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 or 9. 13. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A copper clad laminate, which is made of the material for an insulating substrate according to 8 or 9. 14. Claims 1, 2, 3, 4, 5, 6, 7,
A polyimide film comprising the insulating substrate material described in 8 or 9. 15. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A film for TAB comprising the material for an insulating substrate according to 8 or 9. 16. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A prepreg made of the material for an insulating substrate according to 8 or 9.