JP2003292802A - Resin varnish composition, resin sheet and resin coating layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin varnish composition suitable for production of a thin resin sheet having excellent mechanical properties, dimensional stability and heat resistance and further excellent fire retardancy due to its form retention effect upon burning without using a halogen type fire retardant which corrodes instruments and gives bad influence upon human bodies, the composition being capable of obtaining high reliability because of the above characteristics. <P>SOLUTION: The resin varnish composition comprises 100 pts.wt. of a resin comprising at least one thermosetting resin and/or thermoplastic resin, 0.1-100 pts.wt. of a layered silicate and 30-1,000 pts.wt. of an organic solvent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin varnish suitable for producing a resin sheet having excellent mechanical properties, dimensional stability, heat resistance and the like, and particularly having excellent flame retardancy due to a shape retaining effect during combustion. It relates to a composition.

[0002]

2. Description of the Related Art Generally, in the production of resin sheets and prepregs, a solution casting method is mainly used in the case of a thermosetting resin, and a calendar method, a T-die method and an inflation method are used in the case of a thermoplastic resin. In addition to the widely used melt molding represented by the method, the solution casting method is also used. Further, the solution coating method is widely used in the production of the resin coating layer.

The resin sheet and prepreg produced from the solution include, for example, a transparent resin sheet made of an alicyclic hydrocarbon resin and an acrylic resin; a photocurable resin sheet;
Examples thereof include a thermosetting resin sheet made of a phenol resin, an epoxy resin and an unsaturated polyester resin; a thermosetting resin prepreg; a thermosetting resin prepreg obtained by impregnating glass cloth with a thermosetting resin. Examples of the resin coating layer prepared from the solution include a hard coat formed on the resin sheet. These are used, for example, as an insulating substrate in a multilayer printed circuit board for electronic equipment, which is composed of a plurality of insulating substrates.

In recent years, downsizing and low cost have been especially required for resin sheets, and in the field of multi-layer printed circuit boards, performance such as strength, heat resistance and flame retardancy has been improved as the board becomes higher in density and thinner. There is a demand for a thin resin sheet that has been improved to ensure high reliability.

On the other hand, it has been widely practiced to add an inorganic filler to improve the physical properties. Examples of the insulating substrate include those made of a thermoplastic resin containing a large amount of an inorganic filler, those made of a thermosetting resin modified with rubber (elastomer) or acrylic resin, and the like.
Patent Document 1 discloses a multilayer insulation in which a varnish containing a high molecular weight epoxy polymer and a polyfunctional epoxy resin as a main component is mixed with an inorganic filler having a predetermined particle diameter and applied to a support to form an insulating layer. A method of manufacturing a substrate is disclosed.

However, in the multilayer insulating substrate manufactured by the above manufacturing method, the area of the interface between the inorganic filler and the high molecular weight epoxy polymer or polyfunctional epoxy resin, which is necessary for improving mechanical properties such as mechanical strength, is increased. In order to obtain a sufficient amount, it is necessary to mix a large amount of inorganic filler, and it is difficult to reduce the thickness, and there are problems such as an increase in the number of processes.

On the other hand, in recent years, there has been a demand for conversion of polymer materials used for industrial applications to environment-friendly materials which are environmentally friendly due to problems such as waste treatment and environmental hormones. Specifically, for example, conversion from a halogen-containing flame retardant to a non-halogen flame retardant is being considered, and it is strongly desired to establish a so-called non-halogen flame retardant treatment technology that does not use a halogen-containing flame retardant. . The halogen-containing flame retardant has a high flame-retardant effect, and has the advantage that the deterioration of the moldability and the mechanical properties of the molded product are relatively small.
A large amount of halogen-based gas such as dioxins may be generated during molding or combustion, and the generated halogen-based gas may corrode equipment or adversely affect the human body.

Therefore, in recent years, even in the case of materials for insulating substrates such as resin sheets, in order to switch to environment-friendly materials,
Materials using non-halogen flame retardants have been developed. However, in order to develop the required flame retardancy, it is necessary to add a large amount of non-halogen flame retardant,
There is a problem that it is inferior to the conventional insulating substrate material using the halogen-containing flame retardant in heat resistance and dimensional stability.

As described above, there is a need for a material for an insulating substrate which has necessary mechanical properties, heat resistance, dimensional stability and the like during the manufacturing process and has been made thinner and converted to a halogen-free flame retardant. Has been done.

[0010]

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

[0011]

SUMMARY OF THE INVENTION In view of the above situation, the present invention is a resin sheet having excellent mechanical properties, dimensional stability, heat resistance and the like, and particularly excellent flame retardancy due to the shape retaining effect during combustion. It is an object of the present invention to provide a resin varnish composition suitable for the production of

[0012]

SUMMARY OF THE INVENTION The present invention comprises at least one
0.1 to 100 parts by weight of a layered silicate and 30 to 1000 parts by weight of an organic solvent are contained with respect to 100 parts by weight of a resin composed of one kind of thermosetting resin and / or thermoplastic resin. It is a resin varnish composition. The present invention is described in detail below.

The resin varnish composition of the present invention contains at least one kind of thermosetting resin and / or thermoplastic resin. The thermosetting resin is a liquid having a relatively low molecular weight that is liquid at room temperature, semi-solid or solid, and exhibits fluidity at room temperature or under heating, and is a curing agent,
It means an insoluble and infusible resin formed by a chemical reaction such as a curing reaction or a cross-linking reaction by the action of a catalyst or heat to increase the molecular weight and form a three-dimensional network structure.

The thermosetting resin is not particularly limited, and examples thereof include epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, urea resin, allyl resin, silicon resin, benzoxazine resin. Resin, phenolic resin, unsaturated polyester resin, bismaleimide triazine resin, alkyd resin,
Furan resin, melamine resin, polyurethane resin,
An aniline resin etc. are mentioned. Among them, epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, urea resin, allyl resin, silicon resin, benzoxazine resin, phenol resin, unsaturated polyester resin, bismaleimide triazine Resin or the like is preferable. 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 1
The number 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 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 resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, bisphenol S type epoxy resins and other bisphenol type epoxy resins; phenol novolac type epoxy resins, Examples thereof include novolac type epoxy resins such as cresol novolac type epoxy resins; aromatic epoxy resins such as trisphenolmethane triglycidyl ether and hydrogenated products and bromides thereof.

Examples of the epoxy resin (2) include 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-epoxy)
Cyclohexanone-meta-dioxane, bis (2,3-
Examples thereof include alicyclic epoxy resins such as epoxycyclopentyl) ether. Examples of commercially available epoxy resins (2) include, for example, trade name "EHP
E-3150 "(softening temperature 71 ° C., manufactured by Daicel Chemical Industries, Ltd.) and the like.

Examples of the epoxy resin (3) include diglycidyl ether of 1,4-butanediol,
Diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, carbon number of 2 to 9 (preferably 2 to 9). An aliphatic epoxy resin such as polyglycidyl ether of a long-chain polyol containing polyoxyalkylene glycol containing an alkylene group or polytetramethylene ether glycol of 4) can be used.

Examples of the epoxy resin (4) include phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, salicylic acid glycidyl ether-glycidyl ester. , 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 glycidylamine type epoxy resins such as N, N, O-triglycidyl derivatives and hydrogenated products thereof.

Examples of the epoxy resin (6) include copolymers of glycidyl (meth) acrylate and radically polymerizable monomers such as ethylene, vinyl acetate and (meth) acrylic acid ester. In addition, in this specification, (meth) acryl means acryl or methacryl.

The above-mentioned epoxy resin (7) is, for example, one obtained by epoxidizing a double bond of unsaturated carbon in a polymer mainly containing a conjugated diene compound such as epoxidized polybutadiene or a polymer of a partially hydrogenated product thereof. Etc.

Examples of the epoxy resin (8) include a polymer block mainly composed of a vinyl aromatic compound such as epoxidized SBS and the like, and a polymer block mainly composed of a conjugated diene compound or its partial hydrogenation. Examples include block copolymers having the polymer block of the product in the same molecule, in which the double bond of the unsaturated carbon of the conjugated diene compound is epoxidized.

Examples of the epoxy resin (9) include polyester resins having one or more, preferably two or more epoxy groups per molecule.

Examples of the epoxy resin (10) 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 epoxy resins (1) to (9). Can be mentioned.

As the epoxy resin (11), for example, NBR, CT may be added to the epoxy resins (1) to (10).
Examples thereof include rubber-modified epoxy resin containing a rubber component such as BN, polybutadiene, and acrylic rubber.

The curing agent used in the curing reaction of the epoxy resin is not particularly limited, and conventionally known curing agents for epoxy resin can be used. For example, amine compounds,
Compounds such as polyaminoamide compound synthesized from amine compound, tertiary amine compound, imidazole compound, hydrazide compound, melamine compound, acid anhydride, phenol compound, thermal latent cationic polymerization catalyst, photolatent cationic polymerization initiator, dicyanamide And derivatives thereof. These curing agents may be used alone,
Two or more kinds may be used in combination.

The above amine compound is not particularly limited, and examples thereof include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine and derivatives thereof;
Mensendiamine, isophoronediamine, 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-xylenediamine, α- (m / p aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, α, α-bis (4- Aminophenyl) -p-
Examples thereof include aromatic amines such as diisopropylbenzene and derivatives thereof.

The compound synthesized from the above amine compound is not particularly limited, and, for example, the above amine compound and
Polyaminoamide compounds and their derivatives synthesized from carboxylic acid compounds such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadioic acid, isophthalic acid, terephthalic acid, dihydroisophthalic acid, tetrahydroisophthalic acid and hexahydroisophthalic acid A polyaminoimide compound and its derivative synthesized from the above amine compound and a maleimide compound such as diaminodiphenylmethane bismaleimide; a ketimine compound and its derivative synthesized from the above amine compound and a ketone compound; the above amine compound and an epoxy compound , Polyamino compounds synthesized from compounds such as urea, thiourea, aldehyde compounds, phenol compounds and acrylic compounds, and their derivatives.

The tertiary amine compound is not particularly limited, and examples thereof include N, N-dimethylpiperazine, pyridine, picoline, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethyl). Aminomethyl) phenol, 1,8-diazabiscyclo (5,4,0) undecene-1 and derivatives thereof and the like can be mentioned.

The imidazole compound is not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole and derivatives thereof. Can be mentioned.

The hydrazide compound is not particularly limited and includes, for example, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadiene-1,18-dicarbohydrazide and eicosane di. Examples thereof include acid dihydrazide, adipic acid dihydrazide and derivatives thereof.

The melamine compound is not particularly limited, and for example, 2,4-diamino-6-vinyl-1,3,
5-triazine and its derivative etc. are mentioned.

The acid anhydride is not particularly limited, and examples thereof include phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydrotrimellitate, and glycerol. Trisanhydro trimellitate, methyl tetrahydro phthalic anhydride, tetrahydro phthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyl tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, 5-
(2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride,
Examples thereof include trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, polyazelaic anhydride, polydodecanedioic anhydride, chlorendic anhydride and derivatives thereof.

The above-mentioned phenol compound is not particularly limited, and examples thereof include phenol novolac, o-cresol novolac, p-cresol novolac, t-butylphenol novolac, dicyclopentadiene cresol and derivatives thereof.

The above-mentioned thermal latent cationic polymerization catalyst is not particularly limited, and examples thereof include benzylsulfonium salt, benzylammonium salt and benzylpyridinium with counter anions such as antimony hexafluoride, phosphorus hexafluoride, and boron tetrafluoride. Salts, ionic thermal latent cationic polymerization catalysts such as benzylphosphonium salts; N-benzylphthalimide,
Nonionic thermal latent cationic polymerization catalysts such as aromatic sulfonic acid esters are mentioned.

The photolatent cationic polymerization initiator is not particularly limited, and examples thereof include an aromatic diazonium salt and an aromatic halonium salt in which antimony hexafluoride, phosphorus hexafluoride, boron tetrafluoride and the like are used as counter anions. And onium salts such as aromatic sulfonium salts, and iron-allene complexes,
Ionic photolatent cationic polymerization initiators such as organometallic complexes such as titanocene complex and arylsilanol-aluminum complex; nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester,
Examples thereof include nonionic photolatent cationic polymerization initiators such as diazonaphthoquinone and N-hydroxyimide sulfonate.

The thermosetting modified polyphenylene ether-based resin is not particularly limited, and examples thereof include resins obtained by modifying the polyphenylene ether-based resin with a thermosetting functional group such as a glycidyl group, an isocyanate group, and an amino group. Can be mentioned. These thermosetting modified polyphenylene ether resins may be used alone or in combination of two or more.

As the thermosetting polyimide resin,
It is not particularly limited as long as it is a resin having an imide bond in the molecular main chain, and specifically, for example, a condensation polymer of an aromatic diamine and an aromatic tetracarboxylic acid, an addition weight of an aromatic diamine and a bismaleimide. Examples thereof include a bismaleimide resin which is a combination, a polyamino bismaleimide resin which is an addition polymer of aminobenzoic acid hydrazide and bismaleimide, and a bismaleimide triazine resin which is composed of a dicyanate compound and a bismaleimide resin. Among them, bismaleimide triazine resin is preferably used. These thermosetting polyimide-based resins may be used alone or in combination of two or more.

The urea resin is not particularly limited as long as it is a thermosetting resin obtained by an 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 and the like.

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. The catalyst for the curing reaction is not particularly limited, but for example, the combined use of t-butyl perbenzoate and di-t-butyl peroxide is suitable.

The above-mentioned silicon resin is not particularly limited as long as it has a silicon-silicon bond, a silicon-carbon bond, a siloxane bond or a silicon-nitrogen bond in its molecular chain, and specifically, for example, polysiloxane. , Polycarbosilane, polysilazane and the like.

The benzoxazine resin is not particularly limited as long as it is obtained by ring-opening polymerization of the oxazine ring of the benzoxazine monomer. The benzoxazine monomer is not particularly limited, and for example,
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 thermoplastic resin is not particularly limited, and examples thereof include polyphenylene ether resins, functional group-modified polyphenylene ether resins; polyphenylene ether resins or functional group-modified polyphenylene ether resins, and polystyrene resins. A mixture of a thermoplastic resin compatible with a polyphenylene ether resin or a functional group-modified polyphenylene ether resin such as; alicyclic hydrocarbon resin, thermoplastic polyimide resin, polyether ether ketone (PEEK) resin resin,
Polyether sulfone resin, polyamide imide resin, polyester imide resin, polyester resin,
Polyolefin resin, polystyrene resin, polyamide resin, polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl acetate 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, polyphenylene ether resin or a mixture of functional group-modified polyphenylene ether resin and polystyrene resin, alicyclic hydrocarbon resin, thermoplastic Polyimide-based resin, polyether ether ketone-based resin, polyether sulfone resin, polyamide-imide-based resin and polyester-imide-based resin are preferably used. These thermoplastic resins may be used alone or in combination of two or more kinds.

The above polyphenylene ether resin is
A polyphenylene ether homopolymer or a polyphenylene ether copolymer having a repeating unit represented by the following formula (1).

[0047]

[Chemical 1]

In the above formula (1), R1, R2, R3 and R
4 represents 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 for example, a copolymer partially containing alkyl trisubstituted phenol such as 2,3,6-trimethylphenol in the repeating unit of the polyphenylene ether homopolymer. Examples thereof include polymers and copolymers obtained by graft-copolymerizing one or more styrene-based monomers such as styrene, α-methylstyrene and vinyltoluene with these polyphenylene ether copolymers. These polyphenylene ether resins may be used alone or in combination of two or more having different compositions, components, molecular weights and the like.

The functional group-modified polyphenylene ether resin is not particularly limited. For example, the polyphenylene ether resin may be one or two of functional groups such as maleic anhydride group, glycidyl group, amino group and allyl group. Examples thereof include those modified with at least one species. 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 a thermoplastic resin, it is possible to further improve the mechanical properties, heat resistance, dimensional stability and the like of the resin varnish composition of the present invention by a crosslinking reaction.

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 styrene-based monomers such as α-methylstyrene, ethylstyrene, t-butylstyrene, and vinyltoluene; polystyrene-based resins such as styrene-based elastomers And a mixture thereof. The polystyrene resins may be used alone or in combination of two or more. Also,
The polyphenylene ether-based resin or the mixture of the functional group-modified polyphenylene ether-based resin and the polystyrene-based resin may be used alone or in combination of two or more kinds.

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. For example, a cyclic olefin, that is, a norbornene-based monomer may be used alone. Examples thereof include coalesce and copolymers. These alicyclic hydrocarbon resins may be used alone or in combination of two or more.

The cyclic olefin is not particularly limited, and examples thereof include norbornene, methanooctahydronaphthalene, dimethanooctahydronaphthalene, dimethanodecahydroanthracene, dimethanodecahydroanthracene, trimethanodecahydroanthracene, dicyclopentadiene, 2,3-dihydrocyclopentadiene, methanooctahydrobenzoindene, dimethanooctahydrobenzoindene, methanodecahydrobenzoindene,
Examples thereof include dimethanodecahydrobenzoindene, methanooctahydrofluorene, dimethanooctahydrofluorene, and substitution products thereof. These cyclic olefins may be used alone or in combination of two or more.

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.

Examples of commercially available alicyclic hydrocarbon resins 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.

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

The resin material obtained by distilling off the organic solvent is
Then, it may be used after being cured by a means such as a curing agent, a catalyst, heat or light. Upon curing, the resin has a higher molecular weight and a crosslinking reaction occurs.

The resin varnish composition of the present invention contains a layered silicate. In addition, in the present specification, the layered silicate means a layered silicate mineral having an exchangeable metal cation between layers, and may be a natural product or a synthetic product. The layered silicate is not particularly limited and examples thereof include smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite and nontronite, swelling mica, vermiculite, halloysite and the like. Among them, at least one selected from the group consisting of montmorillonite, hectorite, and swelling mica is preferably used. These layered silicates may be used alone or in combination of two or more kinds.

The crystal shape of the layered silicate is not particularly limited, but the preferable lower limit of the average length is 0.01 μm.
m, the upper limit is 3 μm, and the preferable lower limit of the thickness is 0.001 μm.
m, the upper limit is 1 μm, and the preferable lower limit of the aspect ratio is 2
0, the upper limit is 500, the more preferable lower limit of the average length is 0.05 μm, the upper limit is 2 μm, the more preferable lower limit of the thickness is 0.01 μm, the upper limit is 0.5 μm, and the more preferable lower limit of the aspect ratio is 50, The upper limit is 200.

The layered silicate preferably has a large shape anisotropy effect defined by the following formula (2). By using the layered silicate having a large shape anisotropy effect, the resin obtained from the resin varnish composition of the present invention has excellent mechanical properties.

[0064]

[Equation 1]

The exchangeable metal cation existing between the layers of the layered silicate means a metal ion such as sodium or calcium existing on the surface of the flaky crystal 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 /
100 g, the upper limit is 200 milliequivalents / 100 g. 5
When it is less than 0 milliequivalent / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate due to cation exchange becomes small, so that the crystal layers are not sufficiently depolarized (hydrophobicized). Sometimes. If it exceeds 200 milliequivalents / 100 g, the bonding force between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may become difficult to peel off.

The above layered silicate is preferably one which has been improved in dispersibility in a resin comprising a thermosetting resin and / or a thermoplastic resin by being chemically treated. Hereinafter, such a layered silicate is also referred to as an organized layered silicate. The chemical treatment can be carried out, for example, by the following chemical modification (1) method to chemical modification (6) method. These chemical modification methods may be used alone or in combination of two or more.

The chemical modification (1) method is also referred to as a cation exchange method using a cationic surfactant, and specifically,
This is a method in which when a low-polarity resin such as a polyphenylene ether resin is used to obtain the resin varnish composition of the present invention, the layers of the layered silicate are cation-exchanged with a cationic surfactant to make them hydrophobic. By preliminarily making the layers of the layered silicate hydrophobic, the affinity between the layered silicate and the low-polarity resin is enhanced, and the layered silicate can be finely dispersed in the low-polarity resin more uniformly.

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 containing an alkylammonium ion having 6 or more carbon atoms and having an alkyl chain having 6 or more carbon atoms is preferably used because it can sufficiently hydrophobize the crystal layers of the layered silicate.

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 and polyethylene glycol chains
A dialkyl quaternary ammonium salt having one, a dialkyl quaternary ammonium salt having two polypropylene glycol chains, a trialkyl quaternary ammonium salt having one polyethylene glycol chain, a trialkyl quaternary ammonium salt having one polypropylene glycol chain, and the like. Can be mentioned. Among them, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured 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.

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 above-mentioned chemical modification (2) means that the hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) is combined with a functional group or a hydroxyl group capable of chemically bonding with the hydroxyl group. This is a method of chemically treating with a compound having at least one functional group having a high chemical affinity at the molecular end.

The functional group capable of chemically bonding to the hydroxyl group or the functional group having a large chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include an alkoxy group, a glycidyl group, a carboxyl group (including a dibasic acid anhydride). ), A hydroxyl group, an isocyanate group, an aldehyde group and the like. The compound having a functional group capable of chemically bonding with the hydroxyl group or the compound having a functional group having a large chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include a silane compound, a titanate compound, and a glycidyl compound having the functional group. , Carboxylic acids, alcohols and the like. These compounds may be used alone or in combination of two or more.

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 in combination of two or more.

The above-mentioned chemical modification (3) means that the hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) is chemically combined with a functional group capable of chemically bonding with the hydroxyl group. It is a method of chemically treating a functional group having a high affinity with a compound having one or more reactive functional groups at a molecular end.

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

The compound having anionic surface activity is not particularly limited as long as it can chemically treat the layered silicate by ionic interaction, and examples thereof include sodium laurate, sodium stearate, sodium oleate, and higher alcohols. Examples thereof include sulfate ester salts, secondary higher alcohol sulfate ester salts, unsaturated alcohol sulfate ester salts and the like. These compounds may be used alone or in combination of two or more.

The chemical modification (5) method is a method of chemically treating the above-mentioned compounds having anionic surface activity with one or more reactive functional groups other than the anion site in the molecular chain.

The above-mentioned chemical modification (6) means the organically modified layered silicate chemically treated by any one of the chemical modification (1) to the chemical modification (5), and further, for example, maleic anhydride. In this method, a resin having a functional group capable of reacting with a layered silicate such as a modified polyphenylene ether resin is used as a resin composed of a thermosetting resin and / or a thermoplastic resin.

The resin varnish composition of the present invention contains 0.1 to 100 parts by weight of a layered silicate with respect to 100 parts by weight of a resin composed of a thermosetting resin and / or a thermoplastic resin. If it is less than 0.1 part by weight, the effect of improving flame retardancy and mechanical properties will be small, and if it exceeds 100 parts by weight, the solution viscosity of the resin varnish composition of the present invention will be too high, resulting in coating. Not only becomes difficult, but the density of the resin obtained by drying becomes high and the mechanical strength also decreases, so that it becomes impractical. The preferable lower limit of the compounding amount is 1 part by weight,
The upper limit is 50 parts by weight. When the amount is less than 1 part by weight, sufficient flame retardancy may not be obtained when a resin material such as a thin resin sheet or resin coating layer is obtained from the resin varnish composition of the present invention. If it exceeds 50 parts by weight, the moldability may decrease. The more preferable lower limit of the compounding amount is 5 parts by weight and the upper limit thereof is 20 parts by weight. When the amount is 5 to 20 parts by weight, there is no problematic area in mechanical properties and process suitability, and sufficient flame retardancy can be obtained.

The method for dispersing the layered silicate in the resin is not particularly limited. For example, a method using an organically modified layered silicate, a method in which the resin and the layered silicate are mixed by a conventional method, and then the resin is foamed with a foaming agent. Examples of the method include a method of using, a method of using a dispersant, and the like. By using these dispersion methods, the layered silicate can be more uniformly and finely dispersed in the resin.

A method in which the resin and the layered silicate are mixed by a conventional method and then the resin is foamed with a foaming agent uses the energy of foaming to disperse 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.

The method of foaming the resin with a foaming agent after the resin and the layered silicate are mixed by a conventional method is not particularly limited. For example, a resin composition comprising a resin and a layered silicate may be mixed with a gaseous foaming agent. After impregnating under high pressure, the gaseous foaming agent is vaporized in the resin composition to form a foam; a thermal decomposition type foaming agent is preliminarily contained between layers of the layered silicate, and its thermal decomposition is carried out. Examples include a method of decomposing a mold foaming agent by heating to form a foam.

The resin varnish composition of the present invention contains an organic solvent. The organic solvent is not particularly limited, and for example, hexane, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran,
1,4-dioxane, ethyl acetate, N, N-dimethylformamide, hexamethylphosphoramide, acetic acid, acetone, methyl ethyl ketone, methanol, ethanol,
Examples thereof include nitromethane, dimethyl sulfoxide, sulfolane, benzene, toluene, xylene, naphthalene, chlorobenzene, anisole, diphenyl ether, pyridine and nitrobenzene. Among them, a polar organic solvent is preferable for dispersing the layered silicate, and an aprotic polar organic solvent is more preferable. The aprotic polar organic solvent means a polar organic solvent having no hydrogen suitable for forming a strong hydrogen bond, specifically, acetone,
Methyl ethyl ketone, acetonitrile, dimethyl sulfoxide, n, n-dimethylformamide, hexamethylphosphoramide and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.

Although the optimum amount of the above organic solvent varies depending on the amount of the above resin or layered silicate and the type of organic solvent, it is generally preferable that both the resin concentration and the layered silicate concentration are low, and at least one kind is used. 30 to 1000 parts by weight is mixed with 100 parts by weight of the resin composed of the thermosetting resin and / or the thermoplastic resin and 0.1 to 100 parts by weight of the layered silicate. If the amount is less than 30 parts by weight, the viscosity of the solution comprising the resin varnish composition of the present invention is too high, which makes casting difficult. If it exceeds 1000 parts by weight, coating defects may occur during solution casting, or it may be difficult to form a thick film. The preferable lower limit of the amount of the organic solvent blended is 100 parts by weight, and the more preferable lower limit thereof is 150 parts by weight or more, and it is preferable to blend more than the layered silicate.

The resin varnish composition of the present invention preferably further contains a flame retardant containing no halogen-based composition. Note 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; metal oxides; red phosphorus. And phosphorus compounds such as ammonium polyphosphate; melamine,
Nitrogen-based compounds such as melamine cyanurate, melamine isocyanurate, melamine phosphate and surface-treated melamine derivatives, layered double hydrates such as fluororesins, silicone oils and hydrotalcites; silicone-acrylic composite rubbers, etc. Is mentioned. Of these, metal hydroxides and melamine derivatives are preferable. Among 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 preferred content of the flame retardant is 0.1 part by weight, and the upper limit is 100 parts by weight, based on 100 parts by weight of the resin comprising at least one thermosetting resin and / or thermoplastic resin. . If the amount is less than 0.1 part by weight, the flame retarding effect due to the inclusion of these may not be sufficiently obtained. When it exceeds 100 parts by weight, the viscosity of the solution comprising the resin varnish composition of the present invention becomes too high, which makes coating difficult, or the density (specific gravity) of the material obtained by drying the varnish becomes too high. , It becomes less practical,
Flexibility and elongation may be extremely reduced. A more preferred lower limit is 5 parts by weight and an upper limit is 80 parts by weight. If it is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained when the resin material obtained by drying the resin varnish composition of the present invention is made thin. If it exceeds 80 parts by weight, mechanical properties may be deteriorated or defects such as swelling may increase in the step of performing high temperature treatment when applied to an insulating substrate. A more preferred lower limit is 10 parts by weight and an upper limit is 70 parts by weight. Mechanical properties in the range of 10 to 70 parts by weight,
There is no problematic area in electrical properties, process suitability, etc., and sufficient flame retardancy is exhibited.

The resin varnish composition of the present invention contains, if necessary, thermoplastic elastomers, crosslinked rubbers, oligomers, moldings, etc., for the purpose of modifying the properties within a range not hindering the achievement of the present invention. Nucleating agent, antioxidant (aging inhibitor), heat stabilizer, light stabilizer, ultraviolet absorber, lubricant, flame retardant aid, antistatic agent, antifogging agent, filler, softening agent, plasticizer,
Additives such as colorants may be added. These may be used alone or in combination of two or more.

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 functional group-modified in order to enhance compatibility with the resin. 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, urethane rubber and the like. To be In order to improve the compatibility with the resin, it is preferable that these crosslinked rubbers are functional group-modified. The crosslinked rubber modified with the functional group is not particularly limited, and examples thereof include epoxy modified butadiene rubber and epoxy modified nitrile rubber.
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 oligomer and the like. These oligomers may be used alone or in combination of two or more kinds.

As a method for producing the resin varnish composition of the present invention, a method in which a layered silicate and an organic solvent are mixed in advance and the resulting mixture is mixed with a resin or a resin solution is generally used. For the mixing, it is preferable to use a meteor stirrer, a homogenizer, a mechanochemical stirrer and the like.

The resin varnish composition of the present invention can be processed into a resin material in any solid form by distilling off the organic solvent. The resin material is not particularly limited, and examples thereof include a resin sheet and a resin coating layer. A resin sheet, a prepreg, and a coating material obtained by using the resin varnish composition of the present invention are also included in the present invention. In addition, in the present specification, the sheet means a planar material, and also includes a film.

When the organic solvent is distilled off from the resin varnish composition of the present invention, the layered silicate has an average interlayer distance of 3 nm or more on the (001) plane measured by the wide-angle X-ray diffraction measurement method, and It is possible to obtain a resin material in which a part or all of the laminate is dispersed in 5 layers or less. The layered silicate has an average inter-layer distance of 3 nm or more, and part or all of the layered silicate is dispersed as a laminate of 5 layers or less to be a thermosetting resin and / or a thermoplastic resin. The interface area between the resin and the layered silicate is sufficiently large, and the distance between the flaky crystals of the layered silicate becomes appropriate, and a sufficient effect due to the dispersion of the layered silicate can be obtained. Greater improvement in mechanical properties and flame retardancy than in the case of using a normal inorganic filler is obtained.

The preferable upper limit of the average interlayer distance is 5 nm.
Is. If it exceeds 5 nm, the crystal flakes of the layered silicate are separated into layers and the interaction is weakened so that the interaction is negligible, so that the film formation at the time of combustion is delayed and the flame retardance may not be sufficiently improved. . In the present specification, the average interlayer distance of the layered silicate means the average of the distances between the layers when the flaky crystal of the layered silicate is regarded as a layer, and the X-ray diffraction peak and transmission electron micrograph That is, it can be calculated by the wide-angle X-ray diffraction measurement method.

Dispersing part or all of the layered silicate as a laminated body of 5 layers or less means, specifically, that the interaction between the flaked crystals of the layered silicate is weakened and the laminated body of the flaked crystals is weakened. Means that a part or all of is dispersed. Preferably, 10% or more of the layered silicate is dispersed as a laminated body having 5 layers or less, and more preferably 20% or more of the layered silicate is dispersed as a laminated body having 5 layers or less. The proportion of the layered silicate dispersed as a laminated body of 5 layers or less was obtained by observing the resin varnish composition of the present invention at a magnification of 50,000 to 100,000 times with a transmission electron microscope and observing it in a certain area. Total number of observable layered silicate laminates X and 5
It can be calculated from the following formula (3) by measuring the number of layers Y of the laminated body dispersed as a laminated body of layers or less.

[0098]

[Equation 2]

The number of layers in the layered silicate laminate is preferably 5 layers or less, more preferably 3 layers or less, and further preferably in order to obtain the effect of dispersing the layered silicate. It is one layer.

The above resin material has a sufficiently large interfacial area between the resin and the layered silicate, so that the interaction between the resin and the surface of the layered silicate becomes large, so that the melt viscosity is increased and the moldability is improved. In addition, the mechanical properties such as elastic modulus are improved in a wide temperature range from normal temperature to high temperature, and the mechanical properties can be maintained even at high temperatures above the glass transition point or melting point of the resin, and the linear expansion coefficient at high temperature. Can be kept low. 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 a kind of pseudo-crosslinking point, so that these physical properties are exhibited. On the other hand, when the distance between the flaky crystals of the layered silicate becomes appropriate, the above resin material easily forms a sintered body that can move the flaky crystals of the layered silicate to form a flame-retardant film during combustion. Become. Since this sintered body is formed at an early stage of combustion, not only the supply of oxygen from the outside can be blocked, but also the combustible gas generated by the combustion can be blocked, and the resin material is excellent. Expresses flame retardancy.

Further, in the above resin material, gas molecules are much more likely to diffuse in the resin than inorganic substances, and when diffusing in the resin, the gas molecules diffuse while bypassing the inorganic substances, so that the gas barrier property is high. improves. Similarly, the barrier property against components other than gas molecules is also improved, and solvent resistance, hygroscopicity, water absorption, etc. are also improved. Thereby, for example, migration of copper from a copper circuit in a multilayer printed wiring board can be suppressed. Further, it is possible to suppress the generation of defects such as defective plating due to bleeding out of a trace amount of additives in the resin on the surface.

When the above organic solvent was distilled off from the resin varnish composition of the present invention, the varnish composition was heated to 50 kW / m ^{2 under} a radiant heating condition.
The rate of combustion residue of the combustion residue burned by heating for 0.
A resin material having a yield stress of 4.9 kPa or more when compressed at 1 cm / s can be obtained. When the above-mentioned yield point stress is 4.9 kPa or more, the combustion residue does not collapse due to a minute force, and sufficient flame retardancy can be obtained. That is, in order to obtain sufficient flame retardancy, it is necessary that the sintered body retains its shape until the end of combustion and sufficiently exhibits the function as a flame retardant coating. Preferably 15.0 kP
It is a or more. The combustion test is based on ASTM E
It can be carried out according to 1354.

The resin material obtained by distilling off the organic solvent from the resin varnish composition of the present invention contains at least one thermosetting resin and / or thermoplastic resin and a layered silicate. Have excellent mechanical properties, transparency, moisture resistance, etc., improved heat resistance due to increase in glass transition temperature and heat distortion temperature due to restraint of molecular chains, reduction of thermal linear expansion coefficient, layer formation in crystal formation It has been attempted to improve the dimensional stability based on the swelling suppression effect accompanying the nucleation effect of silicate and the improvement of moisture resistance. Further, the resin material,
Since a sintered body of layered silicate is formed at the time of combustion, the shape of the combustion residue is retained, fire spread can be prevented, and excellent flame retardancy is exhibited. Furthermore, by combining with a non-halogen flame retardant such as a metal hydroxide, it is possible to achieve both high mechanical properties and high flame retardancy while considering the environment. The above resin material can be processed into a thin molded body because the layered silicate imparts excellent mechanical properties and the like even if it is not blended in a large amount like an ordinary inorganic filler, and thus it can be processed into a thin multilayered printed board with high density and thinness. Insulating substrate material consisting of the resin sheet of the present invention, which has been thinned to meet the demand for excellent flame retardancy,
Various properties such as mechanical properties, high temperature properties, heat resistance, and dimensional stability can be exhibited.

[0104]

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

Example 1 Bisphenol F type epoxy resin (Epiclon 830L manufactured by Dainippon Ink and Chemicals, Inc.)
87.1 parts by weight of an epoxy resin composition consisting of 57.7 parts by weight of VP), 15.7 parts by weight of BT resin (BT2100B manufactured by Mitsubishi Gas Chemical Co., Inc.) and 15.7 parts by weight of neopentyl glycol diglycidyl ether, and coupling. 2.1 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Nippon Unicar, A-187) as an agent, iron acetylacetone (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a curing catalyst
1.1 parts by weight of a swellable fluorine mica organically treated with distearyldimethyl quaternary ammonium salt as a layered silicate (Somasif MAE-10 manufactured by Corp Chemical)
0) 7.7 parts by weight and 200 parts by weight of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, special grade) as an organic solvent were added to a beaker and stirred for 1 hour with a stirrer, followed by defoaming to obtain a resin varnish. . Then, the obtained resin varnish was placed in a mold and heated at 60 ° C. for 3 hours to evaporate the solvent, and then 1
It was heated at 10 ° C. for 3 hours and further heated at 160 ° C. for 3 hours to be hardened to prepare a material for an insulating substrate which is a plate-shaped molded body having a thickness of 2 mm and 100 μm.

(Example 2) Bisphenol F type epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc., Epicron 830L)
87.1 parts by weight of an epoxy resin composition consisting of 57.7 parts by weight of VP), 15.7 parts by weight of BT resin (BT2100B manufactured by Mitsubishi Gas Chemical Co., Inc.) and 15.7 parts by weight of neopentyl glycol diglycidyl ether, and coupling. 2.1 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Nippon Unicar, A-187) as an agent, iron acetylacetone (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a curing catalyst
1.1 parts by weight of a swellable fluorine mica organically treated with distearyldimethyl quaternary ammonium salt as a layered silicate (Somasif MAE-10 manufactured by Corp Chemical)
0) 7.7 parts by weight, 70 parts by weight of magnesium hydroxide (manufactured by Kyowa Chemical Industry Co., Ltd., Kisuma 5J) as a flame retardant, and
200 parts by weight of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, special grade) as an organic solvent was added to a beaker and stirred for 1 hour with a stirrer, followed by defoaming to obtain a resin varnish. Then, the obtained resin varnish was put in a mold and heated at 60 ° C. for 3 hours to distill off the solvent, then heated at 110 ° C. for 3 hours, and further heated at 160 ° C. for 3 hours to cure, A material for an insulating substrate, which is a plate-shaped molded body having a size of 2 mm and 100 μm, was produced.

Example 3 In a small extruder (TEX30 manufactured by Japan Steel Works, Ltd.), 90 parts by weight of a solid epoxy resin (Epicoat 1007 manufactured by Yuka Shell Epoxy Co., Ltd.) and distearyl dimethyl quaternary as a layered silicate were used. 10 parts by weight of natural montmorillonite (New S-Ben D, manufactured by Toyojun Yoko Co., Ltd.) that has been subjected to an organic treatment with an ammonium salt, and
Magnesium hydroxide as a flame retardant (Kyowa Chemical Industry Co., Ltd.
Kisuma 5J) (100 parts by weight) was added, melt-kneaded at 100 ° C., extruded into a strand, and the extruded strand was pelletized by a pelletizer.

100 parts by weight of the pellets were dissolved in 150 parts by weight of a mixed solvent of methyl ethyl ketone / dimethylformamide (DMF; special grade, manufactured by Wako Pure Chemical Industries, Ltd.) (1: 1; weight ratio), and dicyandiamide (B.T.
3 parts by weight of a solid epoxy content of 90 parts by weight of CG-1200 manufactured by i Japan Co., Ltd., and 3 parts by weight of a curing catalyst (Curesol 2E4MZ, manufactured by Shikoku Kasei Co., Ltd.) of 90 parts by weight of a solid epoxy content. Was thoroughly stirred and then defoamed to obtain a resin varnish. Then, the obtained resin varnish was placed in a mold and heated at 60 ° C. for 3 hours to distill away the solvent, and then heated at 110 ° C. for 3 hours, and further 16
Heat at 0 ° C for 3 hours to cure, thickness 2 mm and 100
A material for an insulating substrate, which is a plate-shaped molded body of μm, was produced.

(Example 4) 90 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 distearyl dimethyl quaternary as a layered silicate. Natural montmorillonite (Toyojun Yoko, New S-Ben D) 10 parts by weight organic synthetic treatment with ammonium salt, synthetic silica (Mitsubishi Materials, Elsil (spherical product)) 7
Add 0 parts by weight and 70 parts by weight of magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5J) as a flame retardant, and add 10 parts by weight.
The mixture was melt-kneaded at 0 ° C. and extruded into a strand, and the extruded strand was pelletized by a pelletizer.

100 parts by weight of these pellets were dissolved in 200 parts by weight of a mixed solvent of methyl ethyl ketone / DMF (1: 1; weight ratio), and dicyandiamide (CG-1200, manufactured by BT Japan Co., Ltd.) was solidified as a curing agent. 3 parts by weight of curing agent (Curezol 2E4MZ, manufactured by Shikoku Kasei Co., Ltd.) was added to 9 parts by weight of an epoxy content of solid epoxy content 9
3 parts by weight with respect to 0 parts by weight was added to this solution and stirred sufficiently, followed by defoaming to prepare a resin varnish. Next, the resin varnish thus obtained was coated on a polyethylene terephthalate sheet and heated at 60 ° C. for 3 hours to distill off the solvent, then heated at 110 ° C. for 3 hours and further heated at 160 ° C. for 3 hours. By curing, an insulating substrate material, which is a plate-shaped molded body having a thickness of 2 mm and 100 μm, was produced.

(Example 5) A polyphenylene ether resin (made by Asahi Kasei, 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, swellable fluorine mica (Somasif MAE-manufactured by Coop Chemical Co., Ltd.) that has been organically treated with distearyldimethyl quaternary ammonium salt as a layered silicate.
100) 10 parts by weight and 50 parts by weight of magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5J) as a flame retardant are added, melt-kneaded at 280 ° C. and extruded in a strand form,
The extruded strands were pelletized by a pelletizer.

100 parts by weight of these pellets were mixed with 20 parts of toluene.
It is dissolved in 0 part by weight, and a liquid bisphenol A type epoxy resin (D.E.R.
31 L) is added to 150 parts by weight with respect to 100 parts by weight of the polyphenylene ether resin, and dicyandiamide (CG-1200, manufactured by BITI Japan Co., Ltd.) as a curing agent is added to 100 parts by weight of the solid epoxy content. On the other hand, 3 parts by weight, 3 parts by weight of a curing catalyst (manufactured by Shikoku Kasei Co., Ltd., Curesol 2E4MZ) with respect to 100 parts by weight of a solid epoxy content, and 200 parts by weight of DMF as an organic solvent were added to this solution and sufficiently stirred, followed by removal of the mixture. It foamed and produced the resin varnish. Then, the resin varnish thus obtained was coated on a polyethylene terephthalate sheet at 60 ° C. for 3 hours.
After heating for 1 hour to evaporate the solvent, it is heated at 110 ° C for 3 hours and further heated at 160 ° C for 3 hours to cure, and the thickness is 2m.
A material for an insulating substrate, which is a plate-shaped molded body of m 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 swellable 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, a material for an insulating substrate which was a plate-shaped molded body having a thickness of 2 mm and 100 μm was produced.

<Evaluation> The performance of the insulating substrate materials produced in Examples 1, 2, 3, 4, 5 and Comparative Example 1 was evaluated for the following items. 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 is measured, and the (0) of the layered silicate is calculated by the black diffraction formula (4) below.
01) The interplanar spacing d was calculated, and the obtained d was taken as the average interlayer distance (nm). λ = 2 dsin θ (4) In the above formula (4), λ is 0.154, and θ represents a diffraction angle.

(2) Ratio of layered silicate dispersed as a laminated body of 5 layers or less A plate-shaped molded body having a thickness of 100 μm is observed with a transmission electron microscope at a magnification of 100,000, and a layered state can be observed in a certain area. The total number of layers X of the silicate laminate and the number of layers Y of the layered silicate dispersed in 5 layers or less were measured, and the layered silicate dispersed as a layered body of 5 layers or less by the following formula (3). The ratio (%) was calculated.

[0117]

[Equation 3]

(3) Shape retention during combustion, maximum heat release rate, and yield point stress (film strength) of combustion residue ASTM E 1354 "Combustibility test method for 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 to measure the maximum heat generation rate (kW / m ² ). The combustion residue was compressed at a speed of 0.1 cm / s using a strength measuring device, and the stress at yield point (coating strength) (kPa) was measured. The shape retention during combustion was evaluated according to the following criteria with respect to the change in shape of the plate-shaped molded product before and after combustion. ◯: The change in shape was slight. X: The shape change was severe.

[0119]

[Table 1]

From Table 1, it can be seen that in the plate-shaped compacts produced in Examples 1, 2, 3, 4 and 5, the average interlayer distance of the layered silicates contained therein is 3 nm or more and 5 or less layers are included. The proportion of the layered silicate dispersed as a laminate was 10% or more, and the shape retention during combustion was excellent. In addition, since it was easy to form a sintered body that became a flame-retardant coating, the maximum heat generation rate was slow, and the yield point stress (coating strength) of the combustion residue was 4.9 kPa or more. On the other hand, in the plate-shaped compact of Comparative Example 1 produced using calcium carbonate instead of the layered silicate, calcium carbonate was not dispersed in a layered form,
The shape retention during combustion was poor, the maximum heat generation rate was fairly fast, and the yield point stress (coating strength) of the combustion residue was extremely low.

[0121]

Industrial Applicability According to the present invention, a resin varnish suitable for producing a resin sheet having excellent mechanical properties, dimensional stability, heat resistance and the like, and particularly having excellent flame retardancy due to the shape retaining effect during combustion. A composition can be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/00 C08K 5/00 F term (reference) 4F072 AB09 AB28 AD04 AD05 AD08 AD09 AD20 AD23 AD25 AD26 AD27 AD28 AD29 AD31 AD34 AD37 AD42 AD44 AD45 AD46 AD47 AF06 AG03 AH02 4J002 BB001 BC031 BD122 BE021 BE061 BF021 BF051 BG041 BG051 CB001 CC031 CC161 CC181 CD001 CE001 CF001 CF011 CF2 DE570 DE0 CM0 DE770 DE0 CM0 DE770 DJ056 EA018 EA028 EA058 EA068 EB028 EB128 EC038 ED028 ED058 EE038 EF038 EH038 EL068 EL108 EP018 ER008 ES008 EU038 EU187 EV208 EV308 EW047 EW048 FD016 FD132 FD137 FD206 GQ01 HA05

Claims (13)

[Claims] 1. 100 parts by weight of a resin composed of at least one thermosetting resin and / or thermoplastic resin, 0.1 to 100 parts by weight of a layered silicate, and 30 to 1000 of an organic solvent.
A resin varnish composition characterized by containing parts by weight. 2. The thermosetting resin is epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, urea resin, allyl resin, silicon resin, benzoxazine resin, phenol resin, unsaturated polyester resin. The resin varnish composition according to claim 1, wherein the resin varnish composition is at least one selected from the group consisting of, and a bismaleimide triazine resin. 3. 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 a 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. Claim 1 or 2
The resin varnish composition described. 4. The resin varnish composition according to claim 1, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite and swelling mica. 5. The resin varnish composition according to claim 1, wherein the layered silicate contains an alkylammonium ion having 6 or more carbon atoms. 6. The resin varnish composition according to claim 1, wherein the organic solvent is an aprotic polar solvent. 7. The resin varnish composition according to claim 1, further comprising 0.1 to 100 parts by weight of a flame retardant containing no halogen-based composition. . 8. The resin varnish composition according to claim 7, wherein the flame retardant is a metal hydroxide. 9. A resin material obtained by distilling off an organic solvent, wherein 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 diffraction measurement method, and The resin varnish composition of claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein all or part of the laminate is dispersed in 5 layers or less. 10. A resin material obtained by distilling off an organic solvent is obtained by heating a combustion residue for 30 minutes under a radiant heating condition of 50 kW / m ² and compressing the combustion residue at a speed of 0.1 cm / s. Yield point stress is 4.9 kPa or more, The resin varnish composition of Claim 1, 2, 3, 4, 5, 6, 7, 8 or 9. 11. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A resin sheet comprising the resin varnish composition according to item 8, 9, or 10. 12. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A prepreg characterized by using the resin varnish composition described in 8, 9, or 10. 13. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A coating material comprising the resin varnish composition described in 8, 9, or 10.