CN100360597C - Material for insulating substrate and products therefrom - Google Patents

Abstract

A material for insulating substrates which is excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc. and, in particular, produces an excellent flame-retardant effect due to the effect of shape retention during combustion. The material for use in producing insulating substrates comprises 100 parts by weight of a thermoplastic resin or a mixture thereof with a thermosetting resin and 0.1 to 100 parts by weight of a phyllosilicate.

Description

The raw material of insulating substrate reaches the goods by its production

The application divides an application, the international application no of its original application is PCT/JP01/10771, the China national application number is 01820176.8, the applying date is December 10 calendar year 2001, and denomination of invention is " raw material of insulating substrate, printed circuit board (PCB), veneer sheet, the Copper Foil that adheres to resin, copper plate pressing plate, Kapton, the film that is used for TAB and a prepreg ".

Technical field

The present invention relates to raw material, printed circuit board (PCB), veneer sheet, the Copper Foil that adheres to resin, copper plate pressing plate, Kapton, the film that is used for TAB and the prepreg of insulating substrate, they all have excellent physicals, dimensional stability, thermotolerance, flame retardant resistance etc., and especially when burning because of keeping profile to show the excellent fire retardant effect.

Background technology

Usually, multi-sheet printed base material used in the electronics is made of the multilayer insulation base material, this layer insulation base material has adopted the thermosetting resin prepreg, and this prepreg has the woven fiber glass with the thermosetting resin dipping, or has the film of being made up of thermosetting resin or photo-curable resin.

Because multi-sheet printed base material is made thinlyyer and high compaction more in recent years, thus need very thin interlayer base material, and the layer insulation base material that needs to adopt the woven fiber glass that approaches or do not adopt woven fiber glass.Layer insulation base material well known in the prior art comprises, for example, and by rubber (elastomerics), with acrylic resin maleimide-cyanate resin material or be mixed with the material that the thermoplastic resin material of a large amount of mineral fillers is formed.

For example, the spy open the 2000-183539 communique disclose " method for preparing the multilayer insulation base material; described method adopts and is attached with the film of Resins, epoxy as insulation layer; the formation method of described film is; to make median size be 0.8 to 5m non-fiber mineral filler with based on the polymer epoxy polymer; polyfunctional epoxy resin; the varnish of solidifying agent and linking agent mixes, one or two surface that then described mixture is coated to base material upward forms described film, described polymer epoxy polymer is polymerized by bifunctional Resins, epoxy and bifunctional phenol, its weight-average molecular weight is 50,000 or higher.”

Yet, in the multilayer insulation base material that obtains according to above-mentioned preparation method, the interfacial area that is used for improving between for example necessary mineral filler of physicals such as physical strength and polymer epoxy polymer or the polyfunctional epoxy resin is limited, therefore, need sneak into a large amount of mineral fillers, thereby be difficult to obtain thin interlayer base material, and cause inconvenience such as for example preparation process increase.

In addition, the problem that adopts thin woven fiber glass or do not adopt the layer insulation base material of woven fiber glass to exist is, for example, thermotolerance and dimensional stability deficiency, and because it is brittle are so for example exist inconvenience such as fragmentation easily in preparation process.

On the other hand, owing to have for example waste plastic and the problems such as disposal that upset endocrine chemical substance,, thereby need to transfer to adopt environment amenable material so the polymer materials of industrial use should be the material of environmental sound.Specifically, the someone has studied the fire retardant that contains halogen from use and has transferred the not halogen-containing fire retardant of use to, and the burning back produces problems such as Er Evil compounds so that for example solve.In addition, the fire retardant effect that contains halogen is strong, the physicals of moldability and foundry goods is difficult for degenerating, but when having used these fire retardants, in mold pressing or combustion processes, can produce a large amount of halogen gass, the halogen gas that produced can etching apparatus or human body is produced undesirable action, so for the purpose of safety, presses for the technology and the method that provide the not halogen-containing fire retardant of employing to replace containing the fire retardant of halogen.

In order to realize transformation to environment amenable material, also developed a kind of raw material of insulating substrate in recent years, wherein adopted not halogen-containing fire retardant.Yet, in order to produce essential flame retardant resistance, need to add a large amount of this not halogen-containing fire retardants, therefore and the problem that produces is, when the raw material of insulating substrate has adopted this not halogen-containing fire retardant in a large number, its thermotolerance and dimensional stability have adopted the fire retardant that contains halogen not as good as the raw material of traditional insulating substrate in the raw material of traditional insulating substrate.

Also be, the problem of the raw material of this insulating substrate is, when it forms for example thin insulating substrate, it is difficult to keep thermotolerance, dimensional stability and physicals, and because in order to produce essential flame retardant resistance, need to add not halogen-containing in a large number fire retardant, so this material has required physicals and thermotolerance in the process such as process for processing hardly.

Summary of the invention

In view of the foregoing, the raw material, printed circuit board (PCB), veneer sheet, the Copper Foil that adheres to resin, copper plate pressing plate, Kapton, the film that is used for TAB and the prepreg that the purpose of this invention is to provide insulating substrate, they all have excellent physicals, dimensional stability, thermotolerance, flame retardant resistance etc., and especially when burning because of keeping profile to show the excellent fire retardant effect.

First aspect of the present invention relates to a kind of raw material of insulating substrate, and the raw material of described insulating substrate contains the mixture of 100 parts by weight of thermoplastic resin or thermoplastic resin and thermosetting resin, and the layered silicate of 0.1 to 100 weight part.

Described thermoplastic resin is at least a in the group that following resin is formed preferably: polyphenylene oxide resinoid, the polyphenylene oxide resinoid with functional group modification, polyphenylene oxide resinoid or with the polyphenylene oxide resinoid of functional group modification and mixture, alicyclic hydrocarbon resin, thermoplastic polyimide resinoid, polyether-ether-ketone resin, polyethersulfone resin, polyamide-imide resin and the polyester-imides resin of polystyrene resins.

Second aspect of the present invention relates to a kind of raw material of insulating substrate, the raw material of described insulating substrate contains the thermosetting resin of 100 weight parts and the layered silicate of 0.1 to 100 weight part, and described thermosetting resin is to be selected from least a in the group of being made up of following resin: the polyphenylene oxide resinoid of phenol resins, urea-formaldehyde resin, unsaturated polyester resin, allylic resin, thermoset polyimide resin, bismaleimide-triazine resin, thermosetting modification, silicone resin and benzimidazole dihydrochloride resinoid.

The raw material of the insulating substrate of the present invention first or second aspect preferably contains the fire retardant that is substantially free of halogen composition of 0.1 to 100 weight part.

The 3rd aspect of the present invention relates to a kind of raw material of insulating substrate, wherein, corresponding to per 100 parts by weight of epoxy resin, the raw material of described insulating substrate contains the layered silicate of 0.1 to 100 weight part and the fire retardant that is substantially free of halogen composition of 0.1 to 100 weight part.

Contained fire retardant is preferably metal hydroxides or melamine derivative in the raw material of the insulating substrate of the present invention first, second or the 3rd aspect.

The raw material of insulating substrate of the present invention can prepare by resin combination (A) is mixed with resin combination (B), what described resin combination (A) contained 100 weight parts is selected from least a resin in the group of being made up of thermoplastic resin and/or thermosetting resin and the layered silicate of 1 to 500 weight part, the composition of described resin combination (B) is different from resin combination (A), and described resin combination (B) contains at least a thermoplastic resin and/or thermosetting resin.Preferably, described resin combination (A) contains at least a resin that is selected from the group of being made up of polyamide-based resin, polyphenylene oxide resinoid and vibrin, and described resin combination (B) contains redix.

At least a in the group that the preferred free montmorillonite of the layered silicate of fusion, swelling mica and hectorite are formed in the raw material of insulating substrate of the present invention.Layered silicate preferably contains the alkyl phosphate ion with 6 or more carbon atoms, measure through the wide-angle x-ray diffraction method, the average layer spacing of (001) face of layered silicate is preferably 3nm or bigger, and partly or entirely being separated into below 5 layers or 5 layers of layered silicate quilt.

According to the combustion test of ASTM (American society association) E1354, at 50kW/m ²The radiation heating condition under the heating insulating substrate of the present invention raw material made it in 30 minutes the burning, the yielding stress of the residue of combustion that records under the compression speed of 0.1cm/s is preferably 4.9kPa or bigger.

Scope of the present invention comprises that also employing is according to the resulting veneer sheet of the raw material of insulating substrate of the present invention, printed circuit board (PCB), the Copper Foil that adheres to resin, copper plate pressing plate, Kapton, the film that is used for TAB and prepreg.

Embodiment

To describe the present invention in detail below.

Raw material according to insulating substrate of the present invention comprises thermoplastic resin and/or thermosetting resin.

The example of thermoplastic resin is including, but not limited to: polyolefin resin, polystyrene resins, polyphenylene oxide resinoid with the polyphenylene oxide resinoid of functional group modification; Polyphenylene oxide resinoid or with the polyphenylene oxide resinoid of functional group modification and a kind of thermoplastic resin mixture of polystyrene resins for example, described polystyrene resins and polyphenylene oxide resinoid or compatible with the polyphenylene oxide resinoid of functional group modification; Alicyclic hydrocarbon resin, thermoplastic polyimide resinoid, polyamide-imide resinoid, polyester-imides resinoid, polyester resin, polyether-ether-ketone (PEEK) resinoid, polyethersulfone resin, polyamide-based resin, polyvinyl acetal-based resin, polyvinyl alcohol resin, polyvinyl acetate esters resin, poly-(methyl) acrylic resin and polyoxymethylene resinoid.Particularly, preferably adopt the polyphenylene oxide resinoid, with the polyphenylene oxide resinoid of functional group modification, polyphenylene oxide resinoid or with the polyphenylene oxide resinoid of functional group modification and mixture, alicyclic hydrocarbon resin and the thermoplastic polyimide resinoid of polystyrene resins.

Can use two or more above-mentioned resins individually or simultaneously.In this manual, " (methyl) acrylic " refers to " acrylic " or " methacrylic acid group ".

The polyphenylene oxide resinoid is the homopolymer or the polyphenylene ether copolymer of the polyphenylene oxide be made up of the represented repeating unit of following formula (1):

Wherein, R ¹, R ², R ³And R ⁴Each represents hydrogen atom, alkyl, aralkyl, aryl or alkoxyl group.Described alkyl, aralkyl, aryl or alkoxyl group can be replaced by a substituting group respectively.

The example of described polyphenylene oxide homopolymer including, but not limited to: poly-(2,6-dimethyl-1, the 4-phenylene) ether, poly-(2-methyl-6-ethyl-1, the 4-phenylene) ether, poly-(2,6-diethyl-1, the 4-phenylene) ether, poly-(2-ethyl-6-n-propyl-1, the 4-phenylene) ether, poly-(2,6-di-1, the 4-phenylene) ether, poly-(2-ethyl-6-normal-butyl-1, the 4-phenylene) ether, poly-(2-ethyl-6-isobutyl--1,4-phenylene) ether, poly-(2-methyl-6-hydroxyethyl-1,4-phenylene) ether etc.

The example of polyphenylene ether copolymer is including, but not limited to the multipolymer be made up of above-mentioned polyphenylene oxide repeating unit, and by the multipolymer of forming with the above-mentioned polyphenylene ether copolymer of one or more styrene monomer graft copolymerizations, described polyphenylene oxide repeating unit partly comprises for example alkyl trisubstituted benzene phenol, described alkyl trisubstituted benzene phenol for example 2,3,6-pseudocuminol, described styrene monomer have for example vinylbenzene, alpha-methyl styrene and Vinyl toluene.

These polyphenylene oxide resinoids can use separately, perhaps use the different polyphenylene oxide resinoid of one or more compositions, composition or molecular weight simultaneously.

The described resinoid example of polyphenylene oxide with functional group modification including, but not limited to: with for example polyphenylene oxide resinoid of one or more functional group modification such as maleic anhydride base, glycidyl, amino, allyl group.These polyphenylene oxide resinoids with functional group modification can use separately, perhaps can use its two or more simultaneously.

When described polyphenylene oxide resinoid with functional group modification was used as thermoplastic resin, crosslinking reaction can take place in the raw material of the insulating substrate of gained, thereby further improved physicals, thermotolerance, dimensional stability etc.

Described polyphenylene oxide resinoid or with the example of the mixture of the polyphenylene oxide resinoid of functional group modification and polystyrene resins including, but not limited to: polyphenylene oxide resinoid or with the polyphenylene oxide resinoid of functional group modification and the mixture of styrene homopolymers; Polyphenylene oxide resinoid or with the polyphenylene oxide resinoid of functional group modification and a kind of mixture of multipolymer, described multipolymer is vinylbenzene and for example formed multipolymers of one or more styrene monomers such as alpha-methyl styrene, ethyl styrene, t-butyl styrene, Vinyl toluene; And polyphenylene oxide resinoid or with the mixture of polystyrene resins such as the polyphenylene oxide resinoid of functional group modification and for example styrenic elastomer.Above-mentioned polystyrene resins can use separately, perhaps can use its two or more simultaneously.

These polyphenylene oxide resinoids or can use separately with the polyphenylene oxide resinoid of functional group modification and the mixture of polystyrene resins perhaps can use its two or more simultaneously.

Described alicyclic hydrocarbon resin is had no particular limits, as long as its hydrocarbon compound resinoid for have cyclic hydrocarbon radical on its polymer chain, the example that can mention has cycloolefin homopolymers or multipolymer.These alicyclic hydrocarbon resins can use separately, perhaps can use its two or more simultaneously.

Described cycloolefin is the norborneol vinyl monomer, it for example comprises, norbornylene, methylene radical octalin, dimethylene octalin, dimethylene ten dialins, dimethylene naphthane, trimethylene ten dialins, dicyclopentadiene, 2,3-dihydro cyclopentadiene, methylene radical octahydro benzindene, dimethylene octahydro benzindene, methylene radical decahydro benzindene, dimethylene decahydro benzindene, methylene radical octahydro fluorenes, dimethylene octahydro fluorenes etc. and substitutive derivative thereof.These cycloolefins can use separately, perhaps can use its two or more simultaneously.

The substituent example of the norbornene derivative of these replacements including, but not limited to: known alkyl and polar group be alkyl, alkylidene group, aryl, cyano group, carbalkoxy, pyridyl and halogen atom for example.These substituting groups can use separately, perhaps can use its two or more simultaneously.

The example of the norbornene derivative of above-mentioned replacement is including, but not limited to 5-methyl-2-norbornylene, 5,5-dimethyl-2-norbornylene, 5-ethyl-2-norbornylene, 5-butyl-2-norbornylene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornylene, 5-cyano group-2-norbornylene, 5-methyl-5-methoxycarbonyl-2-norbornylene, 5-phenyl-2-norbornylene, 5-phenyl-5-methyl-2-norbornylene etc.These norbornene derivatives can use separately, perhaps can use its two or more simultaneously.

The Arton that the example of commercially available above-mentioned alicyclic hydrocarbon resin has JSR to produce ^TMSeries product and Nippon Zeon Co., the Zeonor that Ltd. produced ^TMSeries product.

The resinoid example of thermoplastic polyimide including, but not limited to: at the polyetherimide resin that has imide key and ehter bond on the molecular backbone chain, on molecular backbone chain, have the polyamide-imide resin of imide key and amido linkage, and the polyester-imides resin that on molecular backbone chain, has imide key and ester bond.These thermoplastic polyimide resinoids can use separately, perhaps can use its two or more simultaneously.

The example of polyether-ether-ketone resin is including, but not limited to the reaction product by dihalo benzophenone and quinhydrones polycondensation gained.

Described thermosetting resin is formed by the relatively low raw material of molecular weight, these raw materials are liquid, semi liquid state or solid-state at normal temperatures, under normal temperature or heating condition, show flowability, and chemical reactions such as curing reaction or crosslinking reaction take place, thereby form insoluble infusible tridimensional network under solidifying agent, heating or catalytic condition.

The example of described thermosetting resin including, but not limited to: phenolic resin, redix, the polyphenylene oxide resinoid, Thermocurable polyimide resinoid, allylic resin, bismaleimide-triazine resin, silicone resin, benzimidazole dihydrochloride resinoid etc. of unsaturated polyester esters resin, alkyd based resin, furans resin, urea air aldehyde resin, trimeric cyanamide resinoid, polyurethanes resin, phenyl amines resin, thermosetting modification.Especially preferably adopt in the above-mentioned resin redix, polyphenylene oxide resinoid, silicone resin and the benzimidazole dihydrochloride resinoid of phenol resins, urea-formaldehyde resin, unsaturated polyester resin, allylic resin, thermoset polyimide resin, bismaleimide-triazine resin, thermosetting modification.These thermosetting resins can use separately, perhaps can use its two or more simultaneously.

Described Resins, epoxy refers to have the organic compound of at least one oxyethane ring (epoxy group(ing)).The preferred per molecule of the number of the epoxy group(ing) in the Resins, epoxy is one or more, and more preferably per molecule is two or more.Just obtained the epoxy group(ing) number of per molecule divided by the molecule number in the Resins, epoxy with the epoxy radix in the Resins, epoxy.

The example of described Resins, epoxy is including, but not limited to known traditional Resins, epoxy, for example below shown in Resins, epoxy (1) to (11).These Resins, epoxy can use separately, perhaps can use its two or more simultaneously.

Resins, epoxy (1) comprising: bisphenol-type epoxy resin, for example, bisphenol A type epoxy resin, bisphenol f type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, bisphenol-s epoxy resin etc.; Phenolic resin varnish type epoxy resin, for example, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin etc.; Aromatic epoxy resin, for example, tris-phenol triglycidyl group ether etc., and hydrogenated derivatives and bromide.

Resins, epoxy (2) comprises cycloaliphatic epoxy resin, for example, 3,4-oxyethyl group cyclohexyl methyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-2-methyl cyclohexane ylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylic acid ester, two (3, the 4-epoxycyclohexyl) adipic acid ester, two (3,4-epoxycyclohexyl methyl) adipic acid ester, two (3,4-epoxy-6-epoxycyclohexyl methyl) adipic acid ester, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3,4-epoxy) pimelinketone-methyl-dioxane, two (2,3-oxirane ring amyl group) ether etc.Commodity Resins, epoxy (2) for example comprises EHPE-3150 ^TM(Ltd. produces for 71 ℃ of softening temperatures, DaicelChemical Industries).

Resins, epoxy (3) comprises the aliphatic epoxy resin of long-chain poly-hydroxy polyglycidyl ether, for example 1,4-butanediol diglycidyl ether, 1, contains the poly suboxygen alkyl two pure and mild polytetramethylene ether diols of the alkylidene group of (preferred 2 to the 4) carbon atom that has 2 to 9 at 6-hexanediol diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether.

Resins, epoxy (4) comprises the glycidyl ester based epoxy resin, for example phthalic acid diglycidyl ether, tetrahydrophthalic acid diglycidyl ether, hexahydro-phthalic acid diglycidyl ether, diepoxy propyl group P-hydroxybenzoic acid, glycidyl ether-Whitfield's ointment glycidyl ester, dimeracid glycidyl ester etc., and hydrogenated derivatives.

Resins, epoxy (5) comprises glycidyl amine Resins, epoxy, the N of triglycidyl isocyanurate, cycloalkyl urea for example, N '-2-glycidyl radical derivative, p-aminophenol N, N, O-three-glycidyl radical derivative, Metha Amino Phenon N, N, O-three-glycidyl radical derivative and hydrogenated derivatives thereof.

Resins, epoxy (6) comprises the formed multipolymer of monomer of free redical polymerizations such as (methyl) glycidyl acrylate and ethene, ethyl acetate, (methyl) acrylate.

Resins, epoxy (7) comprises the resin that is generated by the unsaturated carbon-to-carbon double bond epoxidation in the polymkeric substance of conjugated diene compound or its partially hydrogenated derivative, for example epoxidized polybutadiene.

Resins, epoxy (8) comprises the resin that is generated by the unsaturated carbon-to-carbon double bond epoxidation in the conjugated diene compound, segmented copolymer (as epoxidized SBS) for example has " based on the polymer segment of vinyl aromatic compounds " and " based on the polymer segment of conjugated diene compound or the polymer segment of its partially hydrogenated derivative " at the same intramolecularly of described multipolymer.

Resins, epoxy (9) is one or more for per molecule has, the vibrin of preferred two or more epoxy group(ing).

Resins, epoxy (10) is introduced urethane bonds or polycaprolactone key, the Resins, epoxy of urethane-modified Resins, epoxy of Xing Chenging or polycaprolactone modification therefrom for passing through in the structure of above-mentioned Resins, epoxy.

Resins, epoxy (11) adds rubber constituent for example NBR (paracril), CTBN (the end capped acrylonitrile-butadiene copolymer of carbonyl), polyhutadiene or acrylic rubber, the Resins, epoxy of the modified rubber of Xing Chenging therefrom for passing through in above-mentioned Resins, epoxy.

Have no particular limits being used for described curing agent for epoxy resin, its example comprises the various known curing agent for epoxy resin that are used for, for example amine compound, for example by amine compound synthetic polyaminoamide compound, tertiary amine compound, imidazolium compounds, hydrazide compound, dicyanamide compound and derivative thereof, melamine compound, acid anhydrides, oxybenzene compound, hot checking exuberance of yang ionic polymerization catalyst, light checking exuberance of yang ionic polymerization initiator etc.These solidifying agent can use separately, also can use its two or more simultaneously.

Described amine compound comprises that for example, straight-chain fatty amine and derivative thereof, described straight-chain fatty amine be quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, polypropyleneoxide diamine, polyoxypropylene triamine etc. for example; Cycloaliphatic amine and derivative thereof, described cycloaliphatic amine is menthene diamines, unusual sym.-diisopropylideneacetone diamines, two (4-amino-3-methylcyclohexyl) methane, diamino-dicyclohexyl methane, two (amino methyl) hexanaphthene, N-aminoethyl piperazine, 3 for example, two (the 3-aminopropyls)-2 of 9-, 4,8,10-four oxaspiros [5,5] undecane etc.; Arylamine and derivative thereof, described arylamine be m-xylene diamine, α-(/ right-aminophenyl) ethamine, m-phenylenediamine, diaminodiphenyl-methane, diamino diphenyl sulfone, α for example, α-two (4-aminophenyl)-and to diisopropyl benzene etc.

Describedly for example comprise by amine compound synthetic polyaminoamide compound, for example, by above-mentioned various amine compound and carboxylic acid cpd institute synthetic polyaminoamide compound and derivative thereof, described carboxylic acid cpd is succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, m-phthalic acid, terephthalic acid, dihydro m-phthalic acid, tetrahydrochysene m-phthalic acid, six hydrogen m-phthalic acids etc. for example; By maleimide synthetic polyaminoamide compound and derivatives thereof such as amine compound and for example diaminodiphenyl-methane bismaleimidess; By amine compound and ketone compound institute synthetic ketimine compound and derivative thereof; And by amine compound and other compounds institute synthetic polyamino compound and derivative thereof, described other compounds are epoxy compounds, urea, thiocarbamide, aldehyde cpd, phenolic compound and acrylic compound for example.

Described tertiary amine compound comprises, for example, and N, N-lupetazin, pyridine, picoline, phenyl dimethyl amine, 2-(dimethylaminomethyl) phenol, 2,4,6-three (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5,4,0] undecene-1 and derivative thereof.

Described imidazolium compounds comprises, for example, and glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenylimidazole and derivative thereof.

Described hydrazides comprises, for example, 1, two (diazanyl the carbonyl ethyl)-5-sec.-propyl glycolylurea, 7 of 3-, 11-18 carbon diene-1,18-dicarbapentaborane hydrazides, octadecane dicarboxylic acid two hydrazides, adipic dihydrazide and derivative thereof.

Described melamine compound comprises, for example, 2,4-diamino-6-vinyl-1,3,5-triazines and derivative thereof.

Described acid anhydrides comprises, for example, Tetra hydro Phthalic anhydride, 1,2, the 4-benzenetricarboxylic anhydride, 1,2,4, the 5-pyromellitic anhydride, the benzophenone tetracarboxylic anhydride, ethylene glycol bis dehydration trimellitate, glycerol three dehydration trimellitates, the methyltetrahydro Tetra hydro Phthalic anhydride, tetrahydronaphthalic anhydride, nadic anhydride, the methyl nadic anhydride, the trialkyl tetrahydronaphthalic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, 5-(2, the 5-dioxotetrahydrofuryl)-and 3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, trialkyl tetrahydronaphthalic anhydride-maleic anhydride adducts, dodecenyl succinic anhydride, poly-nonane diacid acid anhydride, polydecandicarboxylic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride and derivative thereof.

Described oxybenzene compound comprises, for example, and lacquer resins, ortho-cresol lacquer resins, p-cresol lacquer resins, tertiary butyl lacquer resins, Dicyclopentadiene (DCPD) cresols and derivative thereof.

Described hot checking exuberance of yang ionic polymerization catalyst comprises that for example, ion checking exuberance of yang ionic polymerization catalyst hot in nature is for example with antimony hexafluoride, phosphorus hexafluoride or tetrafluoride boron benzyl sulfonium salt, benzyl ammonium salt, benzyl-pyridine salt and the benzyl microcosmic salt as balance anion; And nonionic checking exuberance of yang ionic polymerization catalyst hot in nature for example N-benzylphthalimide, aromatic sulfuric acid salt etc.

Described smooth checking exuberance of yang ionic polymerization initiator comprises, for example, ionic smooth checking exuberance of yang ionic polymerization initiator for example with antimony hexafluoride, phosphorus hexafluoride or tetrafluoride boron as the salt of balance anion for example aryl diazonium salt, aromatic halonium salts and aromatics sulfonium salt; Organometallic complex is iron-aromatic hydrocarbons complex compound, two luxuriant titanium complexs, aryl silanol-aluminium complex etc. for example; And nonionic light checking exuberance of yang ionic polymerization initiator for example nitrobenzyl ester, sulfonic acid, phosphoric acid ester, phenolsulfonate, diazo naphthoquinone, N-hydroxyl imide sulfonate etc.

The resinoid example of the polyphenylene oxide of thermosetting modification including, but not limited to: with resulting resins of thermoset functional group modification polyphenylene oxide resinoid such as glycidyl, isocyanate group and amino for example.The polyphenylene oxide resin of these thermosetting modifications can use separately, also can use its two or more simultaneously.

Described Thermocurable polyimide resinoid is the resin that has imide bond on the molecular backbone, its example including, but not limited to: aromatic diamine/aromatic acid's polycondensate, bimaleimide resin be aromatic diamine/bismaleimides addition polymer, polyaminobismaleimide resin benzaminic acid hydrazides/bismaleimides addition polymer for example for example, and by diisocyanate cpd and the formed bismaleimide-triazine resin of bimaleimide resin.Especially, can preferably adopt bismaleimide-triazine resin.These Thermocurable polyimide resinoids can use separately, also can use its two or more simultaneously.

Described urea-formaldehyde resin is had no particular limits, as long as its thermosetting resin for being generated by the addition polycondensation reaction by urea and formaldehyde.In curing reaction of urea formaldehyde resin reaction the example of used solidifying agent including, but not limited to: by mineral acid, organic acid or the solidifying agent of the dominance formed of acid-salt such as sodium bisulfate for example; And recessive solidifying agent, for example carboxylate salt, acid anhydrides and for example salt such as ammonium chloride, ammonium phosphate.Especially, when factors such as consideration storage stability, preferred recessive solidifying agent.

Allylic resin is had no particular limits, as long as it is for passing through monomeric polymerization of Phthalic acid, diallyl ester and curing reaction gained.Phthalic acid, diallyl ester comprises for example ortho position, dystopy and contraposition monomer.When solidifying, curing catalysts for example t-butylperoxyl benzoate and peroxidation di tert butyl carbonate have been adopted simultaneously.

Described silicone resin intramolecularly contains silicon-silicon bond, silicon-carbon bond, siloxane bond and silicon-nitrogen key, adducible example polysiloxane, Polycarbosilane and polysilazane.

Described benzimidazole dihydrochloride resin carries out ring-opening polymerization by benzimidazole dihydrochloride monomer De oxazine ring and obtains.The monomeric example of benzimidazole dihydrochloride is including, but not limited to benzimidazole dihydrochloride monomer with the functional groups such as for example phenyl, methyl or cyclohexyl on the nitrogen that is attached to benzimidazole dihydrochloride De oxazine ring.

In order to improve the characteristic of resin, if necessary, thermoplastic resin and/or thermosetting resin can be mixed with thermoplastic elastomer, cross-linked rubber, oligomer etc., the proportioning of carrying out each material of blended should reach purpose of the present invention.In addition, can use these resins individually or simultaneously.

The example of described thermoplastic elastomer is including, but not limited to styrenic elastomer, olefin elastomer, polyurethane elastomer and polyester elastomer.These thermoplastic elastomers can use separately, also can use its two or more simultaneously.

The example of described cross-linked rubber is including, but not limited to synthetic polyisoprene, divinyl rubber, 1,2-polyhutadiene, styrene butadiene rubbers, paracril, isoprene-isobutylene rubber, ethylene-propylene rubber(EPR), silicon rubber and urethanes.In order to improve the consistency of above-mentioned rubber and resin, the preferred above-mentioned cross-linked rubber that adopts through functional group modification.These cross-linked rubbers can use separately, also can use its two or more simultaneously.

Described oligomer is including, but not limited to maleic anhydride modified polyethylene oligomer.These oligomers can use separately, also can use its two or more simultaneously.

As the supplementary means that reaches the physicals homogeneous, can mix one or more additives in described thermoplastic resin and/or the thermosetting resin, for example, can be as the nucleator that is used to form fine crystals, oxidation inhibitor (anti-aging agent), thermo-stabilizer, photostabilizer, UV light absorber, lubricant, fire retardant, static inhibitor and the antifogging agent of nucleus.

The raw material of insulating substrate of the present invention contains thermoplastic resin and/or thermosetting resin and layered silicate.

Layered silicate refers to have the silicate minerals of tradable metallic cation between its layer and layer.

The example of layered silicate including, but not limited to: the terre verte ore deposit is montmorillonite, saponite, hectorite, beidellite, lucianite and nontronite, vermiculite, halloysite and swelling mica for example.Especially, preferably adopt montmorillonite and/or swelling mica and/or hectorite.Layered silicate can be natural materials or synthetic materials.These layered silicates can use separately, also can use its two or more simultaneously.

Layered silicate is preferably by the defined shape anisotropy effect of following equation (2) big terre verte ore deposit or swelling mica.By adopting the big layered silicate of shape anisotropy effect, the raw material of insulating substrate of the present invention has obtained more excellent physicals.

Equation (2): the area of the area/crystal surface (B) of shape anisotropy effect=crystal surface (A)

Wherein crystal surface (A) refers to the front of layer, and crystal surface (B) refers to the side of layer.

Shape to layered silicate has no particular limits, but preferably its mean length is 0.01 to 3 μ m, more preferably 0.05 to 2 μ m.Preferred 0.001 to the 1 μ m of its thickness, more preferably 0.01 to 0.5 μ m.Its long-width ratio is preferred 20 to 500, and more preferably 50 to 200.

Be metal ions such as sodium on the crystal surface that for example is present in layered silicate and calcium at the existing tradable positively charged ion of the interlayer of layered silicate, these metal ions have the positively charged ion interchangeability to cationic materials, so these metal ions just can insert between the crystal layer of (embedding) layered silicate.

Cation exchange capacity (CEC) to layered silicate has no particular limits, but preferred 50 to 200 milliequivalents/100 grams.If the cation exchange capacity (CEC) of layered silicate is less than 50 milliequivalents/100 grams, then the cationic substance that is embedded between the crystal layer of layered silicate by cationic exchange reduces, this can cause can not obtaining between the crystal layer enough unpolarizings (hydrophobization), if and cation exchange capacity (CEC) is greater than 200 milliequivalents/100 grams, then the bonding force between the crystal layer of layered silicate is excessive, and this can cause being difficult to a thin crystal layer dissociated and come.

When having adopted low polar resin such as polyphenylene oxide resinoid, preferably adopt cats product that layered silicate is carried out cationic exchange in advance and handle and make the interlayer hydrophobization as thermoplastic resin of the present invention and/or thermosetting resin.Hydrophobization in advance by the layered silicate interlayer, improved the avidity of low polar thermoplastic resin of laminar silicic acid salt pair or thermosetting resin, thereby made that layered silicate can be tiny and be evenly dispersed in low polar thermoplastic resin and/or the thermosetting resin.

The example of described cats product is including, but not limited to quaternary ammonium salt, quaternary alkylphosphonium salt etc.Especially, the preferred employing has the quaternary ammonium salt that carbonatoms is 6 or more alkyl chain (alkylammonium salt with 6 or more a plurality of carbon atoms), because this class salt can make depolarization (hydrophobization) between the crystal layer of layered silicate.

The example of described quaternary ammonium salt is including, but not limited to trimethylalkyl ammonium salt, the triethyl alkylammonium salt, the tributyl alkylammonium salt, dimethyl dialkyl ammonium salt, the dibutyl dialkyl ammonium salt, the methyl-benzyl dialkyl ammonium salt, the dibenzyl dialkyl ammonium salt, trialkyl methyl ammonium salt, trialkyl ethyl ammonium salt, trialkyl butyl ammonium salt, quaternary ammonium salt with aromatic ring, derive and next quaternary ammonium salt by arylamine such as for example trimethylphenyl ammoniums, dialkyl quats salt with two polyglycol chains, dialkyl quats salt with two polypropylene glycol chains, the tri alkyl quaternary ammonium salt that has the tri alkyl quaternary ammonium salt of a polyglycol chain and have a polypropylene glycol chain.Preferred especially dodecyl trimethyl quaternary ammonium salt, octadecyl trimethyl quaternary ammonium salt, trioctylphosphine methyl quaternary ammonium, distearyl dimethyl quaternary ammonium, two hardened tallow base dimethyl quaternary ammoniums, distearyl dibenzyl quaternary ammonium salt and N-polyoxyethylene-N-dodecyl-N in these salt, the N-dimethyl quaternary ammonium.These quaternary ammonium salts can use separately, also can use its two or more simultaneously.

The example of described quaternary alkylphosphonium salt is including, but not limited to dodecyl triphenyl phosphonium salt, first base triphenyl phosphonium salt, ten dialkyl group, three first base phosphonium salts, stearyl three first base phosphonium salts, three hot basic phosphonium salts, distearyl two first base phosphonium salts, distearyl two benzyl base phosphonium salts etc.Zhe Xie phosphonium salt can use separately, also can use its two or more simultaneously.

Can improve the dispersiveness of layered silicate of the present invention in thermoplastic resin and/or thermosetting resin by above-mentioned chemical treatment.

Chemical treatment is not limited to adopt cats product to carry out the method (hereinafter also being referred to as chemical modification method (1)) of cationic exchange, can also adopt the various chemical processes of for example following chemical modification method (2) to (6) to handle.These chemical modification methods can use separately, also can use its two or more simultaneously.

Hereinafter, we also handle having passed through the various chemical processes that comprise chemical modification method (1), thereby the layered silicate that has improved the dispersiveness in thermoplastic resin and/or thermosetting resin is called " layered silicate organises ".

Chemical modification method (2) is, adopt in the end group and have the single or multiple compounds that can form the functional group of chemical bond with hydroxyl, perhaps adopt to have single or multiplely not form chemical bond but have the compound of the end group of high chemical affinity, come carrying out chemical treatment with existing hydroxyl on the layered silicate crystal surface that organises of chemical modification method (1) chemical treatment with hydroxyl with hydroxyl.

Chemical modification method (3) is, adopt and to have the single or multiple functional groups that do not form chemical bond but have high chemical affinity with hydroxyl in the end group with hydroxyl, and have the compound of one or more reactive functional groups, come carrying out chemical treatment with existing hydroxyl on the layered silicate crystal surface that organises of chemical modification method (1) chemical treatment.

Chemical modification method (4) is, adopts anionic surfactant compound to come the crystal surface with the layered silicate that organises of chemical modification method (1) chemical treatment is carried out chemical treatment.

Chemical modification method (5) is the method according to chemical modification method (4), and it comprises and adopting on the molecular chain except having anionic sites that the anionic surfactant compound that also has one or more reactive functional groups carries out chemical treatment.

Chemical modification method (6) (for example contains resin for adopting, maleic anhydride modified polyphenylene oxide resinoid) composition, the prior layered silicate of handling with the arbitrary method of chemical modification method (1) to (5) that organises is carried out chemically treated method, described resin have can with the functional group of the described laminar silicic acid reactant salt that organises.

In chemical modification method (2), for the functional group that can form chemical bond with hydroxyl, perhaps do not form chemical bond but the functional group that hydroxyl has a high chemical affinity is had no particular limits with hydroxyl, the example of these functional groups comprises, for example, alkoxyl group, glycidyl, carboxyl (acid anhydrides that comprises diprotic acid), hydroxyl, isocyanate group and aldehyde radical and other functional groups of hydroxyl being had high avidity.Has the compound that can form the functional group of chemical bond with hydroxyl, the compound that perhaps has the functional group that does not form chemical bond with hydroxyl but hydroxyl is had high chemical affinity is including, but not limited to having the compound of above-mentioned functional group, for example, silane compound, titanate compound, glycidyl compound, carboxylic acid and alcohol.These compounds can use separately, also can use its two or more simultaneously.

The example of described silane compound is including, but not limited to vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-An Bingjisanjiayangjiguiwan, γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl dimethyl methyl TMOS, γ-An Bingjisanyiyangjiguiwan, γ-aminopropyl methyldiethoxysilane, γ-aminopropyl dimethylethoxysilane, Union carbide A-162, dimethyldimethoxysil,ne, the trimethylammonium methoxy silane, the hexyl Trimethoxy silane, the hexyl triethoxyl silane, N-β-(amino-ethyl)-γ-An Bingjisanjiayangjiguiwan, N-β-(aminoethyl)-γ-An Bingjisanyiyangjiguiwan, N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane, the octadecyl Trimethoxy silane, octadecyltriethoxy silane, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane and γ-methacryloxypropyl triethoxyl silane.These silane can use separately, also can use its two or more simultaneously.

In chemical modification method (4) and (5), for described anionic surfactant compound, and on the molecular chain except having anionic sites, the anionic surfactant compound that also has one or more reactive functional groups has no particular limits, as long as it is for carrying out chemically treated compound by the layered silicate of ionic interaction partners, the example of these compounds comprises the vitriol of the vitriol of sodium laurate, sodium stearate, sodium oleate, higher alcohols, senior secondary alcohol, the vitriol of unsaturated alcohol etc.These compounds can use separately, also can use its two or more simultaneously.

Layered silicate is preferably, measure through the wide-angle x-ray diffraction method, the average layer spacing of its (001) face is 3nm or bigger, partly or entirely being separated into below 5 layers or 5 layers of layered silicate, layered silicate more preferably, wherein, its average layer spacing is 3 to 5nm, partly or entirely being separated into below 5 layers or 5 layers of layered silicate.In this manual, the interlamellar spacing of layered silicate refers to the mean distance between the thin thin crystal layer of layered silicate, this distance can be by the X-ray diffraction peak, and with the method that transmission electron microscope is taken pictures, also is that the wide-angle x-ray diffraction technology is measured.

The average layer spacing of so-called layered silicate is that 3nm or bigger this situation refer to, separate 3nm or bigger between each layer of described layered silicate, and so-called layered silicate be separated into partly or entirely that this situation refers to below 5 layers or 5 layers, the part or all of quilt of the lamination of layered silicate disperses.Said circumstances means that the interlayer interaction of layered silicate has been weakened.

When the average layer spacing of layered silicate is 3nm or bigger, simultaneously layered silicate partly or entirely be separated into below 5 layers or 5 layers the time, reveal excellent flame, physicals, thermotolerance and dimensional stability by the stock chart that layered silicate is mixed and be dispersed in the insulating substrate of the present invention that obtains in thermoplastic resin and/or the thermosetting resin.When average layer spacing during, can not fully be separated into nano level layered silicate, so this can be limited in the level that those adopt the raw material of the common resulting insulating substrate of mineral filler to the improvement of physicals and flame retardant resistance less than 3nm.More preferably the average layer spacing is 3 to 5nm.When average layer spacing during greater than 5nm, the crystal layer that all of layered silicate are thin is all separated from one another, thereby the interaction that makes layered silicate is reduced to negligible level, so reduced the speed that forms rete when burning, this can cause improving flame retardant resistance fully.

The layered silicate quilt be separated into partly or entirely that this situation specifically refers to below 5 layers or 5 layers, preferred 10% or more, more preferably 20% or more layered silicate be dispersed into below 5 layers or 5 layers.

Can be by using transmission electron microscope 50,000 or 100, observe the dispersion state of layered silicate under 000 times the magnification, determine that in prospective region visible is separated into the sum (X) of the Guinier-Preston zone of the number (Y) of Guinier-Preston zone below 5 layers or 5 layers and layered silicate, and calculate the percentage ratio that is separated into the layered silicate below 5 layers or 5 layers by following equation (3):

Equation (3): the percentage ratio (%)=(Y/X) * 100 that is separated into the layered silicate below 5 layers or 5 layers

In order to obtain above-mentioned effect, layered silicate is separated into below 5 layers or 5 layers, more preferably be separated into below 3 layers or 3 layers, more preferably be separated into individual layer.

In the raw material of insulating substrate of the present invention, when the average layer spacing of layered silicate is 3nm or bigger, when part or all of layered silicate is broken up into below 5 layers or 5 layers simultaneously, promptly when layered silicate when thermoplastic resin and/or thermosetting resin camber disperse, interfacial area between thermoplastic resin and/or thermosetting resin and the layered silicate increases, thereby has reduced the mean distance between the crystal thin layer of layered silicate.

When the interfacial area of thermoplastic resin and/or thermosetting resin and layered silicate increased, the increase of the bonding force on thermoplastic resin and/or thermosetting resin and layered silicate surface was so for example improved physicals such as Young's modulus.In addition, when the bonding force on thermoplastic resin and/or thermosetting resin and layered silicate surface increased, its melt viscosity increased, so improved its moldability.Compare with inorganic materials, because gas molecule is easy to diffuse into polymkeric substance, therefore, when gas molecule diffused into thermoplastic resin and/or thermosetting resin, gas molecule was diffused in around the inorganic materials, thereby showed gas-barrier property.

On the other hand, when the mean distance between the crystal thin layer of layered silicate reduced, the raw material of described insulating substrate is easy to form by layered silicate when burning assembled the crystal thin layer sintered compact that forms.Also promptly, be 3nm or when bigger, the raw material of this insulating substrate is easy to form and can serves as fire-retardant tectal sintered compact when the crystal thin layer of the layered silicate in the raw material of insulating substrate is separated into the average layer spacing.Just formed sintered compact at the burning initial stage, so sintered compact has not only cut off the supply of extraneous oxygen, and cut off the generation of inflammable gas in the combustion processes, thereby made the stock chart of this insulating substrate reveal excellent flame.

In the raw material of the insulating substrate of first aspect present invention,, contain the layered silicate of 0.1 to 100 weight part with respect to the mixture of per 100 parts by weight of thermoplastic resin or thermoplastic resin and thermosetting resin.

In the raw material of the insulating substrate of second aspect present invention,, contain the layered silicate of 0.1 to 100 weight part with respect to the thermosetting resin of per 100 weight parts.

In the raw material of the insulating substrate of third aspect present invention,, contain the layered silicate of 0.1 to 100 weight part with respect to per 100 parts by weight of epoxy resin.

With respect to 100 parts by weight of thermoplastic resin and/or thermosetting resin, if the content of layered silicate is less than 0.1 weight part, then be unfavorable for improving flame retardant resistance or physicals, and work as this content greater than 100 weight parts, then the use properties of the raw material of this insulating substrate is not good, because its density (proportion) has increased, and its physical strength has reduced.This content is preferably 1 to 50 weight part, more preferably 5 to 20 weight parts.If this content is less than 1 weight part, then when the raw material of insulating substrate of the present invention was molded to film, it can not show enough flame retardant effects, and worked as this content greater than 50 weight parts, can reduce its moldability.When this content is 5 to 20 weight parts, it can not produce the problem of mechanical and physical performance and processing characteristics aspect when obtaining enough flame retardant effects.

The method of disperseing layered silicate in thermoplastic resin and/or thermosetting resin is including, but not limited to the method that adopts the above-mentioned layered silicate that organises; With conventional means thermoplastic resin and/or thermosetting resin are mixed with layered silicate, make the method for this mixture foaming then; Or the method for employing dispersion agent.By adopting these dispersing method, layered silicate can be more evenly and slightly is dispersed in thermoplastic resin and/or the thermosetting resin.

With conventional means thermoplastic resin and/or thermosetting resin are mixed with layered silicate, make the method for this mixture foaming then, be to adopt whipping agent to make thermoplastic resin and/or thermosetting resin foaming, make the energy of foaming change the energy that disperses layered silicate into then.

The example of whipping agent is including, but not limited to: gaseous foaming agent, the liquid whipping agent of easy volatile and the solid-state whipping agent of thermal degradation.These whipping agents can use separately, also can use its two or more simultaneously.

Make the thermoplastic resin and/or the thermosetting resin foaming that contain layered silicate, thereby the method that layered silicate is dispersed in thermoplastic resin and/or the thermosetting resin comprises, but be not limited to following two kinds of methods, one is, under high pressure gaseous foaming agent is injected in the resin combination of forming by the layered silicate of 100 parts by weight of thermoplastic resin and/or thermosetting resin and 0.1 to 100 weight part, make the gaseous foaming agent gasification in the described resin combination then, thereby produce foam; Perhaps, other method is, the whipping agent of thermal degradation is added the interlayer of layered silicate, and heating is decomposed the whipping agent of this thermal degradation then, thereby produces foam.

The raw material of insulating substrate of the present invention preferably contains the fire retardant that is substantially free of halogen composition.

So-called " being substantially free of halogen composition " refer to, the very a spot of halogen that allows to contain in the course of processing and be infected with.

The example of described fire retardant is including, but not limited to metal hydroxides, for example aluminium hydroxide, magnesium hydroxide, dosonite, calcium aluminate, gypsum dihydrate and calcium hydroxide; Metal oxide; Phosphorus compound, for example red phosphorus and ammonium polyphosphate; Stratiform coordinated water compound, the nitrogenous compound, fluoro-resin, silicone oil and the hydrotalcite that for example comprise trimeric cyanamide and melamine derivative, described melamine derivative all can pass through surface treatment for for example melamine cyanurate, trimeric cyanamide isocyanuric acid ester and trimeric cyanamide phosphoric acid ester, described melamine derivative; With the silicone-acrylic compounded rubber.Especially preferably adopt metal hydroxides and melamine derivative.

Preferred especially magnesium hydroxide and aluminium hydroxide in metal hydroxides, their available various surface treatment agents carry out surface treatment.The example of described surface treatment agent is including, but not limited to silane coupling agent, titanate coupling agent, PVA surface treatment agent, epoxy surface treatment agent etc.These fire retardants can use separately, also can use its two or more simultaneously.

When fire retardant is metal hydroxides, its content in the raw material of the insulating substrate of first aspect present invention is preferably, with respect to the mixture of 100 parts by weight of thermoplastic resin or thermoplastic resin and thermosetting resin, the content of described fire retardant is 0.1 to 100 weight part.Its content in the raw material of the insulating substrate of second aspect present invention is preferably, and with respect to the thermosetting resin of 100 weight parts, the content of fire retardant is 0.1 to 100 weight part.Its content in the raw material of the insulating substrate of third aspect present invention is preferably, and with respect to 100 parts by weight of epoxy resin, the content of fire retardant is 0.1 to 100 weight part.If its content is lower than 0.1 weight part, then can not obtain enough flame retardant effects, if and its content is higher than 100 weight parts, then the density of the raw material of this insulating substrate (proportion) can become excessive and can't practical application, perhaps can significantly destroy its flexibility and ductility.This content is 5 to 80 weight parts more preferably, and more preferably 10 to 70 weight parts.Be lower than at this content under the situation of 5 weight parts, when forming thin insulating substrate, its flame retardant resistance deficiency, and if this content greater than 80 weight parts, then can increase scrap rate in the swelling under the high temperature process because of it.The content of described fire retardant is preferably 10 to 70 weight parts, when obtaining enough flame retardant resistances, can not have problems at aspects such as mechanical and physical performance, electric physicals and processing characteristicies like this.

When fire retardant is melamine derivative, its content in the raw material of the insulating substrate of first aspect present invention is preferably, with respect to the mixture of 100 parts by weight of thermoplastic resin or thermoplastic resin and thermosetting resin, the content of fire retardant is 0.1 to 100 weight part.Its content in the raw material of the insulating substrate of second aspect present invention is preferably, and with respect to the thermosetting resin of 100 weight parts, the content of fire retardant is 0.1 to 100 weight part.Its content in the raw material of the insulating substrate of third aspect present invention is preferably, and with respect to 100 parts by weight of epoxy resin, the content of fire retardant is 0.1 to 100 weight part.If its content is lower than 0.1 weight part, then can not obtain sufficient flame retardant effect.If its content greater than 100 weight parts, then can significantly damage for example mechanical and physical performance such as flexibility and ductility.This content is 5 to 70 weight parts more preferably, more preferably 10 to 50 weight parts.If this content is lower than 5 weight parts, when forming thin insulating film, its flame retardant resistance deficiency, and if this content greater than 70 weight parts, then can significantly damage for example mechanical and physical performance such as flexibility and ductility.The content of described fire retardant is preferably 10 to 70 weight parts, when obtaining enough flame retardant resistances, can not have problems at aspects such as mechanical and physical performance, electric physicals and processing characteristicies like this.

If necessary, the raw material of insulating substrate of the present invention can mix with one or more additives, described additive has, for example, filler, tenderizer, softening agent, lubricant, static inhibitor, antifogging agent, tinting material, antioxidant (anti-aging agent), thermo-stabilizer, photostabilizer and UV light absorber, these content of additive should be able to reach purpose of the present invention.

The preparation method of the raw material of insulating substrate of the present invention is including, but not limited to following two kinds of methods, one of them method (direct mixing method) comprises the steps: to make thermoplastic resin and/or the thermosetting resin and the layered silicate of predetermined amount, and if necessary, one or more additives directly mix, then mixing this mixture under normal temperature or heating condition; Perhaps, other method is it to be mixed in the solvent, then except that desolvating.Also have a kind of alternative method (mother material) may further comprise the steps: most of layered silicate is mixed with thermoplastic resin and/or thermosetting resin, mixing this mixture is so that make masterbatch, under normal temperature or heating condition, with this masterbatch and remaining thermoplastic resin and/or thermosetting resin, and if necessary, one or more additives of predetermined amount are mixing, and it is mixed in solvent.

Concentration for the layered silicate in the masterbatch has no particular limits, but with respect to 100 parts by weight of thermoplastic resin and/or thermosetting resin, the content of layered silicate is preferably 1 to 500 weight part, more preferably 5 to 300 weight parts.If this content is less than 1 weight part, then this masterbatch will lose its advantage, can be diluted as the ability of any concentration, if and this content is greater than 500 weight parts, then can damage the dispersiveness of this masterbatch itself, the dispersiveness the when layered silicate that perhaps damages predetermined amount dilutes in thermoplastic resin and/or thermosetting resin.

In described mother material, the composition of resin combination (A) can be identical or different with the composition of resin combination (B), described resin combination (A) (masterbatch) has and thermoplastic resin and/or thermosetting resin blended layered silicate, and described resin combination (B) contains and is used for the layered silicate in the masterbatch is diluted to the thermoplastic resin and/or the thermosetting resin of predetermined concentration.

Described resin combination (A) preferably contains at least a resin that is selected from the group of being made up of following resin: polyamide-based resin, polyphenylene oxide resinoid, polyether sulfone resin and vibrin, and layered silicate easily is scattered in above-mentioned resin; Described resin combination (B) preferably contains Resins, epoxy, and Resins, epoxy is cheap, and has excellent electric performance and high-temperature physical property.

The raw material of the insulating substrate that is made by mother material has also constituted one aspect of the present invention.

When adopting thermoplastic resin, might adopt a kind of like this method, wherein, the layered silicate that will contain polymerizing catalyst (polymerization starter) such as transition metal complex for example is mixing with the monomer of forming this thermoplastic resin, described monomer generation polymerization, thus carry out the preparation of the raw material of the polymerization of this thermoplastic resin and insulating substrate simultaneously.

When adopting thermosetting resin, might adopt a kind of like this method, wherein, the layered silicate that will contain amine curing agent (linking agent) for example is mixing with the resin raw material of forming described thermosetting resin, described resin raw material is cured (crosslinked), thereby carries out the preparation of the raw material of the curing (crosslinked) of described thermosetting resin and described insulating substrate simultaneously.

Adopting direct mixing method of the present invention or mother material to prepare in the method for raw material of insulating substrate, the method of compounding mixture is including, but not limited to, the method for coming compounding mixture by for example mixing facilities such as forcing machine, two roller mixer or Banbury mixer.

According to the combustion test of ASTME1354, at 50kW/m ²The radiation heating condition under the raw material of heating insulating substrate of the present invention made it burning in 30 minutes, under the compression speed of 0.1cm/s, measure the residue of combustion of the raw material of insulating substrate of the present invention, its yielding stress is preferably 4.9kPa or higher.When its yielding stress was lower than 4.9kPa, slight external force just can be destroyed this residue of combustion, thus its flame retardant resistance deficiency.Also promptly, the sintered compact of the raw material of described insulating substrate or the sintered compact of veneer sheet preferably keep its shape in whole combustion processes, thereby give full play to it as fire-retardant tectal effect.Its yielding stress is 15.0kPa or higher more preferably.

The raw material of insulating substrate of the present invention preferably is moulded to and is insulating substrate, perhaps is dissolved in the appropriate solvent to form to can be used to the varnish that floods or apply.In addition, the raw material of described insulating substrate preferably is used as the sandwich layer or the enhancement Layer of veneer sheet, printed circuit board (PCB), multi-layer substrate, the Copper Foil that adheres to resin, copper plate pressing plate, Kapton, be used for the film of TAB and be used for the prepreg of aforementioned applications, but the raw material of insulating substrate of the present invention is not limited to such use.

The preparation method of the raw material of insulating substrate of the present invention is including, but not limited to following method: the described raw material of melting mixing in forcing machine, extrude and film forming method (extrusion molding method) by the T shape shape of the mouth as one speaks or the circular shape of the mouth as one speaks then; With described material dissolution or for example be scattered in the organic solvent equal solvent, casting forming is the method (casting forming method) of film then; And the base material of forming by inorganic materials such as for example glass, or in varnish, flood by fabric substrate or the nonwoven substrates that organic polymer is formed, described varnish becomes described base material mold pressing the method (dip mold method) of film subsequently for described material dissolution or for example be scattered in that the organic solvent equal solvent obtains.Especially, preferably adopt extrusion molding method or casting forming method to prepare thin multi-layer substrate.Used base material is including, but not limited to woven fiber glass, Kevlar and polyparaphenylene's benzoxazole fiber in the dip mold method.

The raw material of insulating substrate of the present invention contains thermoplastic resin and/or thermosetting resin and layered silicate, therefore has the excellent physicals and the transparency.Be different from common mineral filler, layered silicate need not add in a large number just can obtain excellent physicals, and therefore, the insulating substrate of employing layered silicate can be made thinner, thereby can be used as highdensity thin multi-sheet printed base material.In the raw material of insulating substrate of the present invention, since the molecular chain and the laminar silicic acid salt binding of resin, so it has high glass transition and heat-resistant deforming temperature, so, the thermotolerance of the raw material of described insulating substrate has improved, and its hotline expansion coefficient has reduced.In addition, because layered silicate is as formation crystalline nucleator, so the dimensional stability of the raw material of insulating substrate of the present invention has also improved.By adding layered silicate, the raw material of insulating substrate of the present invention has the effect that prevents the dimensional stability deterioration that causes because of suction and moisture absorption swelling.

Form the sintered compact of layered silicate during the material combusting of insulating substrate of the present invention, so that keep the profile of its residue of combustion.So residue of combustion can not break, thereby stoped spreading of flame after burning.So the stock chart of insulating substrate of the present invention reveals excellent flame.By further combining, can obtain high physicals and high flame retardant properties simultaneously, and can not have a negative impact environment with for example non-halogen flame retardant such as metal hydroxides or melamine derivative.

Hereinafter will describe the present invention in more detail, but the present invention is not limited to following examples by reference example.

Embodiment 1

To small-sized forcing machine (TEX30, JSW produces) middle (Xyron (PKL) X9102 of the modified polyphenylene ether resin as thermoplastic resin that adds 92.3 weight parts, industry society of Asahi Chemical Industry produces), swelling fluorine mica (Somasif MAE-100 with 7.7 weight parts as layered silicate, Co-op Chemical Co., Ltd. produce), described swelling fluorine mica has carried out the processing that organises with the distearyl dimethyl quaternary ammonium.At 280 ℃ of following melting mixings, be extruded into wire, make the thread of extruding form particle with tablets press then, thereby obtain the raw material of insulating substrate.

Then, the temperature of using lower compression roller is controlled to be the raw material of insulating substrate of 280 ℃ thermocompressor calendering gained respectively, thereby makes the template foundry goods that thickness is 2mm and 100 μ m.

Embodiment 2

The feed particles and the thickness that prepare insulating substrate according to the method identical with embodiment 1 are the template foundry goods of 2mm and 100 μ m, difference has been further to sneak into the magnesium hydroxide as fire retardant (KISUMA 5J, consonance chemical industry society produces) of 20 weight parts.

Embodiment 3

Clicyclic hydrocarbon resinoid (norbornene resin with 70 weight parts as thermoplastic resin, Zeonor 1600R, Nippon Zeon Co., Ltd. produce) and thickness be swelling fluorine mica (the Somasif MAE-100 as layered silicate of 20 weight parts, Co-op Chemical Co., Ltd. produce) adding hexanaphthene (superfine, society produces with the pure pharmaceutical worker's industry of light) in, the concentration that makes resin is 30 weight %, and described swelling fluorine mica has carried out the processing that organises with the distearyl dimethyl quaternary ammonium.Stir this mixture, make its mixing and dissolving.Synthetic silica (the ELSIL (sphere) that in above-mentioned mixing solutions, adds 85 weight parts, Mitsubishi Materials society produces) and the benzenetricarboxylic acid triallyl (TRIAM705 of 30 weight parts, three are total to society produces), make its mixing obtain solution under stirring, dry then gained solution is so that remove solvent, thereby obtains the raw material of insulating substrate.

Then, the temperature of using lower compression roller is controlled to be the raw material of insulating substrate of 280 ℃ thermocompressor calendering gained respectively, thereby makes the template foundry goods that thickness is 2mm and 100 μ m.

Embodiment 4

To small-sized forcing machine (TEX30, JSW produces) the middle inferior amide resins of the polyethers as thermoplastic resin of 92.3 weight parts, swelling fluorine mica (the Somasif MAE-100 as layered silicate of 7.7 weight parts of adding, Co-op Chemical Co., Ltd. produce) and thickness be (the KISUMA 5J of the magnesium hydroxide as fire retardant of 20 weight parts, consonance chemical industry society produces), described swelling fluorine mica has carried out the processing that organises with the distearyl dimethyl quaternary ammonium.Melting mixing also is extruded into wire, makes the thread of extruding form particle with tablets press then, thereby obtains the raw material of insulating substrate.

Then, the temperature of using lower compression roller is controlled to be the raw material of insulating substrate of 350 ℃ thermocompressor calendering gained respectively, thereby makes the template foundry goods that thickness is 2mm and 100 μ m.

Embodiment 5

With the mixture of the mixing following material of stirrer 1 hour: 92.3 parts by weight of epoxy resin compositions, 7.7 swelling fluorine mica (the Somasif MAE-100 as layered silicate of weight part, Co-op Chemical Co., Ltd. produce) and thickness be (the KISUMA 5J of the magnesium hydroxide as fire retardant of 20 weight parts, consonance chemical industry society produces), described composition epoxy resin is by bisphenol f type epoxy resin (the EPICLON 830LVP of 57.7 weight parts, big Japanese ink chemical industry society produces), 15.7 the BT resin (BT2100B of weight part, gas chemistry society of Mitsubishi produces), 15.7 the neopentylglycol diglycidyl ether of weight part, 2.1 γ-glycidoxypropyltrime,hoxysilane (A-187 of weight part, Nippon Unicar Co., Ltd. produce) and (the Nihon Kagaku Sangyo Co. of the ferric acetyl acetonade as curing catalysts of 1.1 weight parts, Ltd. produce) to form, described swelling fluorine mica has carried out the processing that organises with the distearyl dimethyl quaternary ammonium.Carry out froth breaking then, obtain liquid insualtion resin composition.

Then, the liquid insualtion resin composition of gained was heated 3 hours down at 110 ℃, subsequently further 160 ℃ down heating made it in 3 hours to solidify, thereby obtain the raw material of insulating substrate, then the raw material of the insulating substrate of gained being formed thickness is the template foundry goods of 2mm and 100 μ m.

Embodiment 6 to 11

To small-sized forcing machine (TEX30, JSW's product) (Epikote 1007 for the solid epoxy resin of adding 90 weight parts in, oiling shell epoxy society product), (the New S-Ben D of the natural montmorillonite as layered silicate of 10 weight parts, Fengshun society of foreign firm produces) and (the KISUMA 5J of the magnesium hydroxide as fire retardant of 0.1,5,10,70,80 and 100 weight parts, consonance chemical industry society produces), described natural montmorillonite has carried out the processing that organises with the distearyl dimethyl quaternary ammonium.At 100 ℃ of following melting mixings and be extruded into wire, make the thread of extruding form particle with tablets press then.

The particle of gained is dissolved in methylethylketone, solid epoxy resin content with respect to 90 weight parts, the Dyhard RU 100 (CG-1200 that in this solution, adds 3 weight parts as solidifying agent, BTI Japan society produces) and curing catalysts (the Curezol 2E4HZ of 3 weight parts, four countries change into society and produce), fully stir this mixture and make its froth breaking, thereby obtain insualtion resin composition solution.

Then, the insualtion resin composition solution of gained is placed in the mould, or it is coated on the polyethylene terephthalate sheet material, so that removal solvent, then, heating is 3 hours under 110 ℃, further heats down at 160 ℃ subsequently to make it in 3 hours to solidify, thereby obtain the raw material of insulating substrate, then the raw material of the insulating substrate of gained being formed thickness is the template foundry goods of 2mm and 100 μ m.

Embodiment 12 to 17

To small-sized forcing machine (TEX30; JSW's product) (Epikote 1007 for the solid epoxy resin of adding 90 weight parts in; oiling shell epoxy society produces); epoxide modified divinyl rubber (the Denalex R-45EPT as rubber constituent of 10 weight parts; Nagase ChemtexCorporation produces); the magnesium hydroxide as fire retardant of 30 weight parts (KISUMA 5J; consonance chemical industry society produces) and 0.1; 1; 5; 20; the synthetic mica (ME-100 as layered silicate of 50 and 100 weight parts; Co-op Chemical Co.; Ltd. produce); at 100 ℃ of following melting mixings and be extruded into wire, then with making the thread of extruding form particulate state with tablets press then.

The particle of gained is dissolved in methylethylketone, solid epoxy resin content with respect to 90 weight parts, the Dyhard RU 100 (CG-1200 that in this solution, adds 3 weight parts as solidifying agent, BTI Japan society produces) and curing catalysts (the Curezol 2E4HZ of 3 weight parts, four countries change into society and produce), fully stir this mixture and make its froth breaking, thereby obtain insualtion resin composition solution.

Then, the insualtion resin composition solution of gained is placed in the mould, or it is coated on the polyethylene terephthalate sheet material, so that removal solvent, then, heating is 3 hours under 110 ℃, further heats down at 160 ℃ subsequently to make it in 3 hours to solidify, thereby obtain the raw material of insulating substrate, making the raw material formation thickness of the insulating substrate of gained then is the template foundry goods of 2mm and 100 μ m.

Embodiment 18

To small-sized forcing machine (TEX30, JSW produces) middle (the Xyron X9102 of the polyphenylene oxide resin as thermoplastic resin that adds 40 weight parts, industry society of Asahi Chemical Industry system), epoxide modified divinyl rubber (the Denalex R-45EPT as rubber constituent of 10 weight parts, Nagase ChemtexCorporation produces), the synthetic mica (SomasifMAE-100 as layered silicate of 10 weight parts, Co-op Chemical Co., Ltd. produce), the melamine derivative melamine cyanurate as fire retardant of 50 weight parts (producing chemical society daily produces), described synthetic mica has carried out the processing that organises with the distearyl dimethyl quaternary ammonium.At 280 ℃ of following melting mixings and be extruded into wire, then with making the thread of extruding form particle with tablets press then.

The particle of gained is dissolved in toluene, polyphenylene oxide resin with respect to 40 weight parts, the liquid bisphenol A type Resins, epoxy (D.E.R.331L that in this solution, adds 60 weight parts, Dow Chemical Japan society produces), with respect to the solid epoxy resin of 60 weight parts, add the Dyhard RU 100 (CG-1200 as solidifying agent of 2 weight parts, BTI Japan society produces), and, add the curing catalysts (Curezol 2E4HZ, four countries change into society and produce) of 2 weight parts with respect to the solid epoxy resin of 60 weight parts.Fully stir this mixture and make it froth breaking, thereby make insualtion resin composition solution.

Then, the insualtion resin composition solution of gained is placed in the mould, or it is coated on the polyethylene terephthalate sheet material, so that removal solvent, then, heating is 3 hours under 110 ℃, further heats down at 160 ℃ subsequently to make it in 3 hours to solidify, thereby obtain the raw material of insulating substrate, making the raw material formation thickness of the insulating substrate of gained then is the template foundry goods of 2mm and 100 μ m.

Embodiment 19

To small-sized forcing machine (TEX30, JSW produces) the middle nylon-6 resin (T-850 that adds 30 weight parts as thermoplastic resin, Japan spins long-pending society and produces), natural montmorillonite (the Bengel A as layered silicate of 10 weight parts, Fengshun society of foreign firm produces) and the magnesium hydroxide as fire retardant (KISUMA 5J, consonance chemical industry society product) of 40 weight parts.At 250 ℃ of following melting mixings and be extruded into wire, then with making the thread of extruding form particle with tablets press then.

The particle of gained is dissolved in ortho chloro phenol, nylon-6 resin with respect to 30 weight parts, the liquid bisphenol A type Resins, epoxy (D.E.R.331L that in this solution, adds 70 weight parts, Dow Chemical Japan society produces), solid epoxy resin with respect to 70 weight parts, the Dyhard RU 100 (CG-1200 that adds 2.3 weight parts as solidifying agent, BTI Japan society produces), with solid epoxy resin content with respect to 90 weight parts, the curing catalysts (Curezol 2E4HZ, four countries change into society and produce) that adds 2.3 weight parts.Fully stir this mixture and make it froth breaking, thereby make insualtion resin composition solution.

Then, the insualtion resin composition solution of gained is placed in the mould, or it is coated on the polyethylene terephthalate sheet material, so that removal solvent, then, heating is 3 hours under 110 ℃, further heats down at 160 ℃ subsequently to make it in 3 hours to solidify, thereby obtain the raw material of insulating substrate, making the raw material formation thickness of the insulating substrate of gained then is the template foundry goods of 2mm and 100 μ m.

Embodiment 20

To small-sized forcing machine (TEX30, JSW produces) the middle polyether-ether-ketone resin (450G2 that adds 90 weight parts as thermoplastic resin, Victorex, plc. produce), (the New S-Ben D of the natural montmorillonite as layered silicate of 10 weight parts, Fengshun society of foreign firm produces) and the melamine derivative melamine cyanurate as fire retardant (producing chemical society product daily) of 10 weight parts, described natural montmorillonite has carried out the processing that organises with the distearyl dimethyl quaternary ammonium.At 370 ℃ of following melting mixings, be extruded into wire, make the thread of extruding form particulate state with tablets press then, thereby obtain the raw material of insulating substrate.

Then, the temperature of using lower compression roller is controlled to be the raw material of insulating substrate of 370 ℃ thermocompressor calendering gained respectively, thereby makes the template foundry goods that thickness is 2mm and 100 μ m.

Embodiment 21

(the Somasif MAE-100 of the synthetic mica as layered silicate with 10 weight parts, Co-opChemical Co., Ltd. produce) add the thermoset polyimide resin (SKYBOND703 of 90 weight parts, I.S.T. society produces) in and obtain a kind of varnish, described synthetic mica has carried out the processing that organises with the distearyl dimethyl quaternary ammonium.

Then, the varnish of gained is coated on the polyethylene terephthalate thin film, with resulting sheet 120 ℃ of heating 60 hours down, thereby make the sheet material that thickness is 100 μ m, and thereon lamination the thickness of described sheet material be the template foundry goods of 2mm.

Comparative Examples 1

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 1 are the template foundry goods of 2mm and 100 μ m, it is swelling fluorine mica (the Somasif MAE-100 that the lime carbonate of 50 μ m replaces 7.7 weight parts that difference is to adopt the median size of 7.7 weight parts, Co-opChemical Co., Ltd. produces).

Comparative Examples 2

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 2 are the template foundry goods of 2mm and 100 μ m, and difference is not sneak into swelling fluorine mica (Ltd. produces for SomasifMAE-100, Co-op Chemical Co.).

Comparative Examples 3

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 3 are the template foundry goods of 2mm and 100 μ m, and difference is not sneak into swelling fluorine mica (Ltd. produces for SomasifMAE-100, Co-op Chemical Co.).

Comparative Examples 4

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 4 are the template foundry goods of 2mm and 100 μ m, and difference is not sneak into swelling fluorine mica (Ltd. produces for SomasifMAE-100, Co-op Chemical Co.).

Comparative Examples 5

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 5 are the template foundry goods of 2mm and 100 μ m, and difference is not sneak into swelling fluorine mica (Ltd. produces for SomasifMAE-100, Co-op Chemical Co.).

Comparative Examples 6

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 6-11 are the template foundry goods of 2mm and 100 μ m, and difference is that the add-on of magnesium hydroxide is 0.05 weight part, and the add-on of natural montmorillonite is 0.05 weight part.

Comparative Examples 7

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 6-11 are the template foundry goods of 2mm and 100 μ m, and difference is that the add-on of magnesium hydroxide is 120 weight parts.

Comparative Examples 8

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 12-17 are the template foundry goods of 2mm and 100 μ m, and difference is that the add-on of synthetic mica is 0.05 weight part.

Comparative Examples 9

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 12-17 are the template foundry goods of 2mm and 100 μ m, and difference is that the add-on of synthetic mica is 130 weight parts.

Comparative Examples 10

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 18 are the template foundry goods of 2mm and 100 μ m, and difference is that the add-on of melamine derivative is 0.05 weight part, and the add-on of synthetic mica is 0.05 weight part.

Comparative Examples 11

The raw material and the thickness that prepare insulating substrate according to the method identical with embodiment 18 are the template foundry goods of 2mm and 100 μ m, and difference is that the add-on of melamine derivative is 120 weight parts.

＜assessment 〉

Assess every performance (the tectal intensity of shape-holding property, residue of combustion when the average layer spacing of layered silicate, the percentage ratio that is separated into the layered silicate below 5 layers or 5 layers, passage processibility, burning) in accordance with the following methods by the template foundry goods of embodiment 1-21 and Comparative Examples 1-11 gained.The result as table 1 to shown in 6.

(1) the average layer spacing of layered silicate

Adopt X-ray diffraction survey meter (RINT1100, Rigaku Corporation produces) be that the plane of lamination of the template foundry goods laminate silicate of 2mm is carried out diffraction to thickness, 2 θ of the diffraction peak by measuring gained determine average layer spacing (nm), then according to the distance (d) of (001) face of Bragg diffraction equation (4) calculating layered silicate:

λ＝2dsinθ(4)

Wherein λ is 1.54, and d represents the distance (d) of (001) face of layered silicate, and θ represents diffraction angle.

(2) be separated into the percentage ratio of the layered silicate below 5 layers or 5 layers

With transmission electron microscope 50,000 times to 100, observe layered silicate under 000 times the magnification, determine that in certain zone visible is separated into the sum (X) of the Guinier-Preston zone of the number (Y) of Guinier-Preston zone below 5 layers or 5 layers and layered silicate, is separated into the percentage ratio of the layered silicate below 5 layers or 5 layers by following equation (3) calculating:

The percentage ratio of the layered silicate below 5 layers or 5 layers (%)=(Y/X) * 100 (3)

(3) passage processibility

Adopt strong peak short pulse vibration carbon dioxide laser processor (ML605 GTX-5100U, Mitsubishi Electric society produces) in thickness is the template foundry goods of 100 μ m, to form the microchannel.Then, (SEM) observes the surface of described passage under scanning electronic microscope, according to following criterion evaluation passage processibility:

Zero: the shape of passage and the difference of access portal are less, produce minor amount of carbide.

*: differing greatly of the shape of passage and access portal produces a large amount of carbide.

Shape-holding property when (4) burning

According to ASTM E 1354 " the flammability test method of material of construction ", be the specification that the template foundry goods of 2mm is cut into 100mm * 100mm with thickness, with corn calorie meter (cereal heat instrument) at 50kW/m ²The down burning of thermal radiation ray.Estimate the change of shape of template foundry goods before and after burning, the shape-holding property after burning according to following criterion evaluation:

Zero: shaped slightly changes

*: the shape noticeable change

(5) the tectal intensity of maximum heatrelease rate and residue of combustion

According to ASTM E 1354 " the flammability test method of material of construction ", be the specification that the template foundry goods of 2mm is cut into 100mm * 100mm with thickness, with corn calorie meter at 50kW/m ²The down burning of thermal radiation ray.In this burning, measure its maximum heatrelease rate (kW/m ²).Secondly, with the compression speed compression and combustion resistates of 0.1cm/s, measure the tectal intensity of residue of combustion (kPa) with intensity measuring device.

Table 1

		Embodiment 1		Embodiment 2		Embodiment 3		Embodiment 4		Embodiment 5
												Resin combination (weight part)	Resin	MODIFIED PP E resin	92.3	MODIFIED PP E resin	92.3	Alicyclic hydrocarbon resin	70	Polyetherimide resin	92.3	Bisphenol f type epoxy resin	55
The BT resin	15
		Neopentylglycol diglycidyl ether	15
Layered silicate	The swelling fluorine mica			7.7	The swelling fluorine mica	7.7	The swelling fluorine mica	20	The swelling fluorine mica	7.7	The swelling fluorine mica											7.7
		Fire retardant	-										Magnesium hydroxide	20	-		Magnesium hydroxide	20	Magnesium hydroxide	20
Other	-				-		Synthetic silica	85	-		γ-glycidoxypropyltrime,hoxysilane										2
			TRIAM	30									Ferric acetyl acetonade	1
							Assessment	Average layer spacing (nm)			3.5＜				3.5＜		3.5＜		3.5＜		3.5＜
Be separated into the percentage ratio of the layered silicate below 5 layers or 5 layers	10＜		10＜		10＜				10＜				10＜
								The passage processibility			○				○		○		○		○
Shape-holding property during burning	○		○		○				○				○
								Maximum heating speed (kW/m 2)			500				350		300		300		300
The tectal intensity (kPa) of residue of combustion	5		20		6				8				8

Table 2

		Embodiment 6		Embodiment 7		Embodiment 8		Embodiment 9		Embodiment 10		Embodiment 11
														Resin combination (weight part)	Resin	Solid epoxy resin	90	Solid epoxy resin	90	Solid epoxy resin	90	Solid epoxy resin	90	Solid epoxy resin	90	Solid epoxy resin	90
Layered silicate	Montmorillonite	10	Montmorillonite	10	Montmorillonite	10	Montmorillonite	10	Montmorillonite	10	Montmorillonite	10
													Fire retardant		Magnesium hydroxide	0.1	Magnesium hydroxide	5	Magnesium hydroxide	10	Magnesium hydroxide	70	Magnesium hydroxide	80	Magnesium hydroxide	100
Other	Solidifying agent	3	Solidifying agent	3	Solidifying agent	3	Solidifying agent	3	Solidifying agent	3	Solidifying agent	3
													Catalyzer		3	Catalyzer	3	Catalyzer	3	Catalyzer	3	Catalyzer	3	Catalyzer	3
	Assessment	Average layer spacing (nm)	3.5＜		3.5＜		3.5＜		3.5＜		3.5＜															3.5＜
Be separated into the percentage ratio of the layered silicate below 5 layers or 5 layers													10＜		10＜		10＜		10＜		10＜		10＜
		The passage processibility	○		○		○		○		○														○
Shape-holding property during burning													○		○		○		○		○		○
		Maximum heating speed (kW/m 2)	500		450		410		390		380														360
The tectal intensity (kPa) of residue of combustion													7		8		8		9		9		9

Table 3

		Embodiment 12		Embodiment 13		Embodiment 14		Embodiment 15		Embodiment 16		Embodiment 17
														Resin combination (weight part)	Resin	Solid epoxy resin	90	Solid epoxy resin	90	Solid epoxy resin	90	Solid epoxy resin	90	Solid epoxy resin	90	Solid epoxy resin	90
Epoxide modified divinyl rubber	10	Epoxide modified divinyl rubber	10	Epoxide modified divinyl rubber	10	Epoxide modified divinyl rubber	10	Epoxide modified divinyl rubber	10	Epoxide modified divinyl rubber	10
												Layered silicate	Synthetic mica			0.1	Synthetic mica	1	Synthetic mica	5	Synthetic mica	20	Synthetic mica	50	Synthetic mica	100
Fire retardant	Magnesium hydroxide	30	Magnesium hydroxide	30	Magnesium hydroxide	30	Magnesium hydroxide	30	Magnesium hydroxide	30	Magnesium hydroxide				30
												Other	Solidifying agent			3	Solidifying agent	3	Solidifying agent	3	Solidifying agent	3	Solidifying agent	3	Solidifying agent	3
Catalyzer	3	Catalyzer	3	Catalyzer	3	Catalyzer	3	Catalyzer	3	Catalyzer	3
													Assessment		Average layer spacing (nm)	3.5＜		3.5＜		3.5＜		3.5＜		3.5＜		3.5＜
Be separated into the percentage ratio of the layered silicate below 5 layers or 5 layers	10＜		10＜		10＜		10＜		10＜		10＜
														The passage processibility	○		○		○		○		○		○
Shape-holding property during burning	○		○		○		○		○		○
														Maximum heating speed (kW/m 2)	500		480		450		400		380		370
The tectal intensity (kPa) of residue of combustion	6		7		5		7		14		23

Table 4

		Embodiment 18		Embodiment 19		Embodiment 20		Embodiment 21
										Resin combination (weight part)	Resin	Liquid bisphenol A type Resins, epoxy	60	Liquid bisphenol A type Resins, epoxy	70	The PEEK resin	90	Thermoset polyimide resin	90
The PPE resin	40	The nylon-6 resin	30
				Epoxide modified divinyl rubber	10
Layered silicate	Synthetic mica					10	Montmorillonite	10	Montmorillonite			10	Synthetic mica	10
		Fire retardant	Melamine derivative	50	Magnesium hydroxide						40				Melamine derivative	10	-
Other	Solidifying agent					2	Solidifying agent	2.3	-			-
		Catalyzer	2	Catalyzer	2.3
	Assessment					Average layer spacing (nm)	3.5＜				3.5＜			3.5＜		3.5＜
Be separated into the percentage ratio of the layered silicate below 5 layers or 5 layers		10＜		10＜					10＜				10＜
						The passage processibility	○				○				○		○
Shape-holding property during burning		○		○					○				○
						Maximum heating speed (kW/m 2)	410				400				320		300
The tectal intensity (kPa) of residue of combustion		9		8					10				10

Table 5

		Comparative Examples 1		Comparative Examples 2		Comparative Examples 3		Comparative Examples 4		Comparative Examples 5
												Resin combination (weight part)	Resin	MODIFIED PP E resin	92.3	MODIFIED PP E resin	92.3	Alicyclic hydrocarbon resin	70	Polyetherimide resin	92.3	Bisphenol f type epoxy resin	55
The BT resin	15
		Neopentylglycol diglycidyl ether	15
Layered silicate	-			-		-		-		-
			Fire retardant										-		Magnesium hydroxide	20	Magnesium hydroxide	20	Magnesium hydroxide	20	Magnesium hydroxide	20
Other	Lime carbonate	7.7		-		Synthetic silica	85	-		γ-glycidoxypropyltrime,hoxysilane	2
			TRIAM										30	Ferric acetyl acetonade	1
						Assessment	Average layer spacing (nm)			-						-		-		-		-
Be separated into the percentage ratio of the layered silicate below 5 layers or 5 layers	-		-		-			-				-
							The passage processibility			×				×		×		○		○
Shape-holding property during burning	×		×		×			×				×
							Maximum heating speed (kW/m 2)			650				500		400		400		400
The tectal intensity (kPa) of residue of combustion	1		Do not form tectum		Less than 1			1				1

Table 6

		Comparative Examples 6		Comparative Examples 7		Comparative Examples 8		Comparative Examples 9		Comparative Examples 10		Comparative Examples 11
														Resin combination (weight part)	Resin	Solid epoxy resin	90	Solid epoxy resin	90	Solid epoxy resin	90	Solid epoxy resin	90	Liquid bisphenol A type Resins, epoxy	60	Liquid bisphenol A type Resins, epoxy	60
Epoxide modified divinyl rubber	10	Epoxide modified divinyl rubber	10	The PPE resin	40	The PPE resin	40
								Epoxide modified divinyl rubber	10	Epoxide modified divinyl rubber	10
				Layered silicate	Montmorillonite	0.05	Montmorillonite					10	Synthetic mica							0.05	Synthetic mica	130	Synthetic mica	0.05	Synthetic mica	10
Fire retardant	Magnesium hydroxide	0.05	Magnesium hydroxide					120	Magnesium hydroxide	30	Magnesium hydroxide				30	Melamine derivative	0.05	Melamine derivative	120
				Other	Solidifying agent	2	Solidifying agent					2	Solidifying agent							2	Solidifying agent	2	Solidifying agent	2	Solidifying agent	2
Catalyzer	1	Catalyzer	1					Catalyzer	1	Catalyzer	1				Catalyzer	2	Catalyzer	2
					Assessment	Average layer spacing (nm)	3.5＜					3.5＜							3.5＜		3.5＜		3.5＜		-
Be separated into the percentage ratio of the layered silicate below 5 layers or 5 layers	10＜		10＜						10＜		4			10＜		10＜
						The passage processibility	○						×					×		×		○		×
Shape-holding property during burning	×		○						×		○				×		×
						Maximum heating speed (kW/m 2)	850						350						620		350		810		340
The tectal intensity (kPa) of residue of combustion	Less than 1		8						1		23				Less than 1		1

Above table shows, in adopting by the prepared template foundry goods of the raw material of the resulting insulating substrate of embodiment 1-21, the average layer spacing of layered silicate is 3nm or bigger, simultaneously, the percentage ratio that is separated into the layered silicate below 5 layers or 5 layers is 10% or bigger, so shape-holding property and passage processibility when this template foundry goods has excellent burning.In addition, their easy formation can be as fire-retardant tectal sintered compact, so its maximum heatrelease rate is low, and the tectum intensity of residue of combustion is 4.9kPa or bigger.

Corresponding, Comparative Examples 1 adopts lime carbonate to replace swelling fluorine mica (layered silicate), in the template foundry goods of forming by the raw material of Comparative Examples 1 resulting insulating substrate, lime carbonate is not separated into stratiform, so shape-holding property and the passage processibility of this template foundry goods when burning is not good, they almost can not form as fire-retardant tectal sintered compact, so its maximum heatrelease rate is very high, and the tectum intensity of residue of combustion is extremely low.

Do not add layered silicate in the Comparative Examples 2 to 5, the template foundry goods of being made up of the raw material of Comparative Examples 2 to 5 resulting insulating substrates is when burning, its shape-holding property and passage processibility are relatively poor mostly, and some residue of combustion do not form tectum, and perhaps the tectal intensity of some residue of combustion is extremely low.

Laminar silicic acid salts contg in the Comparative Examples 8 is lower, the template foundry goods of being made up of the raw material of Comparative Examples 8 resulting insulating substrates is when burning, its shape-holding property and passage processibility are relatively poor mostly, and the tectal intensity of some residue of combustion is lower, and in Comparative Examples 9, the add-on of layered silicate is higher, in the template foundry goods of forming by the raw material of Comparative Examples 9 resulting insulating substrates, the percentage ratio that is separated into the layered silicate below 5 layers or 5 layers is 4%, and its passage processibility is relatively poor.

Comparative Examples 6 and 10 laminate silicate and flame retardant agent content are lower, the template foundry goods of being made up of the raw material of Comparative Examples 6 and 10 resulting insulating substrates is when burning, its shape-holding property is relatively poor, and its maximum heatrelease rate is bigger, and the tectal intensity of its residue of combustion is extremely low.The content of fire retardant is lower in the Comparative Examples 7 and 11, and there is for example problem such as passage poor in processability in the template foundry goods of being made up of the raw material of Comparative Examples 7 and 11 resulting insulating substrates.

The present invention can provide raw material, the veneer sheet of insulating substrate, the Copper Foil that adheres to resin, copper plate pressing plate, the film that is used for TAB and prepreg, they all have excellent physicals, dimensional stability, thermotolerance, flame retardant resistance etc., and especially when burning because of keeping profile to show the excellent fire retardant effect.

Claims (18)

1. the raw material of an insulating substrate, it contains the mixture of 100 parts by weight of thermoplastic resin or thermoplastic resin and thermosetting resin, and the layered silicate of 1 to 50 weight part, and silicon-dioxide, to measure through the wide-angle x-ray diffraction method, the average layer spacing of (001) face of layered silicate is 3nm or bigger, and partly or entirely being separated into below 5 layers or 5 layers of layered silicate quilt, wherein, in combustion test, at 50kW/m according to ASTM E 1354 ²The radiation heating condition under the heating described insulating substrate raw material made it in 30 minutes the burning, the yielding stress of its residue of combustion that records under the compression speed of 0.1cm/s is 4.9kPa or higher.

2. the raw material of insulating substrate according to claim 1, wherein, layered silicate contains the alkyl phosphate ion with 6 or more carbon atoms.

3. the raw material of insulating substrate according to claim 1, wherein, described thermoplastic resin is to be selected from least a by in polyphenylene oxide resinoid, the polyphenylene oxide resinoid, polyphenylene oxide resinoid with functional group modification or the group formed with mixture, alicyclic hydrocarbon resin, thermoplastic polyimide resinoid, polyether-ether-ketone resin, polyethersulfone resin, polyamide-imide resin and the polyester-imides resin of the polyphenylene oxide resinoid of functional group modification and polystyrene resins.

4. the raw material of an insulating substrate, wherein, the raw material of described insulating substrate contains the thermosetting resin of 100 weight parts, the layered silicate of 1 to 50 weight part, and silicon-dioxide, measure through the wide-angle x-ray diffraction method, the average layer spacing of (001) face of layered silicate is 3nm or bigger, and partly or entirely being separated into below 5 layers or 5 layers of layered silicate quilt, described thermosetting resin is to be selected from least a in the group of being made up of following resin: phenol resins, urea-formaldehyde resin, unsaturated polyester resin, allylic resin, thermoset polyimide resin, bismaleimide-triazine resin, the polyphenylene oxide resinoid of thermosetting modification, silicone resin and benzimidazole dihydrochloride resinoid, and wherein, according to the combustion test of ASTM E 1354, at 50kW/m ²The radiation heating condition under the heating described insulating substrate raw material made it in 30 minutes the burning, the yielding stress of its residue of combustion that records under the compression speed of 0.1cm/s is 4.9kPa or higher.

5. the raw material of insulating substrate according to claim 4, wherein, layered silicate contains the alkyl phosphate ion with 6 or more carbon atoms.

6. the raw material of insulating substrate according to claim 1, it also contains the fire retardant that is substantially free of halogen of 1 to 50 weight part.

7. the raw material of insulating substrate according to claim 4, it also contains the fire retardant that is substantially free of halogen of 1 to 50 weight part.

8. the raw material of an insulating substrate, wherein, corresponding to per 100 parts by weight of epoxy resin, the raw material of described insulating substrate contains the layered silicate of 1 to 50 weight part, 0.1 the fire retardant that is substantially free of halogen composition to 100 weight parts, and silicon-dioxide, measure through the wide-angle x-ray diffraction method, the average layer spacing of (001) face of layered silicate is 3nm or bigger, and partly or entirely being separated into below 5 layers or 5 layers of layered silicate quilt, and wherein, according to the combustion test of ASTM E 1354, at 50kW/m ²The radiation heating condition under the heating described insulating substrate raw material made it in 30 minutes the burning, the yielding stress of its residue of combustion that records under the compression speed of 0.1cm/s is 4.9kPa or higher.

9. the raw material of insulating substrate according to claim 8, wherein, layered silicate contains the alkyl phosphate ion with 6 or more carbon atoms.

10. according to the raw material of claim 6,7 or 8 described insulating substrates, wherein, described fire retardant is a metal hydroxides.

11. according to the raw material of claim 6,7 or 8 described insulating substrates, wherein, described fire retardant is a melamine derivative.

12. according to the raw material of claim 1,4 or 8 described insulating substrates, wherein, layered silicate is to be selected from least a in the group of being made up of montmorillonite, swelling mica and hectorite.

13. a veneer sheet, its raw material by claim 1,4 or 8 described insulating substrates makes.

14. a printed circuit board (PCB), its raw material by claim 1,4 or 8 described insulating substrates makes.

15. a copper plate pressing plate, its raw material by claim 1,4 or 8 described insulating substrates makes.

16. a Kapton, its raw material by claim 1,4 or 8 described insulating substrates makes.

17. a film that is used for TAB, its raw material by claim 1,4 or 8 described insulating substrates makes.

18. a prepreg, its raw material by claim 1,4 or 8 described insulating substrates makes.