JP2003313313A - Mold release film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mold release film that is excellent in heat resistance, mold release properties, antifoulancy and follow-up properties to the unevenness of a circuit pattern and is excellent in cushioning properties, strength and dimensional stability at a hot-press molding temperature; that has excellent flame retardancy and low flame spread without containing a halogen flame retardant and is high in safety; and that is small in environmental load when subjected to waste disposal. <P>SOLUTION: The mold release film has at least one layer formed from a resin composition which comprises 100 pts.wt. resin comprising at least one kind of a thermoplastic resin and/or a thermosetting resin and 0.1-100 pts.wt. phyllosilicate. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, releasability,
The present invention relates to a release film that is excellent in non-staining property, does not contain a halogen-based flame retardant, has excellent flame retardancy, and is easily disposed of.

[0002]

2. Description of the Related Art Conventionally, in a manufacturing process of a printed wiring board, a flexible printed wiring board, a multilayer printed wiring board, etc., when a copper clad laminate or a copper foil is hot-pressed via a prepreg or a heat resistant film, it is separated. Mold film is used. Further, in the manufacturing process of the flexible printed circuit board, when the cover lay film is heat-pressed and bonded to the flexible printed circuit board body on which the electric circuit is formed by the thermosetting adhesive, the cover lay film and the hot-pressed plate are bonded. Release films are widely used to prevent this.

In recent years, in addition to functions such as heat resistance to withstand hot press molding and mold releasability with respect to printed wiring boards and hot press plates, release films have been increasingly socially demanded for environmental problems and safety. Therefore, there is a growing demand for ease of disposal. Further, in order to improve the product yield at the time of hot press molding, non-contamination of copper circuits is becoming important.

Conventionally, as a release film, Patent Document 1
Fluorine-based films, silicone-coated polyethylene terephthalate films, polymethylpentene films, polypropylene films, and the like as disclosed in US Pat.

However, although the fluorine-based film is excellent in heat resistance, releasability and non-staining property, it is expensive and it is difficult to burn when incinerated in a waste treatment, and a toxic gas is generated. was there. On the other hand, the silicone-coated polyethylene terephthalate film and the polymethylpentene film have a problem that the migration of the silicone or the low-molecular weight component in the constituent components may cause contamination of the printed wiring board, especially the copper circuit, and impair the quality. . Further, the polypropylene film has a problem that it has poor heat resistance and insufficient releasability.

[0006]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2-175247

[Patent Document 2] Japanese Unexamined Patent Publication No. 5-283862

[0007]

In view of the above situation, the present invention is excellent in heat resistance, releasability and non-staining property, is excellent in flame retardance without containing a halogen-based flame retardant, and is a waste treatment. It is an object of the present invention to provide a release film that is easy to remove.

[0008]

SUMMARY OF THE INVENTION The present invention comprises at least one
A release film having at least one layer made of a resin composition containing 100 parts by weight of a resin made of one kind of thermoplastic resin and / or thermosetting resin and 0.1 to 100 parts by weight of a layered silicate. The present invention is described in detail below.

The release film of the present invention has at least one layer made of a resin composition. The resin composition contains a resin composed of at least one kind of thermoplastic resin and / or thermosetting resin. The thermoplastic resin is not particularly limited, and examples thereof include polyphenylene ether resin, functional group-modified polyphenylene ether resin; polyphenylene ether resin or functional group-modified polyphenylene ether resin, and polystyrene resin or other polyphenylene ether resin or functional group. A mixture of a modified polyphenylene ether resin and a compatible thermoplastic resin; an alicyclic hydrocarbon resin, a thermoplastic polyimide resin, a polyether ether ketone (PEEK) resin, a polyether sulfone resin, a polyamideimide resin, a polyester Imide resin, polyester resin, polyolefin resin, polystyrene resin, polyamide resin,
Examples thereof include polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl acetate resin, poly (meth) acrylic acid ester resin, and polyoxymethylene resin. Among them, a non-halogen resin is preferable, and a non-halogen crystalline resin having an aromatic ring structure in the main chain is more preferable. These thermoplastic resins may be used alone or in combination of two or more kinds.

Since the non-halogen resin is a non-halogen resin, it does not generate a toxic gas in the treatment after disposal. Among them, a resin having high heat resistance such as a polyphenylene ether resin, an alicyclic hydrocarbon resin, or a halogen-free crystalline resin having an aromatic ring structure in its main chain is preferable.

Examples of the polyphenylene ether resin include polyphenylene ether homopolymers and polyphenylene ether copolymers. The polyphenylene ether homopolymer is not particularly limited, and examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, and poly (2-methyl-6-ethyl-1,4-phenylene) ether. (2,6-diethyl-1,4-
Phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6)
-Di-n-propyl-1,4-phenylene) ether,
Poly (2-ethyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-)
6-hydroxyethyl-1,4-phenylene) ether and the like can be mentioned.

The polyphenylene ether copolymer is not particularly limited, and for example, a copolymer containing a part of alkyl trisubstituted phenol such as 2,3,6-trimethylphenol in the repeating unit of the polyphenylene ether homopolymer may be used. Examples thereof include polymers and copolymers obtained by graft-copolymerizing one or more styrene-based monomers such as styrene, α-methylstyrene and vinyltoluene with these polyphenylene ether copolymers. These polyphenylene ether resins may be used alone, and those having different compositions, components, molecular weights, etc.
You may use together 1 or more types.

The functional group-modified polyphenylene ether resin is not particularly limited. For example, the polyphenylene ether resin may be one or more of functional groups such as maleic anhydride group, glycidyl group, amino group and allyl group. And the like. These functional group-modified polyphenylene ether resins may be used alone or in combination of two or more kinds.

The mixture of the polyphenylene ether resin or the functional group-modified polyphenylene ether resin and the polystyrene resin is not particularly limited. For example, the polyphenylene ether resin or the functional group-modified polyphenylene ether resin and styrene alone are used. Combined; styrene and α-methylstyrene, ethylstyrene,
Examples thereof include copolymers with one or more styrene-based monomers such as t-butylstyrene and vinyltoluene; mixtures with polystyrene resins such as styrene-based elastomers. The polystyrene resins may be used alone or in combination of two or more. Further, a mixture of these polyphenylene ether resins or functional group-modified polyphenylene ether resins and polystyrene resins,
They may be used alone or in combination of two or more.

The alicyclic hydrocarbon resin is not particularly limited as long as it is a hydrocarbon resin having a cyclic hydrocarbon group in the polymer chain. For example, a cyclic olefin, that is, a homopolymer of a norbornene monomer or Examples thereof include copolymers. These alicyclic hydrocarbon resins may be used alone or in combination of two or more.

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

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

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

Among the above alicyclic hydrocarbon resins, commercially available products include, for example, JS (JS).
R) company name "Arton" series, Nippon Zeon company name "Zeonor" series, Mitsui Chemicals company name "Apel" series and the like.

The non-halogenated crystalline resin having an aromatic ring structure in the main chain means a benzene ring, a substituted benzene ring,
An aromatic ring such as a naphthalene ring, a substituted naphthalene ring, an anthracene ring or a substituted anthracene ring constitutes a part of the main chain, and means a crystalline resin having no halogen atom such as fluorine, chlorine or bromine. The halogen-free crystalline resin having an aromatic ring structure in the main chain is not particularly limited, and examples thereof include crystalline aromatic polyester resins, polyphenylene sulfide resins, polyether ether ketone resins, aromatic polyamide resins, and the like. To be Above all,
A crystalline aromatic polyester resin that does not contain a hetero atom in the molecule and can reduce the environmental load during incineration and is economically advantageous is preferable.

The above crystalline aromatic polyester resin is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, butanediol terephthalate polytetramethylene glycol copolyester. Examples include coalescence. Of these, polybutylene terephthalate is preferable. By including the butylene terephthalate component as the crystalline skeleton of the crystalline aromatic polyester resin, the non-staining property and the crystallinity become excellent.

The crystalline aromatic polyester resin is obtained by reacting an aromatic dicarboxylic acid or a derivative of an aromatic dicarboxylic acid capable of forming an ester with a low molecular weight aliphatic diol or a high molecular weight diol. You can Among them, an aromatic dicarboxylic acid, or a crystalline aromatic polyester resin obtained by reacting a derivative of an aromatic dicarboxylic acid capable of forming an ester with a low molecular weight aliphatic diol, and an aromatic dicarboxylic acid, or A mixed resin of a crystalline aromatic polyester resin obtained by reacting a derivative of an aromatic dicarboxylic acid capable of forming an ester with a low molecular weight aliphatic diol and a high molecular weight diol is preferably used.

The mixing ratio of the above-mentioned mixed resin is not particularly limited, but is crystalline obtained by reacting an aromatic dicarboxylic acid or a derivative of an aromatic dicarboxylic acid capable of forming an ester with a low molecular weight aliphatic diol. Crystals obtained by reacting an aromatic dicarboxylic acid or a derivative of an aromatic dicarboxylic acid capable of forming an ester with a low molecular weight aliphatic diol and a high molecular weight diol, wherein the aromatic polyester is 50 to 100% by weight. It is preferable that the content of the aromatic aromatic polyester is 0 to 50% by weight.

The aromatic dicarboxylic acid or the derivative of the aromatic dicarboxylic acid capable of forming an ester is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid,
Examples thereof include orthophthalic acid, naphthalene dicarboxylic acid, paraphenylenedicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, dimethyl orthophthalate, dimethyl naphthalene dicarboxylate and dimethyl paraphenylenedicarboxylate. These may be used alone,
Two or more kinds may be used in combination.

The low molecular weight aliphatic diol is not particularly limited, and examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol and 1,3-.
Examples include butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol and 1,4-cyclohexanedimethanol. These may be used alone 2
One or more species may be used in combination.

The high molecular weight diol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol and the like. These may be used alone or in combination of two or more.

The above-mentioned mixed resin has a heat resistance and a release property because the crystalline aromatic polyester containing a high molecular weight diol component is finely dispersed in a matrix made of a crystalline aromatic polyester not containing a high molecular weight diol component. Since it has excellent flexibility while maintaining moldability, the release film obtained by using this mixed resin is resistant to heat resistance and mold release, and to circuit patterns, through holes and other irregularities on the substrate. It is extremely excellent in balance with followability.

The thermosetting resin is a liquid, semi-solid or solid at room temperature, and a relatively low molecular weight substance which shows fluidity at room temperature or under heating is a curing agent, catalyst or heat. It means an insoluble and infusible resin formed by a chemical reaction such as a curing reaction or a cross-linking reaction to increase the molecular weight while forming a three-dimensional network structure.

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

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

The above-mentioned epoxy resin is not particularly limited, and conventionally known epoxy resins can be used, and examples thereof include the epoxy resins (1) to (11) shown below. These epoxy resins may be used alone or in combination of two or more kinds.

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

The above epoxy resin (2) is 3,4
-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2
-Methylcyclohexylmethyl-3,4-epoxy-2
-Methylcyclohexanecarboxylate, bis (3,3
4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro Examples thereof include alicyclic epoxy resins such as -3,4-epoxy) cyclohexanone-meta-dioxane and bis (2,3-epoxycyclopentyl) ether. Examples of commercially available epoxy resin (2) include, for example, trade name "EHPE-3".
150 "(softening temperature 71 ° C, manufactured by Daicel Chemical Industries, Ltd.) and the like.

As the above-mentioned epoxy resin (3), 1,4
-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, carbon number 2-9 (preferably 2-4)
And aliphatic epoxy resins such as polyglycidyl ether of a long-chain polyol containing polyoxyalkylene glycol containing an alkylene group or polytetramethylene ether glycol.

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

Examples of the epoxy resin (5) include triglycidyl isocyanurate and N of cyclic alkylene urea.
Glycidyl amine type epoxy resins such as N′-diglycidyl derivative, p-aminophenol N, N, O-triglycidyl derivative, and m-aminophenol N, N, O-triglycidyl derivative, and hydrogenated products thereof can be used. Can be mentioned.

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

Examples of the epoxy resin (7) include those obtained by epoxidizing a double bond of unsaturated carbon in a polymer containing a conjugated diene compound such as epoxidized polybutadiene as a main component or a polymer of a partially hydrogenated product thereof. Can be mentioned.

As the epoxy resin (8), a polymer block mainly containing a vinyl aromatic compound such as epoxidized SBS and a polymer block mainly containing a conjugated diene compound or a partially hydrogenated product thereof. Examples thereof include block copolymers having a polymer block in the same molecule in which the unsaturated carbon double bond of the conjugated diene compound is epoxidized.

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

Examples of the epoxy resin (10) include urethane-modified epoxy resin and polycaprolactone-modified epoxy resin in which a urethane bond or a polycaprolactone bond is introduced into the structures of the epoxy resins (1) to (9). .

Examples of the epoxy resin (11) include a rubber-modified epoxy resin in which a rubber component such as NBR, CTBN, polybutadiene, and acrylic rubber is contained in the epoxy resins (1) to (10).

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

The amine compound is not particularly limited, and examples thereof include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine and polyoxypropylenetriamine, and their derivatives;
Mensendiamine, isophoronediamine, bis (4-
Amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5 , 5) Cycloaliphatic amines such as undecane and derivatives thereof; m-xylenediamine, α- (m / p aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, α, α-bis (4- Aminophenyl) -p-
Examples thereof include aromatic amines such as diisopropylbenzene and derivatives thereof.

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

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

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

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

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

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

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

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

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

The thermosetting modified polyphenylene ether resin is not particularly limited. For example, the polyphenylene ether resin may be a glycidyl group, an isocyanate group,
Examples thereof include resins modified with a thermosetting functional group such as an amino group. These thermosetting modified polyphenylene ether resins may be used alone or in combination of two or more kinds.

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

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

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

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

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

The above resin composition contains a layered silicate. In addition, in the present specification, the layered silicate means a layered silicate mineral having an exchangeable metal cation between layers, and may be a natural product or a synthetic product.

The layered silicate is not particularly limited,
Examples thereof include smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite and nontronite, swelling mica, vermiculite and halloysite. Above all,
At least one selected from the group consisting of montmorillonite, hectorite, and swelling mica is preferably used. These layered silicates may be used alone,
Two or more kinds may be used in combination.

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

The layered silicate preferably has a large shape anisotropy effect defined by the following formula (1). By using a layered silicate having a large shape anisotropy effect, the resin composition has excellent mechanical properties.

[0064]

[Equation 1]

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

The cation exchange capacity of the layered silicate is not particularly limited, but the preferred lower limit is 50 milliequivalents /
100 g, the upper limit is 200 milliequivalents / 100 g. 5
When it is less than 0 milliequivalent / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate due to cation exchange becomes small, so that the crystal layers are not sufficiently depolarized (hydrophobicized). Sometimes. If it exceeds 200 milliequivalents / 100 g, the bonding force between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may become difficult to peel off.

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

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

The cationic surfactant is not particularly limited, and examples thereof include a quaternary ammonium salt and a quaternary phosphonium salt. Among them, a quaternary ammonium salt containing an alkylammonium ion having 6 or more carbon atoms and having an alkyl chain having 6 or more carbon atoms is preferably used because it can sufficiently hydrophobize the crystal layers of the layered silicate.

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

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

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

The functional group capable of chemically bonding to the hydroxyl group or the functional group having a large chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include an alkoxy group, a glycidyl group, a carboxyl group (including a dibasic acid anhydride). ), A hydroxyl group, an isocyanate group, an aldehyde group and the like.

The compound having a functional group capable of chemically bonding to the hydroxyl group or the compound having a functional group having a large chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include a silane compound and a titanate compound having the functional group. , Glycidyl compounds, carboxylic acids, alcohols and the like. These compounds may be used alone or 2
One or more species may be used in combination.

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

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

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

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

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

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

The above-mentioned layered silicate is measured by a wide-angle X-ray diffractometry in a layer made of a resin composition (0
It is preferable that the average interlayer distance of the (01) plane is 3 nm or more, and that part or all of the laminates are dispersed in 5 layers or less. The layered silicate has an average inter-layer distance of 3 nm or more, and part or all of the layered silicate is dispersed as a laminate of 5 layers or less to be a thermosetting resin and / or a thermoplastic resin. The interfacial area between the resin and the layered silicate is sufficiently large, and the distance between the flaky crystals of the layered silicate becomes appropriate, and a sufficient effect can be obtained by dispersing the layered silicate. In the above, the effect of improving mechanical properties and flame retardancy, which is greater than when using a normal inorganic filler, can be obtained.

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

Dispersing part or all of the layered silicate as a laminated body of 5 layers or less means, specifically, that the interaction between the flaky crystals of the layered silicate is weakened and the laminated body of the flaked crystals. Means that a part or all of is dispersed. Preferably, 10% or more of the layered silicate is dispersed as a laminated body having 5 layers or less, and more preferably 20% or more of the layered silicate is dispersed as a laminated body having 5 layers or less. The proportion of the layered silicate dispersed as a laminated body of 5 layers or less is a layered state that can be observed in a certain area by observing the resin composition with a transmission electron microscope at a magnification of 50,000 to 100,000 times. It can be calculated from the following formula (2) by measuring the total number of layers X of the silicate laminate and the number of layers Y of the laminate dispersed as a laminate of 5 or less layers.

[0084]

[Equation 2]

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

Since the resin composition has a sufficiently large interface area between the resin and the layered silicate, the interaction between the resin and the surface of the layered silicate is increased, so that the melt viscosity is increased and the moldability is improved. In addition, the mechanical properties such as elastic modulus are improved in a wide temperature range from normal temperature to high temperature, and the mechanical properties can be maintained even at high temperature above the glass transition point or melting point of the resin, and the linear expansion at high temperature. The rate can also be suppressed to a low level, and the releasability at high temperatures can be improved. Although the reason for this is not clear, it is considered that even in the region above the glass transition point or the melting point, the finely dispersed layered silicate acts as a kind of pseudo-crosslinking point, so that these physical properties are exhibited. On the other hand, when the distance between the flaky crystals of the layered silicate becomes appropriate, the resin composition forms a sintered body that can move the flaky crystals of the layered silicate during combustion to form a flame-retardant coating. It will be easier. Since this sintered body is formed at an early stage of combustion, not only the supply of oxygen from the outside can be blocked, but also the combustible gas generated by combustion can be blocked, and the resin composition is Exhibits excellent flame retardancy.

Further, in the above resin composition, gas molecules are much more likely to diffuse in the resin than inorganic substances, and when diffusing in the resin, the gas molecules diffuse while circumventing the inorganic substance, so that the gas barrier property is improved. Is improved. In the same way, the barrier property against other than gas molecules is improved, solvent resistance, hygroscopicity,
Water absorption and the like are improved. As a result, it is possible to prevent the trace additive from the resin composition from bleeding out on the surface to cause defects such as defective plating and improve the cleanliness during hot press molding. By exhibiting such high temperature physical properties, dimensional stability, solvent resistance, moisture absorption resistance, and barrier properties,
The quality of the resin composition is improved.

The lower limit of the amount of the layered silicate compounded is 0.1 part by weight, and the upper limit is 100 parts by weight, relative to 100 parts by weight of a resin composed of at least one thermosetting resin and / or thermoplastic resin. is there. If it is less than 0.1 part by weight, the effect of improving flame retardancy and mechanical properties becomes small. If the amount exceeds 100 parts by weight, the film strength of the release film of the present invention decreases, and the practicality becomes poor. The preferred lower limit is 0.
5 parts by weight, the upper limit is 50 parts by weight. If the amount is less than 0.5 part by weight, sufficient mechanical properties and flame retarding effect may not be obtained when the release film of the present invention is thinly formed. Fifty
If it exceeds the weight part, the moldability may decrease. A more preferred lower limit is 2 parts by weight and an upper limit is 20 parts by weight. Two
When it is up to 20 parts by weight, there is no problem in mechanical properties and process suitability, and a sufficient flame retardant effect can be obtained.

In order to modify the characteristics of the above resin composition as needed, the characteristics of the resin composition may be modified within a range that does not hinder the achievement of the object of the present invention.
Thermoplastic resin for modification, rubber component, oligomers, nucleating agent, antioxidant (antiaging agent), heat stabilizer, light stabilizer,
Additives such as a lubricant, a flame retardant, an antifogging agent, a fiber, an inorganic filler, a flame retardant, an ultraviolet absorber, an antistatic agent and a higher fatty acid salt may be blended. These may be used alone 2
One or more species may be used in combination. The nucleating agent serves as a crystal nucleus for refining the crystal and can be an auxiliary means for homogenizing the physical properties.

The modifying thermoplastic resin is not particularly limited, and examples thereof include polyolefin resin, modified polyolefin resin, polystyrene resin, polyvinyl chloride resin,
Examples thereof include polyamide resin, polycarbonate resin, polysulfone resin, polyester resin and the like.

The rubber component is not particularly limited, and examples thereof include natural rubber, styrene-butadiene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer (EP
M, EPDM), polychloroprene, butyl rubber, acrylic rubber, silicone rubber, urethane rubber, olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, ester-based thermoplastic elastomer, amide-based thermoplastic elastomer, etc. Can be mentioned.

The antioxidant is not particularly limited,
For example, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl} -2,4,8,1
Examples thereof include hindered phenolic antioxidants such as 0-tetraoxaspiro [5,5] undecane.

The heat stabilizer is not particularly limited, and examples thereof include tris (2,4-di-t-butylphenyl) phosphite, trilaurylphosphite and 2-t-butyl-α- (3-t-. Butyl-4-hydroxyphenyl)-
p-cumenylbis (p-nonylphenyl) phosphite, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythyryltetrakis (3-laurylthiopropionate), ditridecyl 3,3'-thiodipropionate and the like can be mentioned.

The above-mentioned fibers are not particularly limited, and examples thereof include glass fibers, carbon fibers, boron fibers, silicon carbide fibers, alumina fibers, amorphous fibers, inorganic fibers such as silicon / titanium / carbon fibers; and organic materials such as aramid fibers. Fiber etc. are mentioned.

The inorganic filler is not particularly limited,
Examples thereof include layered double hydrates such as calcium carbonate, titanium oxide, mica, talc, barium sulfate, alumina, silicon oxide and hydrotalcite.

The flame retardant is not particularly limited, and examples thereof include hexabromocyclododecane and tris- (2,3-
Dichloropropyl) phosphate, pentabromophenyl allyl ether and the like can be mentioned.

The ultraviolet absorber is not particularly limited, and examples thereof include pt-butylphenyl salicylate and 2
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone and the like can be mentioned.

The antistatic agent is not particularly limited,
For example, N, N-bis (hydroxyethyl) alkylamine, alkylallyl sulfonate, alkyl sulfanate and the like can be mentioned.

The higher fatty acid salt is not particularly limited, and examples thereof include sodium stearate, barium stearate, sodium palmitate and the like.

The release film of the present invention has at least one layer composed of the above resin composition. The release film of the present invention may be a release film (hereinafter also referred to as a release film (I)) composed of only a layer made of the above resin composition, and does not contain a layered silicate. The release film (I) is provided on at least one surface of the film.
It may be a laminated release film (hereinafter, also referred to as a release film (II)) in which are laminated.

The release film (I) of the present invention may have a single layer structure or a multilayer structure. When the release film (I) of the present invention has a multilayer structure, for example,
Aromatic dicarboxylic acid or a crystalline aromatic polyester obtained by reacting a derivative of an aromatic dicarboxylic acid capable of forming an ester with a low molecular weight aliphatic diol is used as a surface layer, and an aromatic dicarboxylic acid or ester By forming a resin composition containing a crystalline aromatic polyester obtained by reacting a derivative of an aromatic dicarboxylic acid capable of forming with a low molecular weight aliphatic diol and a high molecular weight diol, it is resistant to hot press molding. Flexibility can be obtained while maintaining the obtained heat resistance and releasability. The release film formed by laminating such layers has heat resistance and releasability,
The balance between the circuit pattern and the conformability to the irregularities on the substrate such as through holes is extremely excellent. With respect to the thickness of the inner layer in the release film of the present invention having the above-mentioned multilayer structure, when the total thickness is 1, the preferable upper limit is 0.
It is 5.

The surface of the release film (I) of the present invention preferably has smoothness, but may have slip properties, anti-blocking properties and the like required for handling. In addition, an appropriate embossed pattern may be provided on at least one surface for the purpose of releasing air during hot press molding.

The lower limit of the thickness of the release film (I) of the present invention is preferably 5 μm, and the upper limit thereof is 300 μm. If it is less than 5 μm, the strength may be insufficient, and if it exceeds 300 μm, the thermal conductivity during hot press molding may be deteriorated. More preferable lower limit is 10 μm, and upper limit is 100 μm.
Is. When the thickness is less than 100 μm, the cross-sectional area of the release film is small, so that the shrinkage force of the release film generated during hot press molding can be reduced, and the influence of the hot press molding on the circuit pattern can be reduced. A more preferable upper limit is 50 μm or less.

The release film (I) of the present invention, which comprises the above resin composition, can have a storage elastic modulus at 170 ° C. of 20 to 200 MPa. 20MP
If it is less than a, heat resistance that can withstand hot press molding may not be exhibited. If the pressure exceeds 200 MPa, the release film does not deform sufficiently during hot press molding, and the followability to irregularities on the substrate such as the circuit pattern and through holes decreases, and for example, to the circuit pattern of the coverlay film in the flexible printed circuit board. Uniform adhesion may be reduced. The preferred upper limit is 150
It is MPa. The storage elastic modulus is obtained by dynamic viscoelasticity measurement and can be measured by a viscoelasticity spectrometer.

Since the release film (I) of the present invention comprises the above resin composition, the tensile elongation at break at 170 ° C. can be 500% or more. If it is less than 500%, it may be torn by the unevenness on the substrate during hot press molding, and the substrate may be contaminated. Preferably 80
It is 0% or more. The tensile elongation at break is based on JIS
It can be measured according to K7127.

Since the release film (I) of the present invention comprises the above resin composition, it has a pressure of 3 MPa at 170 ° C.
The dimensional change rate of the pressed surface when pressed for 60 minutes can be 1.5% or less. If it exceeds 1.5%, the circuit pattern may be damaged during hot press molding. It is preferably 1.0% or less. In addition, the above-mentioned dimensional change rate, before pressing, enter the marking lines at intervals of 100 mm in the extrusion molding direction (MD direction) and the direction perpendicular thereto (TD direction), and measure the distance between the marking lines after pressing. , _Where L _MD and L _TD are the average values, they are defined by the following equation (3). Dimensional change rate _{MD or TD} (%) = L _MD
Or L _TD- 100 (3)

The method for producing the release film (I) of the present invention is not particularly limited, and examples thereof include a solution casting method and a melt molding method. The solution casting method is not particularly limited, and for example, a solution obtained by dissolving the resin in a solvent is coated on a support such as a metal endless belt or a smooth resin film, and then the coating film is uniformly heated. And a method of forming a film by drying. Also,
The solution casting method may be a solid printing method. In the case of the above-mentioned thermosetting resin, it is common to obtain a release film (I) of the present invention by obtaining a dry coating film by a solution casting method and then curing it. The solvent is not particularly limited as long as it dissolves the resin, and two or more kinds may be used in combination. The coater for applying the solution is not particularly limited and is appropriately selected according to properties such as desired coating thickness and viscosity of the solution, for example, a comma coater, a roll coater, a usual die coater and the like. A coating coater can be used. The method for drying the coating film is not particularly limited, and an ordinary drying method can be used, but infrared heating is preferable because the coating film can be uniformly heated and dried.

The melt molding method is not particularly limited,
A conventionally known method for forming a thermoplastic resin film can be used, and specific examples thereof include an air-cooling type and water-cooling type inflation extrusion method and a T-die extrusion method.

In the production of the release film (I) of the present invention, heat treatment may be carried out in order to improve heat resistance, releasability and dimensional stability. If the temperature of the heat treatment is lower than the melting point of the resin composition constituting the release film (I) of the present invention, the higher the temperature is, the more effective it is, and 170 ° C.
The above is preferable, and 200 ° C. or more is more preferable.

In the production of the release film (I) of the present invention, in order to improve heat resistance, releasability and dimensional stability, a method of stretching in a uniaxial or biaxial direction, the surface is rubbed with a buff roll or the like. The method etc. may be performed.

The release film (II) of the present invention is a release film obtained by laminating the release film (I) of the present invention on at least one surface of a resin film containing no layered silicate. The release film (II) of the present invention is
It has the cushioning property and strength required to apply pressure uniformly during hot press molding, and is excellent in uniform adhesion to the circuit pattern of the cover lay film in the flexible printed circuit board, for example.

The resin composition constituting the above-mentioned resin film is not particularly limited. For example, polyethylene resin, polypropylene resin, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer may be used because of the ease of disposal after use. Olefin resins such as coalesced are preferred. These may be used alone or in combination of two or more.

In order to improve the adhesiveness with the release film (I) of the present invention, which is laminated on the above resin film,
A modified polyolefin resin such as an acid-modified polyolefin resin or a glycidyl-modified polyolefin resin, or a resin composition constituting the release film (I) may be mixed. The resin composition thus mixed may be used for forming an adhesive resin layer with the release film (I) of the present invention laminated with the above resin film, and for forming the above resin film itself. You may use.

The preferable lower limit of the melting point of the resin composition constituting the resin film is 50 ° C., and the upper limit thereof is 130 ° C.
When the melting point is 50 ° C. to 130 ° C., oozing of the prepreg or thermosetting adhesive into the through hole is suppressed, and
Uniform adhesion to the circuit pattern can be obtained.

The preferable lower limit of the complex viscosity at 170 ° C. of the resin composition constituting the resin film is 100 P.
a · s, the upper limit is 10000 Pa · s. 100-1
When it is 0000 Pa · s, uniform adhesion to the circuit pattern can be obtained.

The preferable lower limit of the thickness of the release film (I) of the present invention laminated on the above resin film is 0.5 μm.
m, the upper limit is 100 μm. If it is less than 0.5 μm, the strength may be insufficient. If it exceeds 100 μm, the thermal conductivity may decrease and the cost also increases.

The lower limit of the thickness of the release film (II) of the present invention is preferably 5 μm and the upper limit is 300 μm. 5 μm
If it is less than the above range, the strength may be insufficient. 300 μm
When it exceeds, the thermal conductivity at the time of hot press molding may decrease. More preferable lower limit is 25 μm, and upper limit is 200 μm.
m.

The lower limit of the softening temperature of the release film (II) of the present invention is preferably 40 ° C and the upper limit is 120 ° C. 40
When the temperature is 120 ° C., it is possible to prevent the prepreg and the thermosetting adhesive from seeping into the through hole and obtain uniform adhesion to the circuit pattern. The softening temperature can be measured according to JIS K 7196.

The method for producing the release film (II) of the present invention is not particularly limited, and examples thereof include a water-cooling type and air-cooling type coextrusion inflation method, a method of forming a film by a coextrusion T-die method, and a release agent of the present invention. A method of laminating a resin composition constituting a resin film on the film (I) by an extrusion lamination method, a method of dry laminating the release film (I) of the present invention and the resin film, a solution casting method, a hot press molding. Law etc. are mentioned. Among them, the method of forming a film by the coextrusion T-die method is preferable because it is excellent in controlling the thickness of each layer.

In the above solution casting method, for example,
After undercoating the anchor layer on the resin film,
A solution of a non-halogenated crystalline resin dissolved in a solvent is applied onto the anchor layer, and the coating film is uniformly heated and dried to form the release film (I) of the present invention.

In the hot press molding, for example, the resin film and the release film (I) of the present invention are superposed and hot press molded. Co-extrusion in advance before hot press molding,
The adhesive resin layer of the resin film may be provided on the release film (I) of the present invention by a known method such as laminating.

In the production of the release film (II) of the present invention, a heat treatment, a treatment of rubbing the surface with a buff roll or the like may be carried out in order to improve heat resistance, releasability and dimensional stability. . If the temperature of the heat treatment is lower than the melting point of the resin composition constituting the release film (I) of the present invention, the higher the temperature, the more effective the temperature is. 170 ° C. or higher is preferable, and 200 ° C. or higher is more preferable. .

Since the release film of the present invention is excellent in heat resistance, release property and non-staining property and can be safely and easily disposed of, it is possible to manufacture a printed wiring board, a flexible printed wiring board or a multilayer printed wiring board. In the process
It is preferably used to prevent adhesion between the press hot plate and the printed wiring board, flexible printed wiring board, or multilayer printed wiring board when hot press-molding the copper clad laminate or copper foil through the prepreg or heat resistant film. To be

Since the release film of the present invention is excellent in heat resistance, release property and non-staining property and can be disposed of safely and easily, the cover lay film is heat-pressed by hot press molding in the manufacturing process of the flexible printed circuit board. It is preferably used in order to prevent the cover lay film and the hot press plate or the cover lay films from being adhered to each other when they are adhered with a curable adhesive.

Furthermore, the release film of the present invention is a sports article such as a fishing rod or a golf club shaft produced by curing a prepreg made of glass cloth, carbon fiber or aramid fiber and epoxy resin in an autoclave. It is also preferably used in the production of aircraft parts, polyurethane foam, ceramic sheets, electrical insulating plates and the like.

The release film of the present invention is excellent in heat resistance and mechanical properties and has a small environmental load at the time of disposal. Further, the release film of the present invention, by containing the layered silicate,
It has excellent dimensional stability at hot press molding temperature, can suppress defects such as circuit pattern deviation, and has excellent flame retardancy and low spreadability even in the event of a fire in the manufacturing process. It has and is highly safe. Further, the release film of the present invention, by controlling the melting point and storage elastic modulus,
By suppressing the molecular motion of the constituent molecules at the hot press molding temperature, it is possible to develop an excellent mold releasability, and by controlling the storage elastic modulus and the tensile fracture elongation, the cushioning property and the strength at the hot press molding temperature can be obtained. It is also possible to exhibit excellent followability to the irregularities of the circuit pattern, and to prevent the cushion layer resin from leaking to the substrate surface. Thus, by using the release film of the present invention, the product yield at the time of hot press molding in the production of printed wiring boards can be dramatically improved.

[0127]

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

(Example 1) (1) Preparation of release film 100 parts by weight of Perprene P150B (polyester resin manufactured by Toyobo Co., Ltd.) as a thermoplastic resin, and organically treated with distearyldimethyl quaternary ammonium salt Natural montmorillonite (Toyojun Yoko, New S-Be
n D) (7.7 parts by weight) was put into an extruder, melt-plasticized at 230 ° C. and extrusion-molded from a T-die to obtain a film having a thickness of 50 μm, which was used as a release film (I).

(2) Preparation of resin film Low-density polyethylene resin (Novatec LD LE425, manufactured by Nippon Polychem Co., Ltd.) was put into an extruder, heated to 230 ° C., melted and plasticized, and extruded from a T-die to have a thickness. 1
A resin film of 00 μm was obtained.

(3) Preparation of copper-clad laminate A polyimide film (Kapton manufactured by DuPont) having a thickness of 25 μm was used as a base film, and a copper foil having a thickness of 35 μm and a width of 50 μm was epoxy-based with a thickness of 20 μm on the base film. A copper-clad laminate bonded with an adhesive layer was obtained.

(4) Preparation of Coverlay Film A 25 μm thick polyimide film (Kapton manufactured by DuPont) was coated with an epoxy adhesive having a flow starting temperature of 80 ° C. in a thickness of 20 μm to obtain a coverlay film. It was

(5) Preparation of Flexible Printed Circuit Board A set of the release film (I), the copper-clad laminate, the coverlay film, the release film (I) and the resin film, which were stacked in this order, was set to 32. Place the set on a hot press plate, press temperature 170 ℃, press pressure 300
After hot press molding under the conditions of N / cm ² and a pressing time of 60 minutes, the press pressure is released, the resin film is removed,
The release film (I) was peeled off to obtain a flexible printed board.

(Example 2) A release film (I) was obtained by using Hytrel 4275JB (manufactured by DuPont Toray) instead of Perprene P150B (manufactured by Toyobo Co., Ltd., polyester resin) as the thermoplastic resin. A flexible printed board was obtained in the same manner as in Example 1.

(Example 3) As a thermoplastic resin, Perprene P150B (manufactured by Toyobo Co., Ltd., polyester resin) 1
00 parts by weight, 7.7 parts by weight of natural montmorillonite (New S-Ben D, manufactured by Toyojun Yoko Co., Ltd.) that has been organically treated with distearyl dimethyl quaternary ammonium salt are charged into an extruder and melted at 230 ° C. It was plasticized and extruded from a T-die to obtain a film having a thickness of 25 μm. The obtained film was laminated on a resin film produced in the same manner as in Example 1 (2) and pressure-laminated with a heat press at 180 ° C. to obtain a release film (II). A flexible printed circuit board was produced in the same manner as in Example 1 except that this release film (II) was used instead of the release film (I) and the resin film being laminated.

(Comparative Example 1) Natural montmorillonite (New S-Ben D, manufactured by Toyojun Yoko Co., Ltd.) that had been organically treated with distearyldimethyl quaternary ammonium salt was not used, and as a thermoplastic resin. Pelpren
Instead of P150B (made by Toyobo Co., Ltd., polyester resin), Novatec PP FB3GT (made by Nippon Polychem,
Non-halogenated crystalline resin) is charged into the extruder and
Melt plasticized at ℃, extrusion molded from T-die and thickness 50μ
A flexible printed circuit board was produced in the same manner as in Example 1 except that the film of m was obtained and used as the release film (I).

(Comparative Example 2) A release film (I) was obtained without using natural montmorillonite (New S-Ben D, manufactured by Toyojun Yoko Co., Ltd.) which was organically treated with distearyldimethyl quaternary ammonium salt. A flexible printed circuit board was produced in the same manner as in Example 1 except for the above.

(Evaluation) The release film (I) produced in Examples 1 and 2 and Comparative Examples 1 and 2 and the release film (II) produced in Example 3 were measured for various physical properties by the following methods. It was measured.

(1) Storage Modulus Using a viscoelasticity spectrometer (RSA-2, manufactured by Rheometric Scientific FE), heating rate 5 ° C./min, frequency 1.61 Hz, strain 0.05% It was measured under the conditions.

(2) Tensile Fracture Elongation Based on JIS K 7127, punching test pieces of test piece type 5 were measured at a test speed of 500 mm / min.

(3) Dimensional change rate Mark lines with 100 mm intervals are entered in the extrusion molding direction (MD direction) and the direction perpendicular thereto (TD direction), respectively, and the press temperature is 170 ° C., the press pressure is 3 MPa, and the press time is 60 minutes. After pressing under the conditions described above, the average values L _MD and L _{T D} of the distance between marked lines were measured. The dimensional change rate _{MD or TD} was calculated from the following formula (3). Dimensional change rate _{MD or TD} (%) = L _MD or L _TD -100 (3)

(4) Average interlaminar distance of layered silicate An X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation) was used to measure the diffraction peak 2θ obtained by diffraction of the laminated surface of the layered silicate. The (001) plane spacing d of the layered silicate is calculated by the black diffraction formula of the following formula (4),
The obtained d was taken as the average interlayer distance (nm). λ = 2 dsin θ (4) In the above formula (4), λ is 0.154, and θ represents a diffraction angle.

(5) Percentage of layered silicate dispersed as a laminated body of 5 layers or less Observed at 50,000 to 100,000 times with a transmission electron microscope,
The total number of layers (X) of the layered silicate laminate that can be observed in a certain area and the number of layers (Y) of the layered silicate dispersed as a laminate of 5 layers or less were measured, and the following formula (2) ), The ratio (%) of the layered silicate dispersed as a laminated body of 5 layers or less was calculated.

[0143]

[Equation 3]

(6) Shape retention during burning ASTM E 1354 "Testing method for flammability of building materials"
50 kW / m with a cone calorimeter on a release film cut into 100 mm x 100 mm
It was burned by irradiating it with a heat ray of ² . At this time, changes in the shape of the release film before and after burning were visually observed, and the shape retention during burning was evaluated according to the following criteria. ◯: The change in shape was slight. X: The shape change was severe.

(7) Maximum heat release rate ASTM E 1354 "Test method for flammability of building materials"
According to the above, thickness 5 cut to 100 mm x 100 mm
A 0 μm release film was irradiated with a heat ray of 50 kW / m ² by a cone calorimeter to burn it, and the maximum heat generation rate (kW / m ² ) at this time was measured.

In the flexible printed circuit boards manufactured in Examples 1, 2, 3 and Comparative Example 2, the copper foil was completely exposed even in the electrode portion made of the copper foil without the coverlay film, and the release film ( I) and release film (I
The peelability of I) was good. Further, the coverlay film and the substrate body were completely in contact with each other, no residual air portion (void) was observed, and the adhesion was good. Further, no electrode contamination due to the adhesion of organic substances was observed, the conductivity of the copper foil at the electrode portion was sufficient, and no deformation of the circuit which could be a practical problem was observed. Furthermore, the flow of the adhesive to the surface of the copper foil in the part without the coverlay film is
It was 0.1 mm or less from the edge of the coverlay film, and the flow of the adhesive was sufficiently prevented.

[0147]

[Table 1]

The release films produced in Examples 1, 2 and 3 are excellent in various physical properties, and the flexible printed board obtained by using them has good adhesion without electrode contamination or circuit deformation. Showed sex. On the other hand, the release films produced in Comparative Examples 1 and 2, which did not use the layered silicate, were inferior in shape retention property upon burning.

[0149]

According to the present invention, a release film which is excellent in heat resistance, releasability and non-staining property, is excellent in flame retardance without containing a halogen-based flame retardant, and is easy to dispose of is provided. Can be provided.

[0150]

The release film of the present invention is excellent in heat resistance and mechanical properties and has a small environmental load at the time of disposal. In addition, the release film of the present invention has excellent dimensional stability at the hot press molding temperature by containing the layered silicate, and can suppress defects such as circuit pattern displacement, and the manufacturing process, etc. Even in the unlikely event of a fire, it has excellent flame retardancy and low spreadability, and is highly safe. Further, the release film of the present invention, by controlling the melting point and the storage elastic modulus, suppresses the molecular motion of the constituent molecules at the hot press molding temperature, it is possible to develop an excellent release properties, storage elasticity By controlling the elastic modulus and the tensile elongation at break, it has both cushioning property and strength at the hot press molding temperature, and it exhibits excellent followability to the irregularities of the circuit pattern, and the cushion layer resin leaks to the substrate surface. Can be suppressed. As described above, by using the release film of the present invention, the product yield at the time of hot press molding in the production of printed wiring boards is dramatically improved.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 67/02 C08L 67/02 101/00 101/00 H05K 3/00 H05K 3/00 Z F term (reference) ) 4F071 AA14 AA22 AA28 AA29 AA30 AA33 AA40 AA42 AA43 AA45 AA49 AA51 AA52 AA54 AA58 AA60 AA60 XAA65 AA78 AB26 AB30 AE12 AACBAA ACBAB AC12B11A01B01A17B01A17B01 BB22B01A17B01 BF22B01A17B01 BB22B01B17A01B17B01A17A01B17A01B01A01B17A01B17A01B01A01B17A01B01A17B01B17A01B17A01B01A17B01A17B01A01B01 JK02A JL04A JL06 JL14 JL14B YY00A 4F202 AA03 AA13 AA24 AA25 AA32 AA36 AB07 AB16 AC03 AG01 AG03 AH36 AJ36 CF1 CF07 CF1 CF01 CD011 CF01 CD011 CB1 CD011 CF02 CD1 CF1 CD011 CK021 CL001 CM011 CM021 CM041 CM051 CN031 CP001 DJ006 DJ056 FB086 FB096 FB106 FB146 FD0 16 GQ00

Claims (10)

[Claims] 1. At least one layer composed of a resin composition containing 100 parts by weight of a resin composed of at least one thermoplastic resin and / or thermosetting resin and 0.1 to 100 parts by weight of a layered silicate. A release film characterized in that 2. The release film according to claim 1, wherein the thermoplastic resin is a halogen-free crystalline resin having an aromatic ring structure in the main chain. 3. The release film according to claim 2, wherein the non-halogenated crystalline resin having an aromatic ring structure in the main chain is a crystalline aromatic polyester resin. 4. The release film according to claim 2, wherein the non-halogenated crystalline resin having an aromatic ring structure in the main chain has a crystal component of butylene terephthalate. 5. A layer made of a resin composition containing 100 parts by weight of at least one thermoplastic resin and / or thermosetting resin and 0.1 to 100 parts by weight of a layered silicate has a layer at 170 ° C. Storage elastic modulus of 20 to 200 MPa
The tensile fracture elongation at 170 ° C. is 500% or more, and the dimensional change rate of the pressed surface is 1.5% or less when pressed at 170 ° C. and 3 MPa for 60 minutes. The release film according to claim 1, 2, 3 or 4. 6. The layered silicate is at least one selected from the group consisting of montmorillonite, hectorite, and swelling mica.
The release film according to 2, 3, 4 or 5. 7. The release film according to claim 1, wherein the layered silicate contains an alkylammonium ion having 6 or more carbon atoms. 8. The layered silicate is measured by a wide-angle X-ray diffractometry in a layer made of a resin composition (00).
1) The average interlayer distance of faces is 3 nm or more, and a part or all of the laminated bodies are dispersed as a laminated body of 5 layers or less. The release film according to item 6, 6 or 7. 9. A press hot plate when a copper clad laminate or a copper foil is hot-pressed via a prepreg or a heat-resistant film in a manufacturing process of a printed wiring board, a flexible printed wiring board, or a multilayer printed wiring board. And a printed wiring board, a flexible printed wiring board, or a multi-layered printed wiring board to prevent the adhesion thereof.
The release film described. 10. In the process of manufacturing a flexible printed circuit board, when the cover lay film is bonded by a thermosetting adhesive by hot press molding, the adhesion between the cover lay film and the heat press plate or the cover lay films is prevented. It is used for cutting.
The release film according to 4, 5, 6, 7 or 8.