JPH0392345A - Preparation of printed-wiring board and printed-wiring board obtained by the same method - Google Patents

Abstract

PURPOSE:To prepare a printed-wiring board with excellent dielectric characteristics, dimensional stability, bending characteristics, etc., by compounding a styrene polymer with a specified structure with a fibrous filler, a binding material and/or a binding fiber at a specified ratio and providing a metal layer on the obtd. molding. CONSTITUTION:95-20wt.% styrenepolymer A with a syndiotactic structure, 5-80wt.% fibrous filler B with a fiber length of 1-50mm and 0.1-30 pts.wt. binding material and/or binding fiber based on 100 pts.wt. above described components A and B are dispersed in water and/or an org. solvent to obtain a slurry with a concn. of 0.5-100g/l. Then, the dispersed solid in the slurry is precipitated and water and/or the org. solvent in the slurry are filtered and/or dried and the residue is made into a molding. After it is melted by heating, it is press- molded and a metal layer is provided on the obtd. molding. As the metal constituting the metal layer, it is pref. selected from copper, nickel, aluminum, tin, gold, silver, zinc, etc.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for manufacturing a printed wiring board and a printed wiring board obtained by the method, and more specifically, to a printed wiring board having excellent dielectric properties, dimensional stability, bending properties, etc. The present invention relates to an efficient method for manufacturing a printed wiring board, and a printed wiring board obtained by the method.

[Prior art and problems to be solved by the invention] Epoxy resin,
Composite sheets made by combining thermosetting resins such as phenolic resins and unsaturated polyester resins with base materials such as paper, glass fibers, and composite fibers are widely used. These composite base materials have excellent electrical insulation properties, and demand for them is rapidly increasing in the electrical and electronic fields.

However, composite base materials using such thermosetting resins are
Because a solvent such as styrene monomer was used during the process, the work environment was poor, making it unsuitable for use as a multilayer printed wiring board used in fields such as computers that require high-speed processing. .

Printed wiring boards using fluorinated polyethylene resin as an insulating base material have recently been rapidly developed as multilayer printed wiring boards used in fields such as computers that require high-speed calculation processing. .

However, fluorinated polyethylene resins are extremely difficult to mold, and efforts are therefore being made to develop high-profile products of a grade that can be subjected to conventional melt molding, specifically injection molding, extrusion, or shaping.

In addition, polyphenylene sulfide (a thermoplastic resin)
Printed wiring boards using PPS) as a base material are being researched and efforts are being made to improve production efficiency, but the problem is that the dielectric constant is too high for use in multilayer printed wiring boards that require high-speed calculation processing. .

Therefore, the present inventor has conducted extensive research in order to develop a method that can efficiently manufacture printed wiring boards with excellent dielectric properties, dimensional stability, bending properties, etc., in a favorable working environment.

As a result, the raw material was a mixture of a styrenic polymer with a syndiotactic structure (hereinafter sometimes referred to as SPS), a fibrous filler, a binder and/or a binder fiber in a predetermined ratio, and this was used as a so-called paper making material. It has been discovered that a printed wiring board with the desired properties can be obtained by shaping according to the principles of the law and further providing a metal layer on the obtained molded body.The present invention has been completed based on this knowledge. [Means for Solving the Problems] That is, the present invention provides (A) 95 to 20% by weight of a styrenic polymer having a syndiotactic structure, (B) in water and/or an organic solvent. Fibrous filler with fiber length 1-50IllII1 5-
80% by weight and (C) binder and/or binding fibers at a concentration of 0.5-1. 0 0 gel), 2) Precipitating the dispersed solids in the slurry, 2) Filtering and/or drying the water and/or organic solvent in the slurry, and removing the remainder. The present invention provides a method for manufacturing a printed wiring board, which is characterized by sequentially performing the steps of forming a molded product, (1) applying pressure or shaping after heating and melting, and (2) providing a metal layer on the obtained molded product. . The present invention also provides a method in which, in place of the step (1) of heat-melting and then pressurizing, in the above method, the step (2) of impregnating with a thermosetting resin and then curing is performed.

First, in the method of the present invention, in step (2), components (A), (B), and (C) are added in a predetermined ratio to water and/or an organic solvent to form a dispersed slurry. The styrenic polymer (sps), which is component (A), has a synthiotactic structure. This syndiotactic structure is a syndiotactic structure in which the stereochemical structure is a syndiotactic structure, that is, side chains such as phenyl groups and substituted phenyl groups are located alternately in opposite directions with respect to the main chain formed from carbon-carbon bonds. It has a three-dimensional structure, and its tacticity is based on the nuclear magnetic resonance method (C-NMR method) using carbon isotopes.
It is quantified by Tacticity measured by the 13C-NMR method can be expressed by the abundance ratio of a plurality of consecutive structural units, for example, dyads in the case of 2 units, triads in the case of 3 units, and pentads in the case of 5 units. However, the styrenic polymer having a syndiotactic structure referred to in the present invention is usually a racemic diad having 7
Polystyrene, poly(alkylstyrene), poly(halogenated styrene), poly(alkoxystyrene) having a syndiotacticity of 5% or more, preferably 85% or more, or 30% or more, preferably 50% or more in lase ξ bentad. ). Poly(vinyl benzoate)
, these hydrogenated polymers, mixtures thereof, or copolymers having these as main components. Note that poly(alkylstyrene) here includes poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene).
, poly(phenylstyrene), poly(vinylnaphthalene), poly(vinylstyrene), etc. Poly(halogenated styrene) includes poly(chlorostyrene), poly(bromostyrene), poly(fluorostyrene), etc. There is. Examples of poly(halogenated alkylstyrene) include poly(chloromethylstyrene), and examples of poly(alkoxystyrene) include (methoxystyrene). In addition, as poly(alkoxystyrene),
Poly(methoxystyrene), poly(ethoxystyrene)
and so on. Furthermore, as comonomer components of the copolymer containing these structural units, in addition to the above-mentioned styrene polymer monomers, ethylene, propylene, butene, etc. can be used. Examples include olefin monomers such as hexene and octene, diene monomers such as butadiene and isobrene, cyclic olefin monomers, cyclic diene monomers, and polar vinyl heptanomers such as methyl methacrylate, maleic anhydride, and acrylonitrile.

Among these, particularly preferred styrene polymers include polystyrene. Examples include poly(alkylstyrene), poly(halogenated styrene) dihydrogenated polystyrene, and copolymers containing these structural units.

Styrenic polymers having such a syndiotactic structure can be produced by, for example, producing styrene by using a titanium compound and a condensed compound of water and trialkyl almonium as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing monomers (monomers corresponding to the above-mentioned styrene-based polymers) (Japanese Patent Laid-Open No. 18770/1983).
Publication No. 8). Further, poly(halogenated alkylstyrene) can be obtained by the method described in JP-A-1-46912, and hydrogenated polymers thereof can be obtained by the method described in JP-A-1-178,505.

The molecular weight of this styrenic polymer is not particularly limited, but those having a weight average molecular weight of 2,000 or more, preferably 10,000 or more, particularly 50,000 or more are optimal. Further, there is no restriction on the width or narrowness of the molecular weight distribution, and various types can be used.

In the method of the present invention, the amount of SPS, which is the component (A), is determined by the amount of (A) Jffl and (B) $. It is 95 to 20% by weight, preferably 90 to 30% by weight, more preferably 90 to 40% by weight, based on the total weight of the components. If the amount of SPS is less than 20% by weight, the coating with the fibrous filler component (B) will be insufficient, and the desired physical properties such as heat resistance, mechanical strength, and surface smoothness will not be exhibited. Furthermore, the fluidity during molding is poor, and due to the high rigidity, the upper and lower parts of the mold do not mesh well, which may result in damage to the mold. On the other hand, if it exceeds 95% by weight, heat resistance and mechanical strength will not be exhibited.

In the method of the present invention, there is no particular restriction on the form of the SPS, which is the tc component (A), and various forms can be used, but the bulk density is 0.05 to 1. 0 g/ci, especially 0.
10-0.95g/cm powder and/or fiber diameter 0.0
Fibers or shapes of 1 to 500 μm are preferably used. Here, when SPS is used in powder form, its bulk density is 0.05
If it is less than g/cm or exceeds 1.0 g/d, a uniformly dispersed slurry may not be obtained when producing a molded article by the method of the present invention.

Next, various types of fibrous fillers can be used as the filler (B) in the method of the present invention, including glass fibers, asbestos fibers, carbon fibers, gypsum, potassium titanate, and magnesium sulfate. ．． Ceramic fibers such as magnesium oxide, metal fibers such as copper, argonium, and rope, and boron. Whiskers such as argona, silica, silicon carbide,
Suitable examples include organic synthetic fibers such as wholly aromatic polyamide fibers, short polyester fibers, and aramid fibers, and natural plant fibers such as silk and flax, and these may be used alone or in combination of two or more. use

In the method of the present invention, the amount of the fibrous filler, which is the component (B), is 5% based on the total of the components (A) and (B).
~80% by weight, preferably ~70% by weight, more preferably 10-60% by weight. Moreover, this fibrous filler has a fiber length of 1 to 50 min. Preferably 5-30m
are used. If the fiber length is less than IW, sufficient mechanical strength will not be exhibited, and if it exceeds 50 mm, dispersion in the slurry will be poor when producing a molded article by the method of the present invention.

Component (C) used in the method of the present invention is a binder and a binding fiber, and one or both of these may be used. There are various types of binders, such as natural starch (particularly natural maize starch), starch phosphate ester (Retamil AP or Retabond AP type), carboxymethylated starch, oxidized starch, and enzyme-treated starch (for example, enzyme-treated starch). Using α-amylase as
linear polymer amylose with a distribution of glycol units varying between ~3000), hydroxymethylated starch, industrial carboxymethyl cellulose (sodium chloride 5-30%, degree of substitution: 0.7-0.8), acrylic 87 to 90 parts by weight of ethyl acid units and 1 to 1 acrylonitrile units
An aqueous dispersion with a concentration of 40 to 55% of a polymer containing 8 parts by weight of N-methylolacrylic acid≧1 to 6 parts by weight and 1 to 6 parts by weight of acrylic acid units, 60 ethyl acrylate units
A 40-55% strength aqueous dispersion of a polymer containing ~75 parts by weight, 5-15 parts by weight of acrylonitrile units, 10-20 parts by weight of butyl acrylate units and 1-6 parts by weight of N-methylolacrylamide units, butadiene unit 60
40-55% strength aqueous dispersion of a polymer containing ~65 parts by weight, 35-40 parts by weight of acrylonitrile units and 1-7 parts by weight of methacrylic acid units, 38-50 parts by weight of styrene units.
a polymer containing 53 to 65 parts by weight of styrene units, 32 to 44 parts by weight of butadiene units, and 1 to 6 parts of methyl methacrylamide units; 40-55% strength aqueous dispersions of polymers containing parts by weight, polyvinyl alcohol, casein, carboxymethyl cellulose, gelatin, methyl ethyl cellulose, 40-55% strength aqueous dispersions of carboxylated styrene-butadiene latex, alginates. , dextrin, an aqueous dispersion of a vinylidene chloride-based copolymer at a concentration of 40 to 55%, and an ethylene-vinyl acetate copolymer, which may be used alone or in appropriate combinations. Particularly preferred are latex (acrylic, styrene-butadiene), starch, especially natural starch (obtained from potatoes) and maize natural starch (in linear polymers, containing 100 to 6000 amperes per molecule). linear polymer components such as amylose containing 50 to 6000 anhydroglucose units per molecule;
It is a starch modified by chemical or enzymatic means with 0 to 3000 anhydroglucose units. This binder can ensure the bonding of components such as thermoplastic sheets and enhance their physical properties.

In addition, various types of binding fibers can be mentioned, but the binding fibers here include cellulose fibers and polyolefin fibers (U.S. Pat. No. 2,481.707
(see specification), which suitably binds the other structural components of the composition. Specific examples of such bonding fibers include bleached softwood kraft bulb, semi-bleached softwood kraft bulb, unbleached softwood kraft bulb, bleached softwood sulfite bulb, unbleached softwood sulfite bulb, and bleached hardwood kraft bulb. Semi-bleached hardwood kraft pulp, unbleached mechanical pulp, bleached mechanical pulp. Polyvinyl alcohol fiber, rayon fiber, recovered fiber, polyolefin bulk fibril. There are cellulose fibers.

In the method of the present invention, the binder and/or the binder fibers (
It is used as component C), and its blending amount is 0.1 to 3 parts by weight per 100 parts by weight of the above components (A) and (B).
It is 0 parts by weight. If the amount is less than 0.1 part by weight, the sheet will not have sufficient mechanical strength to be stretched by a paper machine, and if it exceeds 30 parts by weight, the heat resistance will be lowered, which is not preferable.

In the dispersion slurry step (1) of the present invention, the above-mentioned component (A) is added to water, an organic solvent (specifically, alcohols, hydrocarbons, ketones, etc.) or a mixed solvent thereof. (B)
Component and component (C) are added at a predetermined ratio until the concentration is 0.
Adjust to 5-100g/42. If necessary, a dispersant may be added to improve dispersibility, and a sizing agent may be added to improve adhesion between the fibrous filler and SPS. Additionally, flame retardants and flame retardant aids are added as necessary. In particular, the flame retardant aid is added within a range that does not increase the dielectric constant. These are (A). It is desirable that the amount does not exceed 40 parts by weight of the flame retardant and 15 parts by weight of the flame retardant aid for a total of 100 parts by weight of component (B). Furthermore, commonly used additives such as antioxidants, nucleating agents, antistatic agents, thermoplastic resins, rubber-like elastic bodies, etc. may be added.

The form of SPS used as component (A) is not particularly limited, and may be in any form such as powder, fiber, beads, etc., as long as it can be suspended in water or an organic solvent. Further, various forms may be used in combination. When using a fibrous SPS shape, the fiber length is 0.1 m to 30 mm and the fiber diameter is 0.1 m to 30 mm. lμm～500μ
m is preferred. Note that this fibrous molded body can be obtained by dry spinning, wet spinning, melt spinning, melt blowing, flash spinning, or the like. It may be drawn by reheating during spinning or after spinning.

(C) t2 minutes. Dispersants and sizing agents may also be used as long as they can be suspended in water or organic solvents.

The order in which these parts are added does not matter, but the sizing agent or surfactant. Add the dispersant first, then (B
) components, (A) components, and (C) components are preferably added in this order.

In addition, specific examples of the above-mentioned dispersant, sizing agent, and thermoplastic resin include the following. First, as a dispersant, there are the following surfactants (1) to (4).

(1) Anionic surfactant fatty acid soda soap, fatty acid potassium soap, alkyl sulfate sodium salt. Alkyl sulfate salts of alkyl ether sulfate sodium salts, ethylhexyl alkyl sulfate ester sodium salt, dodecyl benzene sulfonic acid sodium salt, dodecyl benzene sulfonic acid, sodium acylmethyl taurate, sodium lauroyl methyl taurate , sodium dioctyl sulfone succinate (2) Cationic surfactant amine type octadecyl amine acetate, tetradecylamine acetate, tallow alkyl propylene diagonal acetate methyl type octadecyl trimethyl ammonium chloride, alkyl trimethyl ammonium chloride, dodecyl trimethyl Ammonium chloride, hexadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkylimidazoline quaternary salt benzylic alkyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride, other dioleyldimethylammonium chloride, polyoxyethylenedodecylmonomethylammonium chloride, oxyethylene Dodecylamine, polyoxyethylene dodecylamine, polyoxyethylene alkylamine,
Polyoxyethylene octadecylamine, polyoxyethylene alkylpropylene diamine, ■-hydroxyethyl-2-alkylimidazoline quaternary salt, alkylisoquinolium bromide, polymeric amine (3) Nonionic surfactant ether type polyoxyethylene olein ether , polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene alkyl ether alkylphenol type polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether ester type polyoxy Ethylene monolaurate, polyoxyene monostearate, polyoxyethylene monooleate sorbitan ester type sorbitan monolaurate, sorbitan monostearate, sorbitan monobalmitate, sorbitan monostearate, sorbitan oleate, sorbitan sesquioleate , sorbitan trioleate sorbitan ester ether type polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monobaltate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and other oxyethylene sorbitan monolaurate mer, alkylalkylolamide, lauric acid diethanolamide, coconut oil fatty acid diethanolamide, oleic acid diethanolamide, beef tallow fatty acid diethanolamide, glycerol monostearate, polyglycerin fatty acid ester, polyoxyethylene distearate (4) amphoteric Specific examples of the surfactant dimethylalkylbetaine, dimethylalkyllaurylbetaine, and alkylglycine sizing agents include the following (1) and (2).
Coupling agents include:

(1) Silane coupling agent triethoxysilane. Vinyl tris(β-methoxyethoxy)silane, γ-methacrylatexybrobyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, β-(1,i-epoxycyclohexyl)ethyltrimethoxysilane N-β-(aminoethyl )-γ-a-short nobrovir trimethoxysilane. N-β-(aminoethyl)-γ-75 nopropylmethyldimethoxysilane, γ
Monoaξnobrobyltriethoxysilane, N-phenyl-γ-aminoprobyltrimethoxysilane, γ-mercaptobutyltrimethoxysilane, γ-chlorobrobyltrimethoxysilane. γ-Agonopropyltrimethoxysilane, γ-Aminopropyltrimethoxysilane Ethoxysilane, triaminopropyltrimethoxysilane, 3-ureidobropyltrimethoxysilane,
3-(4,5-dihydroimidazole)probyltriethoxysilane. Hexamethyldisilazane. Examples include N,O-(bistrinotylsilyl)amide; N,N-bis(trimethylsilyl)urea. Among these, γ−
Aminobropyltriethoxysilane, N-β-(aminoethyl)-aminobropyltrimethoxysilane, γ
-Glycidoxybrobyltrimethoxysilane, β-(3
, 4-epoxycyclohexyl)ethyltrimethoxysilane, and epoxysilane are preferred.

(2) Titanate coupling agent isobrobyl triisostearoyl titanate. Isoprobil tridodecylbenzenesulfonyl titanate, isoprobil tris(dioctyl phosphate) titanate, tetraisoprobil bis(dioctyl phosphite) titanate. Tetraoctyl bis(ditridecyl phosphite) titanate, tetra(l,1-diallyloxymethyl-1-butyl) bis(ditridecyl) phosphite titanate, bis(dioctyl birophosphate) oxyacetate titanate, bis(dioctyl birophosphate) Ethylene titanate, isobrobyl trioctanoyl titanate, isobrobyl dimethacrylic isostearyl titanate, isoprobyl isostearoyl diacryl titanate. Isopropyl tri(dioctyl phosphate) titanate, Isopropyl tri(dioctyl phosphate) titanate, Isopropyl tri(N
-Amidoethyl. (aminoethyl) titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate, and the like. Among these, isopropyltri(N-acdoethyl, acinoethyl)titanate is preferred.

Although various flame retardants can be used, halogen-based flame retardants and phosphorus-based flame retardants are particularly preferred.

Examples of halogenated flame retardants include tetrabromobisphenol A. Tetrabromo phthalic anhydride, hexabromobenzene. Tribromophenyl allyl ether. Pentabromotoluene, pentabromophenol, tribromophenyl-2,3-dibromobrovir ether, tris(2,3-dibromobrovir) phosphate. Tris (2-1 rolo 3-promobrovir) phosphate, octabromodiphenyl ether, decabromodiphenyl ether. Octabromo biphenyl, pentachlorobentacyclodecane, hexabromo-dotecan, hexabromo-benzene. Pentachlorotoluene, hexabmobiphenyl, decabromobiphenyl, decabromobiphenyl oxide, tetrabutan. Decabromodiphenyl ether to xabromodiphenyl ether, ethylene-bis(tetrabu-mophthalimide). Tetrabromobisphenol A, Tetrabromobisphenol A,
Halogenated polycarbonate oligomers such as tetrachloride bisphenol A or tetrabromobisphenol A oligomers and brominated polycarbonate oligomers. Examples include halogenated epoxy compounds, halogenated polystyrenes such as polychlorostyrene and polytribromostyrene, poly(dibromophenylene oxide), and bis(tribromophenoxy)ethane.

On the other hand, examples of phosphorus-based flame retardants include ammonium phosphate. Examples include l-licresyl phosphate, triethyl phosphate, acidic phosphoric acid ester, triphenylphosphine oxide, and the like.

Among these flame retardants, polytribromostyrene, poly(dipromophenylene oxide), decabromodiphenyl ether, bis(tribromophenoxy)ethaneethylene bis(tetrabutyl mophthalide) are particularly suitable. Tetrabromobisphenol A, a brominated polycarbonate oligomer, is preferred.

There are various flame retardant aids that can be used with these flame retardants, such as antimony dioxide, antimony pentoxide, sodium antimonate, antimony metal, antimony trichloride, antimony pentachloride, and antimony trisulfide. , antimony-based flame retardant aids such as antimony pentasulfide.

In addition to these, zinc borate, barium metaborate,
Examples include zirconium oxide.

Among these, antimony dioxide is particularly preferred.

Furthermore, in the present invention, a tetrafluoroethylene polymer can be added to prevent melt dripping. Specific examples of this tetrafluoroethylene polymer include tetrafluoroethylene homopolymer (polytetrafluoroethylene), copolymers of tetrafluoroethylene and hexafluoropropylene, and copolymerizable ethylenic polymers. Examples include tetrafluoroethylene copolymers containing a small amount of saturated monomers. The tetrafluoroethylene polymer used has a fluorine content of 65 to 76% by weight, preferably 70 to 76% by weight.

Furthermore, as the thermoplastic resin, component (A) SP
Examples include those that are compatible with S or those that are incompatible with S. For example, styrene polymers with an atactic structure, styrene polymers with an isotactic structure, polyphenyl ether, etc. are easily compatible with SPS, and can produce attractive products with excellent mechanical properties. In particular, polyphenyl ethers having a polar group such as maleic anhydride are particularly preferred because they have a remarkable effect of improving the adhesion between the fibrous filler and SPS. In addition, examples of the incompatible resin include polyethylene. Polyolefins such as polypropylene, polybutene, polybentene, polyethylene terephthalate. Polyesters such as polybutylene terephthalate and polyethylene naphthalate, polyesters such as nylon-6 and nylon 6/6, polythioethers such as polyphenylene sulfide, polycarbonate, polyarylate, polysulfone, polyetheretherketone, polyethersulfone, polyester polyvinyl alcohol, styrene-maleic anhydride copolymer (SMA)
) etc., all other than the above-mentioned compatible resins are equivalent, and furthermore,
Examples include crosslinked resins containing the above-mentioned compatible resins. The sedimentation step (1) of the method of the present invention is a step in which a flocculant is added to the suspension obtained as a dispersed slurry in the above step (2) to flocculate the particles, and the resulting solids are sedimented. Agglomerated particles (solid matter) settle under their own weight. Flocculant is usually 0.1 to 0
．． 5g/I! ．． However, if the particles in the suspension are large enough to settle under their own weight, it is not necessary to add a flocculant. The flocculants used here include aluminum sulfate; polyaluminum chloride (hydroxyaluminum chloride); sodium and calcium alginate; 5 to 30% (weight/volume) aqueous solution of polyacrylic acid and polyacrylic Blend with Agodo; 2-50% (weight/volume) polyethylene ξ in aqueous solution; Copolymer of acrylic adand and β-methacryloxyethyltrimethylammonium methyl sulfate; 2-50% aqueous solution Polyamine-epichlorohydrin and diamine-propylmethylamine resin; shrimp chlorohydrin in a 2-50% aqueous solution state. Adivic acid, cabbage lactam. Boriaceous-doe-episohydrin resin made from diethylenetriamine and/or ethylenediamine; 2-50%
Shrimp chlorohydrin in aqueous solution, dimethyl ester,
Boria ξ-epichlorohydrin resin made from adivic acid and diethylene triamine; Polyamide polyhydrin made from a blend of adivic acid, diethylene triamine and shrimp chlorohydrin with dimethylamine; cationic polyamide straw resin made from triethylene triamine; combination of aromatic sulfonic acids with formaldehyde Condensation products; aluminum acetate; aluminum formate; acetate of aluminum;
Blends of sulfates and formates; aluminum chloride; and cationic starch.

Subsequently, the filtration and dehydration/drying step (1) of the method of the present invention is a step in which the liquid portion is removed in order to obtain only the precipitated solids.

This is done by passing it through a filter cloth, porous or mesh screen, etc. At this time, mechanical action such as compression or suction, or thermal action such as blowing of heated air may be applied, and most of the liquid portion can be removed more efficiently by such operations. Other drying methods such as infrared irradiation or high frequency irradiation may also be used. If the liquid portion can be sufficiently removed by filtration, the above-mentioned drying is not necessarily necessary. By sufficiently removing the liquid portion, a molded article such as a sheet can be obtained.

In the method of the present invention, after the steps (1) to (2) above, (1) melting,
Perform the molding process or impregnation and curing process.

This melting and forming process generally involves the melting point of SPS
This is a step of heating and melting a dehydrated and dried molded object such as a sheet at a temperature of 80° C. or 350° C. or less, and then pressurizing it into shape. When this step is carried out, the SPS resin in a certain shaped body such as a sheet is melted, so that the bond with the fibrous filler becomes stronger, and a molded body with greater mechanical strength can be obtained. Cooling after melting may be carried out at a temperature between room temperature and the melting point of SPS, preferably at 20°C.
The temperature is below 0°C. Pressurization can be done by any commonly used method, such as pressing, rolling, etc.
10 to 200 kg/cil, better than 30
This is done by applying a pressure of ~150 kg/d.

On the other hand, the process of impregnation and curing, which can be carried out in place of the process of melting and shaping described above, is performed on the molded product (
This process improves the strength of the sheet by impregnating the sheet with a thermosetting resin and then curing it. Here, curing may be performed under pressure. There are no particular restrictions on the method of impregnating the thermosetting resin, but usually it is applied to the sheet with a roller, brush, etc., or it is dipped in a varnish made by adding a curing agent, additives, and solvent to the thermosetting resin and then dried. how to,
The sheet is impregnated with a varnish prepared by blending a hardening agent with a solvent-free liquid thermosetting resin by coating the sheet or by dipping the sheet in the varnish. The amount of thermosetting resin contained in this case may be determined depending on the situation, but in general, (A) 1
0.1 to 100 parts by weight of component (B)
50 parts by weight is preferred.

Various types of thermosetting resins can be used, including unsaturated polyester resins (orthophthalic acid type, isophthalic acid type, terephthalic acid type, alicyclic unsaturated fatty acid type, halogen acid-containing type, aliphatic type). Saturated ML bisphenol type, halogen-containing and sphenol type, molecular terminal (meth)acrylic acid type, vinyl ester type, etc.), epoxy resin (phenol glycidyl ether type, alcohol glycidyl ether type, glycidyl ester type, glycidyl amine type), (type, mixed type, alicyclic type, etc.), phenolic resin, urea resin, melamine resin, diallyl phthalate resin, etc. Among these, epoxy resin is preferred. In addition, when using an epoxy resin, the curing agent may be aliphatic polyamine, adane, boria, or aromatic polyamine. acid anhydride, catalytic curing agent, polymerkabutane,
Polysulfide etc. can also be used together.

In the method of the present invention, after passing through the above steps 1 or 2,
(2) Perform the step of providing a metal layer on the molded body.

Methods for providing a metal layer on a molded body include etching the bonded metal foils (subtractive method), directly plating the circuit (additive method), and laminating circuit foils and foil stamping. There are various methods, such as vacuum evaporation method and sputtering method.

Alternatively, the circuit foil may be placed in a mold used for molding and adhered to the circuit foil at the same time as the molding.

The thickness of the metal layer can be adjusted to 0.000 mm upon request. The thickness may be appropriately selected from a vapor deposited layer of several micrometers to several plates of metal foil. Further, the thickness of the insulating base material may be appropriately selected depending on requirements, but it is preferably within the range described in the JIS standard.

The metals that make up the metal layer include copper, nickel, and aluminum. It is preferable to select from tin, gold, silver, zinc, etc. Furthermore, when bonding metal foil or the like to a molded body, a heat-resistant adhesive, preferably a heat-resistant thermosetting adhesive such as an epoxy resin, is used.

The method of the present invention proceeds by sequentially carrying out each of the above steps, but these steps may be carried out either continuously or batchwise.

Moreover, the printed wiring board obtained by the method of the present invention has a thickness of o. oi to 5III1, and the dielectric constant is preferably 3.5 or less.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Preparation Example I (l) Preparation of contact product of trimethylaluminum and water 47.
4d (492 mmol) was added, and to this sulfuric acid fI was added.
Pentahydrate salt (CuSOn' 5HzO) 35.5g (142
mmol) and reacted at 20°C for 24 hours. After the reaction is complete, the solvent toluene is removed by filtration.
12.4 g of methylaluminoxane as a contact product was obtained.

(2) In a reaction vessel with an internal volume of 2 liters of SPS, 1j2 purified styrene and the above (
7 as an aluminum atom of the contact substance obtained in +)
．． 5 mmol of triisobutylaluminum, 0.038 mmol of pentamethylpentadienyl titanium trimethoxide, and
A time polymerization reaction was performed. After the reaction was completed, a methanol solution of sodium hydroxide was added to the reaction mixture to decompose and remove a portion of the catalyst, followed by repeated washing with methanol and drying to obtain 466 g of styrene polymer (polystyrene) powder.

1.2.4-Trichlorobenzene as a solvent, 135
As measured by gel permeation chromatography at ℃, the weight average molecular weight of this polymer was 290,
000, weight average molecular weight/number average molecular weight is 2.72
Met. Furthermore, it was confirmed by melting point and I:IC-NMR measurements that this polymer was polystyrene (sps) having a syndiotactic structure.

Example 1 To 102 water containing 2 g of Adan-type cationic dispersant and 10 g of T-aminopropyltriethoxysilane, 300 g of glass fiber with 6 cut lengths and a fiber diameter of 9 μm was added with vigorous stirring, and then mixed with water. Polyethylene pulp 10
0g was added under stirring, and after the glass fibers and polyethylene bulk were appropriately dispersed, 600g of SPS powder with a bulk density of 0.2g/1 obtained in Production Example 1 was added, followed by styrene-butadiene type bonding. 100g of the agent was added. Furthermore, while continuing to stir, dry aluminum sulfate 2
After adding 0g as a flocculant, the solution was diluted to contain about 10g of solids per liter, giving a total solution of 1001. This solution is passed through a mesh screen to filter out moisture, and then dried to a mesh size of 160.
A sheet of 0 g/c1l was obtained.

After preheating the above sheet at 300°C for 3 minutes in an infrared heater, it was placed in a mold with a mold temperature of 180°C, and the pressure was 8°C.
Pressure molded at 0 kg/c+fl, holding pressure for 3 minutes, thickness 1.
:2u++ molded product was obtained. The quality of the appearance of the obtained molded product, such as the embossment of the glass fibers, was visually judged.

In addition, the above molded product is coated with epoxy adhesive to a thickness of 7.
A 0 μm copper foil for printed circuit boards was laminated to produce a copper foil-attached printed wiring board. The dielectric properties of the obtained copper foil-attached printed wiring board were measured in accordance with JIS-C-6481. Further, the shaped article was heat treated in an oven at 150° C. for 30 minutes, and the dimensional change rate was determined. This dimensional change rate was calculated as follows.

First, the dimensional changes of the above-mentioned shaped product (flat plate) before and after heat treatment were measured using the following procedure. First, take a point a on the flat plate, draw a line parallel to a certain side from this point a, and draw a line parallel to a certain side.
0lnI! Take point b at a position l away.

Furthermore, draw a line parallel to another side from point a, 50
Take point C at a position mm away. However, side ab and side aC
forms a right angle.

The dimensional changes before and after the heat treatment at sides ab, ac, and point a were determined using the following equations.

% change between ab - 1bz bll/blx1ooac
% change between = l Cz Cl l/ct XIOO
Change in thickness at point a-1h. -t. l, /hl XIO
0: Distance between ab before heat treatment: Distance between ac before heat treatment: Thickness at point a before heat treatment = Distance between ab after heat treatment: Distance between ac after heat treatment: At point a after heat treatment The formulations for each thickness are shown in Table 1, and the measurement results are shown in Table 2.

Production Example 2 (Production of SPS) ゛In a reaction vessel with an internal volume of 2 liters, 7.5 mol of the contact product obtained in purified styrene lffi Production Example 1 (1) was added as aluminum atoms, and 7.5 mol of triisobutylaluminum was added.
, 5 mmol of pentamethylcyclopentadienyl titanium trimethoxide and 0.038 mmol of titanium trimethoxide were supplied, and the polymerization reaction was carried out at 70°C for 3 hours. After the reaction was completed, a methanol solution of sodium hydroxide was added to the reaction mixture to decompose and remove a portion of the catalyst, followed by repeated washing with methanol and drying to obtain 580 g of a polymer. When measured by gel permeation chromatography at 130"C using 1,2.4-t-lichlorobenzene as a solvent, the weight average molecular weight of this polymer was 592,000, and the weight average molecular weight N
/Number average molecular weight was 2.81. Furthermore, it was confirmed by melting point and 13C-NMR measurements that this polymer was polystyrene (SP S ) having a syndiotactic structure.

Production Example 3 (Production of SPS) In a reaction vessel with an internal volume of 2 liters, 1 liter of purified styrene and 1 liter of Production Example
The contact compound obtained in (1) was supplied with 5 mmol of argonium atoms, 5 mmol of triisobutylaluminum, and 0.025ξ mol of pentamethylcyclopentadienyl titanium trimethoxide, and heated to 5 mmol at 70"C. A polymerization reaction was carried out for a period of time. After the reaction was completed, a methanol solution of sodium hydroxide was added to the reaction mixture to decompose and remove a portion of the catalyst, and the mixture was repeatedly washed with methanol and dried to form a polymer 477.
I got g. The weight average molecular weight of this polymer was 802,000 when measured by gel permeation chromatography at 130''C using 1,2.4-}lichlorobenzene as a solvent, and the weight average molecular weight / number average The molecular weight was 2.24. Melting point and C-NMR measurements confirmed that this polymer was polystyrene (SPS) having a syndiotactic structure.

The same operation as in Example 1 was performed except that Examples 2 to 7, 11.12 and Comparative Examples 1 to 7 each had a certain composition as shown in Table 1. The results are shown in Table 2. Note that in Example 6, the SPS of Production Example 2 was used, and in Example 7, the SPS of Production Example 3 was used.

Production Example 4 Bis(2,
0.7 part by weight of 4-di-t-butylphenyl) pentaerythritol diphosphite and 0.1 part by weight of 2.6-di-t-butyl-4-methylphenol were added and mixed in a Henschel mixer.

This mixture was melt-spun using a single-screw extruder equipped with a die at a cylinder temperature of 300°C, and then cut to reduce the fiber length/fiber diameter to 5.
mm7 10 pm, 10 mm/1 am,
A stable of 30 mm/400 um was obtained.

Examples 8 to 10 The same operations as in Example 1 were performed except that the SPS stable obtained in Production Example 4 was used. The results are shown in Table 2.

Examples 13 to 15 and Comparative Example 7 300 g of glass fiber with a cut length of 6 mm and a fiber diameter of 10 μm was vigorously stirred in 10 liters of water containing 2 g of an Ayo-type cationic dispersant and IO g of T-aminoprobyltriethoxysilane. Then, 100 g of polyethylene bulb was added under stirring, and after the glass fibers and polyethylene pulp were dispersed, the 3
600 g of seed SPS stable was added followed by 100 g of a styrene-butadiene type binder.

Further, while stirring, 20 g of dry aluminum sulfate was added as a flocculant, and the mixture was diluted to contain about 10 g of solids per 12 parts to give a total solution of 100 i. This solution was passed through a mesh screen to filter out moisture, and then dried to obtain a basis weight of 600 g/CTa.
I got a sheet of

After immersing the sheet in an alcohol-based glycidyl-type epoxy resin, the epoxy resin is heated to 15% by drying.
parts by weight (relative to 100 parts by weight) were impregnated.

It was further cured under heating to form a base material for printed wiring boards.

A bending test of this substrate was conducted by hand.

Furthermore, a copper foil for a printed circuit board having a thickness of 70 μm coated with an epoxy adhesive was laminated on the above molded product to produce a copper foil-laminated printed wiring board. The dielectric properties of the obtained copper foil-attached printed wiring board were measured in accordance with JIS-C-6481.

The types of SPS stables used are shown in Table 3, and the measurement results are shown in Table 4.

(Hereinafter in the margin) [Effects of the Invention] As described above, the printed wiring board obtained by the method of the present invention has excellent impact resistance, heat resistance, and mechanical strength, as well as good dimensional stability and flexibility. It also has excellent surface smoothness. In particular, this printed wiring board has excellent dielectric properties, making it ideal as a multilayer printed wiring board used in fields that require high-speed arithmetic processing.It also has the advantage of reducing manufacturing costs due to its excellent formability. has.

Therefore, the printed wiring board of the present invention is expected to be widely and effectively used in the electrical and electronic fields.

Claims (4)

[Claims] (1) [1] 95 to 20% by weight of (A) a styrenic polymer having a syndiotactic structure in water and/or an organic solvent. (B) 5 to 80% by weight of a fibrous filler with a fiber length of 1 to 50 mm and (C) a binder and/or binding fibers in an amount of 0.0% to 100 parts by weight of the above (A) and (B) components. A step of dispersing 1 to 30 parts by weight into a slurry at a concentration of 0.5 to 100 g/l, [2] A step of sedimenting the dispersed solids in the slurry, [3] A step of dispersing the solids in the slurry. A step of filtering and/or drying water and/or an organic solvent and forming the remainder into a molded object, [4] A step of heating and melting and then pressure molding, and [5] A step of providing a metal layer on the obtained molded object. A method for manufacturing a printed wiring board, characterized by sequentially performing the following steps. (2) After the steps [1] to [3], the steps of [4] impregnating and curing the thermosetting resin and [5] providing a metal layer on the obtained molded body are sequentially performed. A method for manufacturing a printed wiring board. (3) (A) 95 to 20% by weight of a styrenic polymer having a syndiotactic structure, (B) 5 to 80% by weight of a fibrous filler with a fiber length of 1 to 50 mm, and (C) a binder and/or bond. Printed wiring formed by providing a metal layer on a molded body obtained from a styrenic polymer composition containing 0.1 to 30 parts by weight of fibers based on a total of 100 parts by weight of components (A) and (B). Board. (4) The printed wiring board according to claim 3, having a thickness of 0.01 to 5 mm.