JP2000216511A - Multilayer printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To downsize a multilayer printed wiring board by forming an adhesive layer made of a resin compsn. contg. a specified syndiotactic polystyrene or prepreg with glass cloths impregnated with it which has a lower m.p. than that of printed wiring board layers on both sides between a multilayer printed wiring board. SOLUTION: This multilayer printed wiring board has an adhesive layer B between layers A, B with metal foil layers having circuit patterns. A resin part forming the layer B has a m.p. less than those of resin parts forming the layers A, C and is composed of a resin compd. contg. a syndiotactic polystyrene as a main component or prepreg. A styrene-based polymer having syndiotactic structure mainly in the layer B is a copolymer having structure units shown by formulae I, II and a polymerization degree 5 or more wherein R1 is a substituted group contg. H atom, halogen atom, C, O, N, S, P or Si atom and m, n are 1-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer printed wiring board, and more particularly to a styrenic polymer having a syndiotactic structure (hereinafter simply referred to as "Syndi It may be referred to as "Otactic polystyrene" or "SPS.")
Also, the present invention relates to a multilayer printed wiring board using the resin composition and using a specific syndiotactic polystyrene or the resin composition for adhesion between the layers.

[0002]

2. Description of the Related Art In recent years, electronic devices such as mobile phones, various AV devices, and personal computers have been developed, and they are being used in our daily lives and are becoming deeply penetrated.
Printed wiring boards are frequently used as basic components.
In such a printed wiring board, it is required that the transmission speed of an electronic signal is high in terms of the operation speed of an electronic circuit, and that the transmission loss of an electric signal is small from the viewpoint of reducing generated energy loss. However, these performances are deeply related to the electrical characteristics of the resin forming the main body of the printed wiring board. That is, the magnitude of the dielectric constant and the dielectric loss of the resin greatly affect the transmission speed of the electric signal and the electric signal loss. In particular, it is desired that these values in the high frequency band be as small as possible. Further, mechanical properties such as solder resistance and heat resistance at the time of manufacturing an electronic component, and strength required as a molding material are also important factors required for the resin.

Conventionally, as the resin, a fluorine resin, an epoxy resin, a polyolefin resin such as polyethylene, a polyarylene sulfide resin and the like have been used. However, the injection molding property of the fluorine resin is not good.
In addition, problems such as high cost, insufficient electric characteristics of epoxy resin, and low heat resistance of polyolefin resin have been pointed out. In response to this problem, it has been recently proposed to use syndiotactic polystyrene having excellent properties such as good electrical properties, heat resistance, and solder resistance (see, for example, JP-A-06-275929). No., JP-A-07-1
42830, JP-A-09-77937, etc.).

On the other hand, it is also required to further improve the performance of the printed wiring board. Therefore, in order to reduce the size of the substrate and further increase the density, a resin molded layer constituting the main body of the printed wiring board is required. Have been attempted to be multilayered rather than monolayered. However, in the case of this multilayering, when using the syndiotactic polystyrene, it is necessary to use an epoxy resin-based or polyimide-based adhesive as an adhesive for bonding between the layers,
When these adhesives are used, the good electrical properties of syndiotactic polystyrene are impaired, and there has been a problem that a sufficient effect cannot be obtained.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above, and it is possible to reduce the size of the substrate and increase the density without deteriorating the good electrical characteristics of syndiotactic polystyrene. It is an object of the present invention to provide an intended multilayer printed wiring board.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific syndiotactic polystyrene and a specific syndiotactic polystyrene are used as an adhesive layer for bonding between multilayered molded products for printed wiring boards. A resin composition containing syndiotactic polystyrene or a prepreg impregnated in glass cloth with these, and a multilayer printed wiring board obtained using a material having a lower melting point than a printed wiring board layer bonded on both sides, It has been found that the pattern is maintained with high accuracy, the electrical characteristics are excellent, and the adhesive strength is also excellent. The present invention has been completed based on such findings.

That is, the present invention provides the following multilayer printed wiring board. 1. A multilayer printed wiring board having a portion composed of the following three layers (A) to (C). (I) The layer (A) and the layer (C) are each independently a printed wiring board layer using a resin sheet made of a resin composition obtained by blending the following (1) and (2), or A printed wiring board layer using a prepreg obtained by impregnating the resin composition of (1) with the fibrous filler of (2). (1) 5 to 100% by weight of a resin composition consisting of the following: 100 parts by weight of a resin part consisting of the following (A) to (C):
(A) 10 to 100% by weight of a polystyrene resin mainly having a syndiotactic structure, (B) Polymer 0 having compatibility or affinity with the component (A) and having a polar group
-10% by weight (including 0), (c) the above (a), (b)
Thermoplastic resin and / or rubbery elastic body other than components 0-9
0% by weight (including 0) 0 to 100 parts by weight (including 0) of a flame retardant, and a flame retardant auxiliary agent, if necessary, / = 0 to 10 (not including 0) 0) to 350 parts by weight (including 0) of the inorganic filler (2) 0 to 95% by weight (including 0) of the fibrous filler (II) It is a resin sheet layer comprising a resin composition comprising (1) and (2), wherein the melting point of the resin composition comprising (1) and (2) forming the layer (B) is (A) (A) lower than the melting point of the resin composition forming the layer and (C) the melting point of the resin composition forming the layer;
An adhesive layer disposed between the layer and the layer (C). (1) 5 to 100% by weight of a resin composition consisting of the following: 100 parts by weight of a resin part consisting of the following (A) to (C):
(A) 10 to 100% by weight of a polystyrene resin mainly having a syndiotactic structure, (B) Polymer 0 having compatibility or affinity with the component (A) and having a polar group
-10% by weight (including 0), (c) the above (a), (b)
Thermoplastic resin and / or rubbery elastic body other than components 0-9
0% by weight (including 0) 0 to 100 parts by weight (including 0) of a flame retardant, and a flame retardant auxiliary agent, when using a flame retardant, if necessary, / = 0 to 10 (not including 0) 1.) Weight ratio of inorganic filler: 0 to 350 parts by weight (including 0) (2) Fibrous filler: 0 to 95% by weight (including 0) A multilayer printed wiring board having a portion composed of the following three layers (A) to (C). (I) The layer (A) and the layer (C) are each independently a printed wiring board layer using a resin sheet made of a resin composition obtained by blending the following (1) and (2), or A printed wiring board layer using a prepreg obtained by impregnating the resin composition of (1) with the fibrous filler of (2). (1) 5 to 100% by weight of a resin composition consisting of the following: 100 parts by weight of a resin part consisting of the following (A) to (C):
(A) 10 to 100% by weight of a polystyrene resin mainly having a syndiotactic structure, (B) Polymer 0 having compatibility or affinity with the component (A) and having a polar group
-10% by weight (including 0), (c) the above (a), (b)
Thermoplastic resin and / or rubbery elastic body other than components 0-9
0% by weight (including 0) 0 to 100 parts by weight (including 0) of a flame retardant, and a flame retardant auxiliary agent, when using a flame retardant, if necessary, / = 0 to 10 (not including 0) 0) to 350 parts by weight (including 0) of the inorganic filler (2) 0 to 95% by weight (including 0) of the fibrous filler (II) (1) the resin composition of (2)
Prepreg impregnated with a fibrous filler of
(B) the melting point of the resin composition of the layer (1) is lower than the melting point of the resin composition of the layer (A) and the melting point of the resin composition of the layer (C); ) And an adhesive layer disposed between the layer (C). (1) 5 to 100% by weight of a resin composition consisting of the following: 100 parts by weight of a resin part consisting of the following (A) to (C):
(A) 10 to 100% by weight of a polystyrene resin mainly having a syndiotactic structure, (B) Polymer 0 having compatibility or affinity with component (A) and having a polar group
-10% by weight (including 0), (c) the above (a), (b)
Thermoplastic resin and / or rubbery elastic body other than components 0-9
0% by weight (including 0) 0 to 100 parts by weight (including 0) of a flame retardant, and a flame retardant auxiliary agent, when using a flame retardant, if necessary, / = 0 to 10 (not including 0) 2.) The weight ratio of the inorganic filler is 0 to 350 parts by weight (including 0). (2) The fibrous filler is 0 to 95% by weight (0 is not included). In the (B) layer, (a) the styrene-based polymer mainly having a syndiotactic structure is at least
The degree of polymerization having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) (excluding the structural unit represented by the general formula (1)) is 5: 3. The multilayer printed wiring board according to the above 1 or 2, which is the above copolymer.

[0008]

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(In the formula, R ¹ represents a hydrogen atom, a halogen atom or a substituent containing carbon, oxygen, nitrogen, sulfur, phosphorus, or a silicon atom, and m represents 1, 2, or 3. When there are two or more, each R ¹ may be the same or different.)

[0010]

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(Wherein, R ² represents a hydrogen atom, a halogen atom, or a substituent containing carbon, oxygen, nitrogen, sulfur, phosphorus, or a silicon atom, and n represents 1, 2, or 3. And when R ² is plural, each R ² may be the same or different.) 4. The multilayer printed wiring board according to any one of the above items 1 to 3, wherein the resin composition constituting the layer (B) has a melting point of 250 ° C. or less. 5. The melting point of the resin composition forming the layer (B) is 10 points lower than the melting point of the resin composition forming the layers (A) and (C).
4. The multilayer printed wiring board according to any one of the above items 1 to 3, which is lower by at least C.

[0012]

Embodiments of the present invention will be described below. The multilayer printed wiring board according to the present invention,
It has a portion composed of the following three layers (A) to (C). That is, it is essential that the (B) layer is present as an adhesive layer between the (A) layer and the (C) layer provided with the metal foil layer forming the circuit pattern. The melting point of the resin part forming the layer (B) is lower than the melting points of the resin parts forming the layers (A) and (C). Due to such features, the following advantages are obtained. That is, when a multilayer printed wiring board is manufactured by stacking and pressing these three layers, if a pressing temperature is appropriately selected at the time of pressing,
Even if the resin part forming the layer (B) is melted, the resin part forming the layers (A) and (C) does not melt, so that the layer (B) functions as an adhesive layer, and the layers (A) and ( Since the shape of the layer (C) is maintained as it is, it is possible to accurately maintain the circuit patterns provided on the layers (A) and (C), and the layer (B) is also syndiotactic polystyrene. Since it is composed of a resin composition or a prepreg containing as a main component, the excellent electrical properties of syndiotactic polystyrene can be exhibited without loss.

The multilayer printed wiring board according to the present invention only needs to have these three-layer structure portions, and may be composed of only these three layers. For example, another layer such as a protective layer or a cushion layer, or another single-layer or multilayer printed wiring board may be further laminated. Furthermore, among these three layers,
A structure in which an adhesive layer (B) is laminated outside the layer (A) and a layer (C) is laminated outside the layer (B), that is,
It may be a multilayer printed wiring board having five layers of (C) layer- (B) layer- (A) layer- (B) layer- (C) layer, and furthermore, a protective layer, a cushion layer, etc. May be provided.

The contents of each layer will be described below in detail. 1. Layers (A) and (C) The layers (A) and (C) are printed wiring board layers, and the printed wiring board layer has a metal foil layer on which a circuit pattern is formed on one surface. A metal foil layer on which a circuit pattern is formed or a simple metal foil layer on which no circuit pattern is formed is provided on the other surface. Usually, copper, aluminum,
A thin film of silver, gold, zinc, tin or the like is used.

The layers (A) and (C) use a resin sheet or prepreg, which will be described later, and are provided with the above-mentioned metal foil layers on both surfaces of the resin sheet or prepreg, so that the printed wiring board can be used. Layer. The resin sheet or prepreg used for the layer (A) and the layer (C) may be the same or different.
That is, the (A) layer uses a resin sheet, the (C) layer uses a prepreg, or vice versa,
The layer (A) and the layer (C) may both use a resin sheet, and the layer (A) and the layer (C) may both use a prepreg, and there is no particular limitation. . Furthermore, even when the resin sheet is used for both the layer (A) and the layer (C), the types and the amounts of the components of the resin composition constituting each resin sheet are not necessarily the same. The same applies to the case of prepreg.

Regardless of whether a resin sheet is used or a prepreg is used, the layers (A) and (C) do not need to use one resin sheet or prepreg, and the required insulation is required. Depending on the degree of sex and strength,
A plurality of, for example, three sheets may be stacked. (1) Method for Producing Layer (A) and Layer (C) The layer (A) or the layer (C) is a resin sheet prepared by a known method using a resin composition described below, and further, a resin pellet thereof, or By using a prepreg obtained by impregnating a resin composition described later in a fibrous filler and attaching metal foils to both surfaces thereof, layers (A) and (C), which are printed wiring board layers, can be formed. The production method is not particularly limited, and a known method may be appropriately used.

For example, in the case of the injection molding method, a metal foil is inserted into both inside surfaces of a mold, and a metal-bonded substrate is directly formed by insert molding. In the case of the extrusion method,
A metal foil is inserted between a pair of metal belts on both sides or one side, and a plate-like molten material is sandwiched between the metal belts to directly form a metal-clad substrate. In the case of the compression molding method, the obtained pellet or the flat plate obtained by the above method is mounted in a mold, and a metal foil substrate is directly formed by inserting a metal foil into the mold on both sides or one side. I do.

The prepreg is obtained by impregnating a resin composition with glass cloth. The weave of the glass cloth is not particularly limited. For example, a plain weave, a twill weave, a perforated plain weave, or the like can be arbitrarily selected. The thickness of the glass cloth layer and the ratio of the thickness of the glass cloth layer to the total thickness of the laminate are not particularly limited.

The method for impregnating the glass cloth with the resin composition is not particularly limited, and a conventionally known method can be arbitrarily selected. For example, each component of the resin composition is dry-blended, pelletized by an ordinary method, then formed into a molding material sheet by an extrusion molding method, and the obtained molding material sheet is formed into a glass by a continuous compression molding method or a compression molding method. A method of impregnating the cloth is given.

Here, the continuous compression molding method means that a molding material sheet and a glass cloth are inserted several layers between a pair of metal belts,
This is a method of forming a laminate by cooling after heating and melting. The compression molding method is a method of forming a laminate by mounting a molding material sheet and a glass cloth in a mold. Further, the glass cloth may be impregnated by heating, compressing and cooling with a roll-to-roll or double belt press or single belt press while extruding the resin composition raw material into a film by a T-die extrusion method or the like. S
A glass cloth previously impregnated with a molding material such as PS may be used. (2) Contents of each component of the resin composition Regarding kneading of the following components, a method of blending and melt-kneading at any stage of the syndiotactic polystyrene production process, or a method of blending and melting each component constituting the composition Various methods such as kneading may be used. (A) Styrene-based polymer mainly having a syndiotactic structure A syndiotactic structure in “a styrene-based polymer mainly having a syndiotactic structure” means that a stereochemical structure is a syndiotactic structure, that is, from a carbon-carbon bond. A phenyl group which is a side chain with respect to the formed main chain has a three-dimensional structure in which the phenyl groups are alternately located in opposite directions,
Its tacticity is nuclear magnetic resonance with isotope carbon
(13C-NMR). Tacticity measured by the 13C-NMR method can be represented by the existence ratio of a plurality of continuous structural units, for example, a dyad for two, a triad for three, and a pentad for five. The styrenic polymer having a predominantly syndiotactic structure as referred to in the present invention is usually at least 75%, preferably at least 85% by racemic diad,
Or 30% or more in racemic pentad, preferably 5%
Polystyrene having a syndiotacticity of 0% or more, poly (alkylstyrene), poly (arylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene),
Poly (vinyl benzoate), hydrogenated polymers thereof, mixtures thereof, or copolymers containing these as a main component. Here, the poly (alkyl styrene) includes poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (tertiary butyl styrene), and the like. (Phenylstyrene),
There are poly (vinylnaphthalene), poly (vinylstyrene) and the like, and as poly (halogenated styrene), there are poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and the like. Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

Among these, preferred styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), and poly (p-chlorostyrene). ), Poly (m-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene and copolymers containing these structural units.

Such a styrenic polymer having a predominantly syndiotactic structure can be prepared, for example, by using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent.
It can be produced by polymerizing a styrene-based monomer (a monomer corresponding to the above-mentioned styrene-based polymer) (JP-A-62-187708). For poly (halogenated alkylstyrene), see JP-A-1-4691.
No. 2, these hydrogenated polymers are disclosed in JP-A-1-1785.
It can be obtained by the method described in JP-A-05-2005.

Among these styrenic polymers having a syndiotactic structure, in the present invention, from the viewpoint of heat resistance and mechanical strength, tacticity is particularly 70% or more in racemic pentad, and weight average molecular weight. Is 5-8
A thing of 100,000 is preferable. (B) a polymer having compatibility or affinity with syndiotactic polystyrene and having a polar group; syndiotactic polystyrene and a thermoplastic resin;
Alternatively, it is blended in order to improve the affinity between the rubber-like elastic body and effectively compatibilize it, and to improve the affinity between syndiotactic polystyrene and glass fiber. Specific examples include polymers having compatibility or affinity with syndiotactic polystyrene and having a polar group.

Here, the polymer having compatibility or affinity with syndiotactic polystyrene refers to a polymer having a chain exhibiting compatibility or affinity with syndiotactic polystyrene in a polymer chain. Examples of the polymer exhibiting such compatibility or affinity include, for example, syndiotactic polystyrene, atactic polystyrene, isotactic polystyrene, styrene-based copolymer, polyphenylene ether, polyvinyl methyl ether, and the like. , A block or a graft chain.

The polar group mentioned here may be any group which improves the adhesiveness with an inorganic filler, and specifically includes an acid anhydride group, a carboxylic acid group, a carboxylic ester group, and a carboxylic acid group. Chloride group, carboxylic acid amide group, carboxylic acid group, sulfonic acid group, sulfonic acid ester group, sulfonic acid chloride group, sulfonic acid amide group, sulfonic acid group, epoxy group, amino group, imide group, oxazoline group, etc. No.

This compatibilizer can be obtained by reacting a polymer having compatibility or affinity with the above-mentioned syndiotactic polystyrene and a modifier described below in the presence or absence of a solvent or other resin. it can. As the modifier, for example, a compound containing an ethylenic double bond and a polar group in the same molecule can be used. Specifically, maleic anhydride, maleic acid, maleic ester, maleimide and its N-substituted product, maleic acid derivatives such as maleic acid salt, fumaric acid, fumaric acid ester, and fumaric acid such as fumaric acid salt Derivatives, itaconic anhydride, itaconic acid, itaconic acid esters, itaconic acid derivatives including itaconic acid salts, acrylic acid, acrylic acid esters,
Acrylic acid derivatives such as acrylamide and acrylate, methacrylic acid, methacrylic acid esters, methacrylic acid amides, methacrylic acid salts, and methacrylic acid derivatives such as glycidyl methacrylate are exemplified. Among them, maleic anhydride, fumaric acid and glycidyl methacrylate are particularly preferably used.

A known method is used for the modification.
150 using a mill, Banbury mixer, extruder, etc.
A method of melt-kneading and reacting at a temperature of from 0 to 350 ° C, and a method of heating and reacting in a solvent such as benzene, toluene, and xylene can be exemplified. In order to further facilitate these reactions, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, azobisisovaleronitrile, It is effective to use a radical generator such as 2,3-diphenyl-2,3-dimethylbutane. Of these, 2,3-diphenyl-2,3-dimethylbutane is particularly preferably used.

A preferred modification method is a method of melt-kneading in the presence of a radical generator. Further, at the time of modification, another resin may be added. Specific examples of the compatibilizer include a styrene-maleic anhydride copolymer (SM
A), a styrene-glycidyl methacrylate copolymer,
Carboxylic acid-modified polystyrene, epoxy-modified polystyrene, oxazoline-modified polystyrene, amine-modified polystyrene, sulfonated polystyrene, styrene ionomer, styrene-methyl methacrylate
To-graft polymer, (styrene-glycidyl methacrylate) -methyl methacrylate-graft copolymer, acid-modified acryl-styrene-graft polymer,
(Styrene-glycidyl methacrylate) -styrene-
Graft polymer, polybutylene terephthalate-polystyrene-graft polymer, maleic anhydride-modified P
S, fumaric acid-modified PS, glycidyl methacrylate-modified PS, amine-modified PS and other modified styrenic polymers,
Modified polyphenylene ethers such as (styrene-maleic anhydride) -polyphenylene ether-grafted polymer, maleic anhydride-modified polyphenylene ether, glycidyl methacrylate-modified polyphenylene ether, and amine-modified polyphenylene ether And the like.

Of these, modified PS and modified polyphenylene ether are particularly preferably used. Further, two or more of the above polymers can be used in combination. The polar group content in the compatibilizer is preferably 10
It is in the range of 0.05 to 20% by weight, more preferably 0.05 to 10% by weight, based on 0% by weight. If the content is less than 0.01% by weight, it is necessary to add a large amount of a compatibilizing agent in order to exert an adhesive effect with the inorganic filler, and the mechanical properties, heat resistance, and moldability of the composition may be reduced. Absent. On the other hand, if it exceeds 20% by weight, the compatibility with syndiotactic polystyrene may be undesirably reduced. (C) Thermoplastic resin other than rubber-like elastic body and / or syndiotactic polystyrene In order to improve mechanical properties such as strength, a thermoplastic resin other than rubber-like elastic body and / or syndiotactic polystyrene is further blended. May be.

Specific examples of the rubber-like elastic material include, for example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber Styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer ( SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SI
S), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), or ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPD)
M), olefin rubbers such as linear low-density polyethylene elastomers, or butadiene-acrylonitrile-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene Core-shell rubber (MAS), octyl acrylate-butadiene-styrene-core-shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene-core-shell rubber (AAB)
S), butadiene-styrene-core-shell rubber (SB
R), a core-shell type particulate elastic material such as a siloxane-containing core-shell rubber such as methyl methacrylate-butyl acrylate-siloxane, or a rubber modified from these.

Among these rubber-like elastic materials, in the present invention, hydrogenated styrene-butadiene-styrene block copolymer (SEB) is used in view of heat resistance and dielectric properties.
S) is preferred. Thermoplastic resins other than syndiotactic polystyrene Examples of thermoplastic resins other than syndiotactic polystyrene include linear high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, and syndiotactic polypropylene. , Block polypropylene, random polypropylene, polybutene, 1,2-polybutadiene, 4-methylpentene, cyclic polyolefin and polyolefin resins represented by copolymers thereof, atactic polystyrene, isotactic polystyrene, HIPS, A
BS, AS, styrene-methacrylic acid copolymer, styrene-methacrylic acid / alkyl ester copolymer, styrene-methacrylic acid / glycidyl ester copolymer, styrene-acrylic acid copolymer, styrene-acrylic acid / alkyl ester copolymer Polystyrene resins such as polymers, styrene-maleic acid copolymers and styrene-fumaric acid copolymers, polyester resins such as polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyamide 6, polyamide 6,6 And other polyamide resins, polyphenylene ether, polyarylene sulfide, poly-4
-Any known materials such as fluorinated polyethylene resins such as fluorinated ethylene (PTFE) can be used. Among them, polyolefins such as polyethylene and polypropylene or polyphenylene ethers are preferred.
In addition, these thermoplastic resins can be used alone or in combination of two or more. (D) Flame retardant In the present invention, for those requiring flame retardancy, it is preferable to add the following flame retardants. Various flame retardants can be used, and there is no particular limitation. Particularly, halogen-based flame retardants and phosphorus-based flame retardants are preferable.
Examples of the halogen-based flame retardant include halogenated epoxy compounds, pentabromobenzyl acrylate, halogenated amide compounds, and 1,2-di (pentabromophenyl).
Brominated polystyrene such as ethane, poly (dibromophenylene oxide), polytribromostyrene, polydibromostyrene, tetrabromobisphenol A, tetrabromophthalic anhydride, hexabromobenzene, tribromophenylallyl ether, pentabromotoluene,
Pentabromophenol, tribromophenyl-2,3
-Dibromo-propyl ether, tris (2,3-dibromopropyl) phosphate, tris (2-chloro-3
-Bromopropyl) phosphate, octabromodiphenyl ether, decabromodiphenyl ether, octabromobiphenyl, pentachloropentacyclodecane,
Hexabromocyclododecane, hexachlorobenzene,
Pentachlorotoluene, hexabromobiphenyl, decabromobiphenyl, tetrabromobutane, decabromodiphenyl ether, hexabromodiphenyl ether,
Halogenated polycarbonate oligomers such as ethylene-bis- (tetrabromophthalimide), tetrachlorobisphenol A, tetrabromobisphenol A, oligomers of tetrachlorobisphenol A or tetrabromobisphenol A, brominated polycarbonate oligomers, polychlorostyrene, bis (Tribromophenoxy) ethane and the like.

As the flame retardant, among these, in particular,
2-Di (pentabromophenyl) ethane is preferred.
Brominated polystyrene is polydibromostyrene,
It may be polytribromostyrene or a copolymer thereof. The brominated polystyrene may be produced by brominating polystyrene or may be obtained by polymerizing brominated styrene. The bromine content of these flame retardants is
It is preferably at least 50%. Examples of the phosphorus-based flame retardant include ammonium phosphate, tricresyl phosphate, triethyl phosphate, acidic phosphate, and triphenylphosphine oxide. (E) Flame retardant aid In the present invention, when the above-mentioned component (d) is used, it is desirable to use a flame retardant aid as the component (e).

Here, there are various flame retardant assistants, and there is no particular limitation. For example, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, metal antimony, antimony trichloride, Antimony flame retardants such as antimony chloride, antimony trisulfide and antimony pentasulfide are exemplified. Other than these, zinc borate, barium metaborate, zirconium oxide, and the like can be given. Among these, antimony trioxide is particularly preferred.

Further, a tetrafluoroethylene polymer may be added to prevent dripping from melting. As the tetrafluoroethylene polymer, specifically, in addition to the tetrafluoroethylene homopolymer, a copolymer of tetrafluoroethylene and hexafluoropropylene, and further contains a small amount of a copolymerizable ethylenically unsaturated monomer Examples include a tetrafluoroethylene copolymer. As this tetrafluoroethylene polymer, those having a fluorine content of 65 to 76% by weight, preferably 70 to 76% by weight are used. The tetrafluoroethylene polymer is used in an amount of 0.0 with respect to 100 parts by weight of the total of (a) and (b).
03 to 10 parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.1 to 2 parts by weight. (F) Inorganic filler or organic filler As the inorganic filler, a granular or powdery filler can be used. Granular and powdery fillers include, for example, talc, carbon black, graphite, titanium dioxide,
Silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, glass beads And the like.

Among the various fillers as described above, especially glass fillers such as glass powder, glass flake,
Glass beads are preferred. As these fillers, those subjected to surface treatment may be used. The coupling agent used for the surface treatment is used for improving the adhesiveness between the filler and the resin, and includes a so-called silane-based coupling agent, a titanium-based coupling agent, and the like. Any one can be selected and used.

These inorganic fillers can be used alone or in combination of two or more. Examples of the organic filler include fluororesins and aramid resin fibers. As for these fillers, those subjected to surface treatment using a coupling agent usually used for surface treatment, for example, a silane coupling agent, a titanium coupling agent, or the like are preferably used. The content of the coupling agent is the same as that used for the inorganic filler. (G) Various additives As long as the object of the present invention is not impaired, various additives exemplified below can be blended.

Antiblocking Agent (AB Agent) Examples of the antiblocking agent include the following inorganic particles or organic particles. As the inorganic particles, IA
, IIA, IVA, VIA, VIIA, VIII, IB
Oxides, hydroxides, sulfides, nitrides, halides, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylate salts of Group IIB, IIIB, IIIB and IVB elements, Examples thereof include silicates, titanates, borates and hydrates thereof, composite compounds centered on them, and natural mineral particles.

Specifically, compounds of Group IA such as lithium fluoride, borax (sodium borate hydrate), magnesium carbonate, magnesium phosphate, magnesium oxide (magnesia), magnesium chloride, magnesium acetate, magnesium fluoride, titanium fluoride Magnesium silicate, magnesium silicate, magnesium silicate hydrate (talc), calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate (gypsum), calcium acetate, calcium terephthalate, calcium hydroxide, calcium silicate, calcium fluoride, titanate Group IIA compounds such as calcium, strontium titanate, barium carbonate, barium phosphate, barium sulfate, barium sulfite, titanium dioxide (titania), titanium monoxide, titanium nitride, zirconium dioxide (zirconia), dimonoxide Group VIA element compounds such as IVA element compounds such as conium, molybdenum dioxide, molybdenum trioxide, and molybdenum sulfide; Group VIA element compounds such as manganese chloride and manganese acetate; Group VIII element compounds such as cobalt chloride and cobalt acetate; Group IB element compounds such as cuprous chloride, group IIB compounds such as zinc oxide and zinc acetate, aluminum oxide (alumina), aluminum hydroxide, aluminum fluoride, alumina silicate (alumina silicate, kaolin, kaolinite), etc. III Group B element compounds, silicon oxide (silica, silica gel), graphite, carbon, graphite, glass, etc., Group IVB element compounds, kernalite, kainite, mica (mica, kinunmo), and particles of natural minerals such as byrose ore. Can be

Examples of the organic particles include Teflon, melamine resin, styrene / divinylbenzene copolymer, acrylic resin, and cross-linked products thereof. Antioxidant As the antioxidant, any known antioxidant such as phosphorus-based, phenol-based, and sulfur-based can be used. In addition, these antioxidants may be used alone, or
Two or more can be used in combination.

Nucleating Agents As nucleating agents, metal salts of carboxylic acids such as aluminum di (pt-butylbenzoate) and phosphoric acids such as sodium methylenebis (2,4-di-t-butylphenol) acid phosphate Any of known metal salts, talc, phthalocyanine derivatives and the like can be used. These nucleating agents can be used alone or in combination of two or more. Plasticizers Examples of the plasticizer include polyethylene glycol, polyamide oligomer, ethylene bisstearamide, phthalic acid ester, polystyrene oligomer, and the like. Any known materials such as polyethylene wax and silicone oil can be arbitrarily selected and used. These plasticizers can be used alone or in combination of two or more.

Release Agent The release agent can be arbitrarily selected from known materials such as polyethylene wax, silicone oil, long-chain carboxylic acid and long-chain carboxylic acid metal salt. These release agents may be used alone or in combination of two or more.

Process Oil In the present invention, a process oil may be further blended. Process oils are roughly classified into paraffin-based oils, naphthenic-based oils, and aroma-based oils, depending on the type of oil. Among them, paraffin-based oils are preferred. As the viscosity of the process oil, the kinematic viscosity at 40 ° C. is 15 to 600.
cs is preferable, and 15 to 500 cs is more preferable.

These process oils can be used alone or in combination of two or more. Halogen scavenger Halogen scavenger is intended to improve the thermal stability of halogenated polystyrene resin as a flame retardant, to improve the corrosion resistance of the mold and the retention stability of the composition, for example, Hydrotalcites and the like are preferably used.

Light Stabilizers Light stabilizers include, for example, di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate; 4-benzoyloxy-2,2,6,6-tetramethylpiperidine;
Hindered amine compounds such as 1,2,3,4-tetra- (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, 2- (2-hydroxy-5-methylphenyl) benzotriazole , 2-
(2-hydroxy-5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-
And benzotriazole-based compounds such as (butylphenyl) benzotriazole.

Lubricants Examples of the lubricant include fatty acids such as stearic acid and behenic acid, zinc stearate, calcium stearate, and the like.
Examples include fatty acid metal salts such as magnesium stearate and the like, and ethylene bisstearamide. Examples of the plasticizer include polyethylene glycol, polyamide oligomer, phthalate ester, polystyrene oligomer, polyethylene wax, mineral oil and silicone oil. . (H) Fibrous Filler In the present invention, the fibrous filler is used as one component of a resin composition to be a material of the resin sheet, and is used to impregnate a resin portion when producing the prepreg. Sometimes used as.

Examples of the type of the fibrous filler include glass fibers, carbon fibers, and organic synthetic fibers such as wholly aromatic polyamide fibers, polyimide fibers, and whiskers. The whiskers include whiskers having a composition of carbon, potassium titanate, magnesia, silicon carbide, silicon nitride, zinc oxide, calcium carbonate and the like. As a shape, when used as one component of the resin composition, there are a bundle cut shape, a short fiber, a filament shape, a whisker, and the like. In the case of the bundle cut shape, the length is 0.05 to 50.
mm and a fiber diameter of 5 to 20 μm are preferred. Among the above fillers, glass fiber is particularly preferable. In addition, as a material used when producing a prepreg, a cloth shape or a mat shape is used, and a glass cloth is preferable.

As the above-mentioned glass fibers, those subjected to a surface treatment with a coupling agent are preferably used. The coupling agent used for the surface treatment can be appropriately selected and used from those known as a so-called silane coupling agent and a titanium coupling agent. Specific examples of the silane coupling agent include triethoxysilane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (1,1 -Epoxycyclohexyl) ethyltrimethoxysilane, N-
β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxy Silane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyl-tris (2-methoxy-ethoxy) silane, N-
Methyl-γ-aminopropyltrimethoxysilane, N-
Vinylbenzyl-γ-aminopropyltriethoxysilane, triaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3- (4,5-dihydroimidazole) propyltriethoxysilane, hexamethyldisilazane, N, O- (Bistrimethylsilyl) amide, N, N-bis (trimethylsilyl) urea and the like. Among them, preferred are γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4
-Epoxycyclohexyl) aminosilane such as ethyltrimethoxysilane and epoxysilane.

Specific examples of the titanium-based coupling agent include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl Bis (ditridecylphosphite) titanate, tetra (1,1-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, Isopropyl trioctanoyl titanate,
Isopropyl dimethacryl isostearyl titanate, isopropyl isostearyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate,
Isopropyl tri (N-amidoethyl, aminoethyl)
Titanate, dicumylphenyloxyacetate titanate, diisostearoylethylene titanate and the like can be mentioned. Preferred among these is isopropyl tri (N-amidoethyl, aminoethyl) titanate.

The surface treatment of the glass fiber using such a coupling agent can be carried out by a commonly known method, and is not particularly limited. For example, a method such as a sizing treatment in which an organic solvent solution or suspension of the above-mentioned coupling agent is applied as a so-called sizing agent can be used. Further, a film-forming substance for glass can be used in combination with the above-mentioned coupling agent. The film-forming substance is not particularly limited, and examples thereof include polymers of polyester type, urethane type, epoxy type, acrylic type, vinyl acetate type and the like. (3) Mixing ratio of each component When a resin sheet is used as the (A) layer or the (C) layer, a resin composition obtained by mixing the following (1) and (2) is used. Alternatively, when a prepreg is used as the layer (C), a resin composition comprising the following (1) is used, and the resin composition is impregnated with the fibrous filler (2). (1) 5 to 100% by weight of a resin composition consisting of the following: 100 parts by weight of a resin part consisting of the following (A) to (C):
(A) 10 to 100% by weight of a polystyrene resin mainly having a syndiotactic structure, (B) Polymer 0 having compatibility or affinity with the component (A) and having a polar group
-10% by weight (including 0), (c) the above (a), (b)
Thermoplastic resin and / or rubbery elastic body other than components 0-9
0% by weight (including 0) 0 to 100 parts by weight (including 0) of a flame retardant, and a flame retardant auxiliary agent, when using a flame retardant, if necessary, / = 0 to 10 (not including 0) 0) to 350 parts by weight of inorganic filler (including 0) (2) 0 to 95% by weight of fibrous filler (including 0) The amount of SPS of component (a) is 10 If the amount is less than 10% by weight, the resulting composition does not sufficiently exhibit the properties of SPS, and the object of the present invention cannot be achieved. In order to effectively exhibit the characteristics of SPS, the compounding amount of component (a) should be 30 to 10
A range of 0% by weight is preferable, and a range of 40 to 100% by weight is particularly preferable. When the amount of the component (b) exceeds 10% by weight, the resulting composition has reduced mechanical properties and solvent resistance. Further, the amount of the component (c) is 90% by weight.
If the ratio exceeds the above range, the resulting composition will not sufficiently exhibit the properties of SPS, and the heat resistance and the like will be reduced. In order to effectively exhibit the characteristics of SPS, the amount of the component (iii) is preferably in the range of 0 to 70% by weight, and particularly preferably in the range of 0 to 60% by weight.

The flame retardant is added in an amount of 0 to 100 parts by weight (including 0) based on 100 parts by weight of the resin part composed of the above (a) to (c). If it exceeds 100 parts by weight, the effect of improving the flame-retardant performance is not seen for the amount, and the mechanical properties are rather deteriorated. From the viewpoints of flame-retardant performance and mechanical properties, the preferred compounding amount is in the range of 5 to 100 parts by weight, and particularly preferably in the range of 10 to 80 parts by weight.

The compounding amount of the flame retardant auxiliary is selected so that the weight ratio of / is in the range of 0 to 10 (including 0). If this weight ratio exceeds 10, the effect as a flame retardant aid may be insufficient. Further, the compounding amount of the inorganic filler or the organic filler is 0 to 350 parts by weight (100 parts by weight) per 100 parts by weight of the resin part composed of (a) to (c).
), Preferably in the range of 250 parts by weight or less. If this amount exceeds 350 parts by weight, there is a tendency that toughness, impact resistance and impregnation of the resin into the glass cloth tend to decrease. In terms of mechanical properties such as tensile strength, toughness, and impact resistance, the amount of the inorganic filler or the organic filler is from 0 to 35.
0 parts by weight, more preferably 5 to 300 parts by weight, particularly preferably 10 to 250 parts by weight.

In the case of the prepreg, the amount of the glass cloth used as the fibrous filler is such that the weight of the glass cloth relative to the total weight of the prepreg is 0% by weight or more (0 is not included).
But preferably at least 1% by weight, and more preferably 1% by weight.
0% by weight or more. If the weight of the glass cloth is less than 1% by weight, the rigidity when heat is applied to the prepreg may be reduced. Further, the weight of the glass cloth relative to the total weight of the prepreg is 95% by weight or less,
It is preferable that the content be not more than weight%. If the weight of the glass cloth exceeds 95% by weight, the molding material may start to exhibit an undesirable tendency such as being porous or impairing the strength. 2. (B) Layer The (B) layer is present between the (A) layer and the (C) layer and serves as an adhesive for the two layers. And a prepreg obtained by impregnating a fibrous filler with a resin composition described below using a resin sheet prepared by a known method. (1) Mixing ratio of each component (B) When a resin sheet is used as a layer, a resin composition obtained by mixing the following (1) and (2) is used, and when a prepreg is used as a (B) layer Is carried out by using a resin composition comprising the following (1), and impregnating the fibrous filler of (2) with the resin composition. (1) 5 to 100% by weight of a resin composition consisting of the following: 100 parts by weight of a resin part consisting of the following (A) to (C):
(A) 10 to 100% by weight of a polystyrene resin mainly having a syndiotactic structure, (B) Polymer 0 having compatibility or affinity with the component (A) and having a polar group
-10% by weight (including 0), (c) the above (a), (b)
Thermoplastic resin and / or rubbery elastic body other than components 0-9
0% by weight (including 0) 0 to 100 parts by weight (including 0) of a flame retardant, and a flame retardant auxiliary agent, when using a flame retardant, if necessary, / = 0 to 10 (not including 0) 0) to 350 parts by weight (including 0) of the inorganic filler (2) 0 to 95% by weight (including 0) of the fibrous filler Even in the case of a resin sheet, Even in this case, it is necessary that the melting point of the resin portion has a lower melting point than the melting points of the resin compositions forming the layer (A) and the layer (C) described below. Preferably, the melting point of the resin composition constituting the layers (A) and (C) is at least 10 ° C.
More preferably, it has a melting point lower by 15 ° C. or more. Specifically, the melting point is desirably less than 250 ° C. By exhibiting such a melting point, the effects of the present invention can be achieved. (2) Contents of Each Component Except for “a styrenic polymer mainly having a syndiotactic structure” described in detail below, all the contents described in the section of the (A) layer and the (C) layer apply. (A) Styrene-based polymer mainly having a syndiotactic structure Also in the (B) layer, it can be appropriately selected and used from those described in the section of the (A) layer and the (C) layer. The degree of polymerization having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) (excluding the structural unit represented by the general formula (1)) is 5: The above copolymers are preferably used.

[0053]

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(In the formula, R ¹ represents a hydrogen atom, a halogen atom or a substituent containing carbon, oxygen, nitrogen, sulfur, phosphorus or a silicon atom, and m represents 1, 2 or 3. When there are two or more, each R ¹ may be the same or different.)

[0055]

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(Wherein, R ² represents a hydrogen atom, a halogen atom or a substituent containing carbon, oxygen, nitrogen, sulfur, phosphorus, or silicon atom, and n represents 1, 2, or 3. And when R ² is plural, each R ² may be the same or different.) Here, specific examples of the substituent containing a carbon atom include:
Examples thereof include an alkyl group having 1 to 20 carbon atoms and a halogen-substituted alkyl group having 1 to 20 carbon atoms (eg, chloromethyl group, bromomethyl group, and the like). As the substituent containing carbon and oxygen atoms, specifically, an alkoxy group having 1 to 10 carbon atoms (for example, a methoxy group, an ethoxy group, an isopropoxy group, etc.) or a carboxy ester group having 1 to 10 carbon atoms ( Examples thereof include a carboxymethyl ester group and a carboxyethyl ester group. Specific examples of the substituent containing a carbon atom and a nitrogen atom include an alkylamino group having 1 to 20 carbon atoms (eg, a dimethylamino group) or a cyano group. Specific examples of the substituent containing a carbon atom and a silicon atom include an alkylsilyl group having 1 to 20 carbon atoms (for example, a trimethylsilyl group and the like). Further, specific examples of the substituent containing a sulfur atom include a sulfonyl group, a sulfonic acid alkyl ester group, an alkylthio group and a mercapto group. Specific examples of the substituent containing a phosphorus atom include a phosphate group, a phosphite group, and an alkylphosphinyl group.

As specific examples of the above structural units and
Styrene unit, p-methylstyrene unit, m-methylstyrene unit, o-methylstyrene unit, 2,4-dimethylstyrene unit, 2,5-dimethylstyrene unit, 3,
Alkylstyrene units such as 4-dimethylstyrene unit, 3,5-dimethylstyrene unit, p-tert-butylstyrene unit, p-chlorostyrene unit, m-chlorostyrene unit, o-chlorostyrene unit, p-bromostyrene unit , M-bromostyrene unit, o-bromostyrene unit, p-fluorostyrene unit, m-fluorostyrene unit, halogenated styrene unit such as o-fluorostyrene unit, p-chloromethylstyrene unit, m-
Halogen-substituted alkylstyrene units such as chloromethylstyrene units, o-chloromethylstyrene units, p-bromomethylstyrene units, m-bromomethylstyrene units, o-bromomethylstyrene units, p-methoxystyrene units, m-methoxystyrene Unit, o-methoxystyrene unit, p-ethoxystyrene unit, m-ethoxystyrene unit, alkoxystyrene unit such as o-ethoxystyrene unit, p-carboxymethylstyrene unit, m-carboxymethylstyrene unit, o-carboxymethylstyrene And carboxyalkylstyrene units such as units.

In the present invention, since the copolymer is a copolymer, it is different from the above-mentioned structural units. However, the present invention is not limited to two structural units, but is composed of more structural units. That is, it may be a terpolymer, a quaternary copolymer, or the like. In addition, various embodiments can be applied to the embodiment such as a random copolymer, a block copolymer, and an alternating copolymer. The degree of polymerization needs to be at least 5 or more. (3) Mixing ratio of each of the above components The contents are the same as those described in the section of the (A) layer and the (C) layer. 3. Method for Producing Multilayer Printed Wiring Board According to the Present Invention The method for producing a multilayer printed wiring board according to the present invention is not particularly limited, and the layer (B) serving as the adhesive layer is placed between the layer (A) and the layer (C). A method of arranging and pressing under heating is preferably used. Further, the thickness of each layer and the ratio of the thickness are not particularly limited, and may be appropriately determined depending on the purpose.

[0059]

[Example 1]

[Preparation of Printed Wiring Board (A) Layer and (C) Layer] Syndiotactic homopolystyrene (melting point 270 ° C., MI =
76 (3.0 (300 ° C., load 2.16 kg)), 4.0 g of fumaric acid-modified polyphenylene ether, SEBS (hydrogenated styrene-butadiene copolymer,
Shell Co., trade name: Clayton G1651) 20
g, as a flame retardant, 1,2-di (pentabromophenyl) ethane (trade name “SAYTEX801” manufactured by Ethyl Corporation)
0 ") and 26.5g, Sb ₂ O ₃ (antimony trioxide as a flame retardant agent, Nihonseiko trade name" PATOX-
M ") as an additional component, and" Irganox 1010 "(pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate], manufactured by Ciba-Geigy, trade name: Irganox 1010) at 0.30
g, “PEP36” (bis (2,6-di-t-butyl-
0.30 g of 4-methylphenyl) pentaerythritol diphosphite, manufactured by Asahi Denka Co., Ltd., trade name: PEP36),
“DHT-4A” which is a halogen scavenger (basic aluminum magnesium carbonate hydrate,
1.0 g of Kyowa Chemical's trade name: DHT-4A) was blended.

Next, 134.1 g of this resin composition was impregnated at a rate of 132.5 g of a glass cloth as a fibrous filler, thereby forming a printed wiring board (A) layer and a (C) layer. The melting points of the layers (A) and (C) are 266 ° C.
Met. In addition, about this (A) layer and (C) layer, it is the compounding ratio of 50 weight% of resin compositions and 50 weight% of fibrous fillers.

The fumaric acid-modified polyphenylene ether was prepared as follows. That is, 1 kg of polyphenylene ether (intrinsic viscosity: 0.45 dl / g, in chloroform at 25 ° C.), 30 g of fumaric acid, 2,3-dimethyl-2,3 as a radical generator
20 g of diphenylbutane (NOFMA-BC) was dry-blended and melt-kneaded at a screw rotation speed of 200 rpm and a set temperature of 300 ° C. using a 30 mm twin screw extruder. The strand was cooled and pelletized to obtain a fumaric acid-modified polyphenylene ether. To measure the denaturation rate, 1 gram of the resulting modified polyphenylene ether was dissolved in ethylbenzene, reprecipitated in methanol, the recovered polymer was soxhlet-extracted with methanol, dried, and dried.
The denaturation rate was determined by the intensity of carbonyl absorption in the R spectrum and titration. The modification rate was 1.5% by weight.

The method of forming the printed wiring board (A) layer and (C) layer is as follows. That is, by extrusion-molding the resin composition, a resin sheet having a thickness of 100 μm was obtained, and the resin sheet was 100 μm-glass cloth 100 μm.
-Resin sheets are stacked in order of 100 μm, and 3
The glass-impregnated sheet (thickness: 200) was pressed at 00 ° C. under a pressure of 50 kg / cm ² G for 180 seconds.
μm). Next, three sheets of this glass-impregnated sheet (thickness: 200 μm) were stacked, and copper foil (thickness: 18 μm) was placed on both outermost surfaces.
It was pressed at 70 ° C. under a pressure of 50 kg / cm ² G for 60 seconds. Thereafter, annealing was performed at 150 ° C. under a pressure of 50 kg / cm ² G for 15 minutes to produce a 600 μm-thick copper foil-bonded plate. A circuit pattern was formed by performing an etching treatment on one side of the copper foil-bonded plate, and a printed wiring board (A) layer was completed. The printed wiring board (C) layer was produced in the same manner. [Preparation of Adhesive Layer (B) Layer] In this embodiment, (B)
As a layer, a prepreg prepared as follows was used.

That is, syndiotactic styrene-p-
Methylstyrene copolymer (p-methylstyrene 7.6 mol%, melting point 246 ° C., MI = 13.7 (300 ° C., load 2.1
6 kg)), 4.0 g of fumaric acid-modified polyphenylene ether, 20 g of SEBS (hydrogenated styrene-butadiene copolymer, Shell Co., trade name: Kraton G1651) as a rubber-like elastic material, and as a flame retardant, 1,2-
Di (pentabromophenyl) ethane (ethyl trade name "SAYTEX8010") to 26.5 g, Sb ₂ O ₃ as a flame retardant aid (antimony trioxide, Nihonseiko trade name "PATOX-M") 6.0 g, and as another component, "Irganox 101" which is an antioxidant
0 "(pentaerythrityl-tetrakis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba-Geigy Co., Ltd., trade name: Irganox 1010), and 0.3 g of “PEP36” (bis (2,6
-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, manufactured by Asahi Denka Co., Ltd., trade name: PEP
36) and 0.35 g of the halogen scavenger "DHT-4"
A "(basic aluminum magnesium carbonate hydrate, manufactured by Kyowa Chemical Industry Co., Ltd., trade name: DHT-4
1.0 g of A) was blended.

The resin composition was melt-kneaded at a temperature of 250 to 300 ° C. using a twin screw extruder. The melting point of this resin composition was 243 ° C.
Next, treated with a silane coupling agent, a thickness of 180 μm
m, a glass cloth having a weight per unit area of 210 g / cm ² (7628 manufactured by Asahi Schwebel) is sandwiched between two films obtained by extruding the resin composition, and then heated and pressed. The glass cloth was impregnated with a resin to obtain a prepreg. At this time, the resin composition was 50% by weight and the glass cloth was 50% by weight, and the heating press was performed at 280 ° C. using a heating press machine.
The test was performed under the conditions of 60 kg / cm ² and 180 seconds. [Preparation of Multilayer Printed Wiring Board] The surface on which the circuit pattern has been formed in the layers (A) and (C) is placed inside, that is, the surface on which the circuit pattern is formed is in contact with the layer (B). Then, the layer (B) is arranged between the layers (A) and (C), and is placed at 250 ° C. under the atmospheric pressure for 4 minutes, and then at 250 ° C.
The laminate was pressed for 1 minute at 45 ° C. and a pressure of 45 kg / cm ² , and further pressed at 150 ° C. and a pressure of 45 kg / cm ^2.
By pressing for a minute, a multilayer printed wiring board was obtained. [Evaluation] There was no shift or distortion in the circuit pattern, and the accuracy of the pattern before multilayering was maintained. Also, the adhesion between the prepreg, which is the adhesive layer, and the printed wiring board is strong,
When the prepreg was to be peeled, the prepreg was destroyed by the base material, and peeling at the interface was difficult. [Example 2] [Preparation of printed wiring board (A) layer and (C) layer] Syndiotactic homopolystyrene (melting point 270 ° C, MI = 3.0 (300 ° C) , A load of 2.16 kg), 76 g of fumaric acid-modified polyphenylene ether, SEBS (hydrogenated styrene-butadiene copolymer, manufactured by Shell Co., Ltd., trade name:
20 g of Clayton G1651), 0.3 g of "Irganox 1010" (trade name: Irganox 1010), an antioxidant, and "PEP36" (trade name: Asahi Denka Co., Ltd.) PE
P36) was carried out in the same manner as in Example 1 except that 0.30 g of P36) was blended.

Next, 100 g of this resin composition was impregnated into 100 g of glass cloth as a fibrous filler to form printed wiring board (A) and (C) layers. The melting points of the layers (A) and (C) were 266 ° C. In the layers (A) and (C), the mixing ratio of each component is 50% by weight for the resin composition and 50% by weight for the fibrous filler. [Preparation of Adhesive Layer (B) Layer] The procedure of Example 1 was repeated, except that the flame retardant and the flame retardant auxiliary were not used.

That is, syndiotactic styrene-p-
Methylstyrene copolymer (p-methylstyrene 7.6 mol%, melting point 246 ° C., MI = 13.7 (300 ° C., load 2.1
6 kg)), 4.0 g of fumaric acid-modified polyphenylene ether, 20.0 g of SEBS (hydrogenated styrene-butadiene copolymer, manufactured by Shell Co., trade name: Clayton G1651) as a rubber-like elastic material, and others. As an ingredient,
The antioxidant "Ilganox 1010" (Ciba Geigy Co., trade name: Irganox 1010) was added to 0.3.
0 g, "PEP36" (trade name: PEP3, manufactured by Asahi Denka Co., Ltd.)
0.3 g of 6) was blended.

This resin composition was melt-kneaded at a temperature of 250 to 300 ° C. using a twin screw extruder. The melting point of this resin composition was 244 ° C. [Production of Multilayer Printed Wiring Board] A multilayer printed wiring board was produced in the same manner as in Example 1. [Evaluation] There was no shift or distortion in the circuit pattern, and the accuracy of the pattern before multilayering was maintained. Also, the adhesion between the prepreg, which is the adhesive layer, and the printed wiring board is strong,
When the prepreg was to be peeled, the prepreg was destroyed by the base material, and peeling at the interface was difficult. [Comparative Example 1] [Preparation of Printed Wiring Board (A) Layer and (C) Layer] The melting point of this resin composition is 243 ° C.
Met. [Preparation of Adhesive Layer (B) Layer] The same resin composition as that used for the printed wiring board (A) layer and (C) layer was used.

The resin composition was melt-kneaded at a temperature of 250 to 300 ° C. using a twin screw extruder. The melting point of this resin composition was 243 ° C., which was the same as the melting points of the printed wiring board (A) layer and the (C) layer. The prepreg was manufactured in the same manner as in Example 1. [Production of Multilayer Printed Wiring Board] A multilayer printed wiring board was produced in the same manner as in Example 1. [Evaluation] A shift occurred in the circuit pattern. [Comparative Example 2] [Production of printed wiring board (A) layer and (C) layer] The melting point of this resin composition is 243 ° C.
Met. [Adhesive layer (B) layer] Epoxy resin prepreg (Resho Multi ES3305 manufactured by Risho Kogyo Co., Ltd., resin content 52%)
Was used. [Preparation of Multilayer Printed Wiring Board] The surface of the above-mentioned layers (A) and (C) on which the circuit pattern has been formed faces outward, that is, the surface on which the circuit pattern has not been formed contacts the layer (B). Thus, the layer (B) is arranged between the layer (A) and the layer (C), and at 150 ° C. under a pressure of 15 kg / cm ² for 25 minutes, and subsequently under a pressure of 150 ° C. and a pressure of 30 kg / cm ² . At 150 ° C for 3 minutes.
The multilayer printed wiring board was obtained by pressing under a pressure of 0 kg / cm ² for 100 minutes. [Evaluation] The adhesion between the prepreg as the adhesive layer and the printed wiring board was insufficient, and peeling at the interface was easy.

[0069]

According to the present invention, it is possible to obtain a multilayer printed wiring board in which the dimensions of the substrate are reduced and the density is increased without impairing the good electrical properties of syndiotactic polystyrene. did it.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/30 B32B 27/30 B C08K 7/02 C08K 7/02 C08L 25/02 C08L 25/02 101 / 16 101/00 (72) Inventor Hiroki Fukui 5-6-1 Shiba, Tokyo F-term (reference) 4F100 AA29 AB01D AB01E AB17 AB33 AB33D AB33E AG00 AH05 AK01A AK01B AK01C AK12 AK12A AK12B AK12C AK12K AK29 AL05 AL05 AL01 AL09A AL09B AL09C AN02A AN02B AN02C BA05 BA06 BA10D BA10E CA08 CA08A CA08B CA08C CA08H CA23A CA23B CA23C CA23H DG03A DG03B DG03C DG12 DH01A DH01B EJ82 EJ82A EJ82B GB43 JA04C JB04A JB04B JB04C JB13A JB13B JB13C JL01 JL03 JL11 4J002 AA012 AC012 AC032 AC062 BB012 BB032 BB052 BB122 BB172 BB182 BC011 BC031 BC033 BC041 BC081 BC111 BC114 BC121 BC123 BD125 BF011 BG042 BH013 BN122 BN142 BN162 BN 172 BN183 BN203 BP012 BP022 BP033 CD124 CD193 CG034 CH042 CH074 CL065 CN022 CP032 DA028 DA038 DA068 DA117 DD077 DE097 DE098 DE127 DE138 DE148 DE187 DE238 DG027 DG048 DG058 DH0 DG058 DH036 DJ008 DJ0180 016 DK048 EB009 DK048 DJ0 806 FD136 FD137 FD200 GF00 GQ05

Claims (5)

[Claims] 1. A multilayer printed wiring board having a portion composed of the following three layers (A) to (C). (I) The layer (A) and the layer (C) are each independently a printed wiring board layer using a resin sheet made of a resin composition obtained by blending the following (1) and (2), or A printed wiring board layer using a prepreg obtained by impregnating the resin composition of (1) with the fibrous filler of (2). (1) 5 to 100% by weight of a resin composition consisting of the following: (a) 100 parts by weight of a resin part consisting of (a) to (c), (a) 10 to 100% by weight of a polystyrene resin mainly having a syndiotactic structure (B) 0 to 10% by weight (including 0) of a polymer having compatibility or affinity with the component (a) and having a polar group; (c) the components (a) and (b) 0 to 90% by weight (including 0) of a thermoplastic resin and / or rubber-like elastic material other than 0 to 100 parts by weight (including 0) of a flame retardant; In accordance with the following, the amount becomes a weight ratio of / = 0 to 10 (not including 0), 0 to 350 parts by weight (including 0) of the inorganic filler (2) 0 to 95% by weight of the fibrous filler (0 is included) (II) The (B) layer is a resin sheet made of a resin composition obtained by blending the following (1) and (2). The melting point of the resin composition forming the layer (A) and the melting point of the resin composition forming the layer (A), and the resin composition forming the layer (C). (A)
An adhesive layer disposed between the layer and the layer (C). (1) 5 to 100% by weight of a resin composition consisting of the following: (a) 100 parts by weight of a resin part consisting of (a) to (c), (a) 10 to 100% by weight of a polystyrene resin mainly having a syndiotactic structure (B) 0 to 10% by weight (including 0) of a polymer having compatibility or affinity with the component (a) and having a polar group; (c) the components (a) and (b) 0 to 90% by weight (including 0) of a thermoplastic resin and / or rubber-like elastic material other than 0 to 100 parts by weight (including 0) of a flame retardant; In accordance with the following, the amount becomes a weight ratio of / = 0 to 10 (not including 0), 0 to 350 parts by weight (including 0) of the inorganic filler (2) 0 to 95% by weight of the fibrous filler (0 is included) Including) 2. A multilayer printed wiring board having the following three layers (A) to (C). (I) The layer (A) and the layer (C) are each independently a printed wiring board layer using a resin sheet made of a resin composition obtained by blending the following (1) and (2), or A printed wiring board layer using a prepreg obtained by impregnating the resin composition of (1) with the fibrous filler of (2). (1) 5 to 100% by weight of a resin composition consisting of the following: (a) 100 parts by weight of a resin part consisting of (a) to (c), (a) 10 to 100% by weight of a polystyrene resin mainly having a syndiotactic structure (B) 0 to 10% by weight (including 0) of a polymer having compatibility or affinity with the component (a) and having a polar group; (c) the components (a) and (b) 0 to 90% by weight (including 0) of a thermoplastic resin and / or rubber-like elastic material other than 0 to 100 parts by weight (including 0) of a flame retardant; In accordance with the following, the amount becomes a weight ratio of / = 0 to 10 (not including 0), 0 to 350 parts by weight (including 0) of the inorganic filler (2) 0 to 95% by weight of the fibrous filler (0 is included) (II) The (B) layer comprises the following resin composition (1) (2)
Prepreg impregnated with a fibrous filler of
(B) the melting point of the resin composition of the layer (1) is lower than the melting point of the resin composition of the layer (A) and the melting point of the resin composition of the layer (C); ) And an adhesive layer disposed between the layer (C). (1) 5 to 100% by weight of a resin composition consisting of the following: (a) 100 parts by weight of a resin part consisting of (a) to (c), (a) 10 to 100% by weight of a polystyrene resin mainly having a syndiotactic structure (B) 0 to 10% by weight (including 0) of a polymer having compatibility or affinity with the component (a) and having a polar group; (c) the components (a) and (b) 0 to 90% by weight (including 0) of a thermoplastic resin and / or rubber-like elastic material other than 0 to 100 parts by weight (including 0) of a flame retardant; In accordance with the following, the amount becomes a weight ratio of / = 0 to 10 (excluding 0), 0 to 350 parts by weight of inorganic filler (including 0) (2) 0 to 95% by weight of fibrous filler (0 is Not included) 3. The (B) layer in which the (A) styrene-based polymer mainly having a syndiotactic structure is at least a structural unit represented by the following general formula (1) and the following general formula (2): 3. The multilayer printed wiring board according to claim 1, wherein the copolymer is a copolymer having a degree of polymerization of 5 or more, having a structural unit represented by the formula (excluding the structural unit represented by the general formula (1)). Embedded image (Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a substituent containing a carbon, oxygen, nitrogen, sulfur, phosphorus, or silicon atom, and m represents 1, 2, or 3.
When there are two or more, each R ¹ may be the same or different. ) (Wherein, R ² represents a hydrogen atom, a halogen atom, or a substituent containing carbon, oxygen, nitrogen, sulfur, phosphorus, or a silicon atom, and n represents 1, 2, or 3.
When R is plural, each R ² may be the same or different. ) 4. The multilayer printed wiring board according to claim 1, wherein the melting point of the resin composition constituting the layer (B) is 250 ° C. or less. 5. The resin composition according to claim 1, wherein the melting point of the resin composition forming the layer (B) is lower than the melting point of the resin composition forming the layers (A) and (C) by 10 ° C. or more. The multilayer printed wiring board according to any one of the above.