JPH11186677A - Lamination board for printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce remaining bubbles in an interface of a fabric and obtain enough interlaminar bonding strength for practical use by treating a fabric surface by resin fabrics which is compatible to polystyrene resin in advance. SOLUTION: An insulating base of the lamination board for a printed wiring board consists of resin composition (SPS resin fabrics) formed by adding various additives to polystyrene resin and a reinforcement material. Additives such as flame retardant, plasticizer and processing aid can be added to SPS resin if required. Thermoplastic resin which is compatible to SPS resin such as styrene polymer of atactic structure, styrene polymer of isotactic structure can be added to SPS resin for improving dynamic characteristic, especially impact resistance. As for a reinforcement material, a fabric is used and a glass fiber is preferable from the viewpoint of mechanical strength. As for the form of a reinforcement material, nonwoven fabric such as continuous long fiber, fabric, swirl-like lamination are applicable, and plain fabric is desirable from the viewpoint of surface smoothness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated board for printed wiring boards used in the field of electric and electronic devices, and more particularly, to a laminated board for printed wiring boards having excellent high-frequency characteristics, heat resistance and mechanical strength, and having high long-term environmental reliability. It is about a board.

[0002]

2. Description of the Related Art In general, an insulating base material of a laminated board for a printed wiring board is insufficient in mechanical strength only with a resin, and cannot match a thermal expansion with a metal for wiring. A composite obtained by impregnating a resin with a reinforcing material such as aramid fiber is used. Conventionally, as the above resin, a thermosetting resin has been widely used due to problems of heat resistance and solvent resistance. And, in order to compound the thermosetting resin and the reinforcing material, after impregnating the reinforcing material with a solution obtained by diluting the uncured resin with an organic solvent, the resin is semi-cured by performing a drying treatment, A prepreg method is employed. In this case, the viscosity of the solution is as low as several cp to several hundred cp, and since the reinforcing material has been subjected to a surface treatment with a silane coupling agent or the like, the wettability of the reinforcing material interface is good, and therefore, the obtained insulating property The substrate has sufficient strength and long-term environmental reliability such as migration resistance.

[0003] However, an insulating substrate obtained by combining a thermosetting resin and a reinforcing material is excellent in heat resistance, strength, production efficiency and the like, but is excellent in terms of dielectric constant and dielectric loss tangent. It is not suitable as an insulating base material for a printed wiring board laminate requiring high frequency characteristics. Therefore, in order to improve the dielectric properties, a composite-type insulating base material using a reinforcing material such as glass mat, glass paper, aramid fiber, etc. in the center as an insulating base material combined with glass cloth on the outside has also been proposed. However, at present it has not been sufficiently improved. In addition, instead of a thermosetting resin, a composite insulating base material using a thermoplastic resin has been proposed, but since the melting point of the thermoplastic resin is low,
The range that can be used for a laminate for a printed wiring board is extremely limited.

In recent years, as a resin constituting an insulating base material,
A resin composition mainly composed of a polystyrene-based resin having a syndiotactic structure as a main material (hereinafter, a polystyrene-based resin to which various additives are added is referred to as an SPS resin composition, and a polystyrene-based resin not added is referred to as an SPS resin. ), Which have low dielectric constant and dielectric loss tangent,
Unlike conventional polystyrene, it has excellent heat resistance and solvent resistance, and is inexpensive compared to resins used for other high-frequency substrates. As a resin material for forming an insulating base material of a printed circuit board laminate for use in a small communication device or the like. A laminated board for a printed wiring board using this SPS resin composition is composed of only the SPS resin composition.
Since a generally required mechanical strength (specifically, a flexural modulus of 10 kgf / mm ² or more) cannot be obtained, one prepreg in which a reinforcing material such as glass cloth is impregnated with the SPS resin composition is used. It is manufactured by laminating a plurality of sheets and laminating a conductive metal layer such as a copper foil on one or both sides thereof. In this case, in order to prepare a prepreg, there is no general-purpose solvent suitable for the surface treatment of the reinforcing material. Therefore, after forming the SPS resin composition into a sheet, it is superposed with the reinforcing material surface-treated with an appropriate silane coupling agent. In addition, a method of performing heat and pressure treatment has been adopted.

[0005]

However, the viscosity of the SPS resin composition in the molten state is as high as several thousand poise, and it is not easy to impregnate the resin composition when the reinforcing material is a woven fabric. For example, the SPS resin composition penetrates relatively quickly between twisted yarns of glass cloth, which is a general-purpose woven fabric, but hardly enters between the fibers of the twisted yarn itself. Therefore, in order to produce a laminated board for a printed wiring board using the SPS resin composition, it takes about 5 minutes or more in a pressurized state, and the production efficiency is extremely poor.

[0006] In addition, if the impregnation of the SPS resin composition into the woven fabric is low, the affinity state with the woven fabric tends to be incomplete,
For this reason, there have been problems in that sufficient mechanical strength cannot be obtained, and that residual bubbles existing between the SPS resin composition and the woven fabric are swollen during the soldering process during the production of a printed wiring board. Furthermore, when using the printed wiring board, there is a danger that dielectric breakdown may occur due to an electromigration phenomenon.

On the other hand, when a material other than a woven fabric is used as a reinforcing material, mechanical strength cannot be obtained as much as a woven fabric. Therefore, there is a method of obtaining mechanical strength by compounding a filler, but sufficient mechanical strength cannot be obtained simply by compounding.

A conventional printed wiring board laminate using an SPS resin composition has excellent dielectric properties of the SPS resin composition itself, but has a high dielectric constant and a high dielectric loss tangent of a woven fabric generally used. Therefore, the dielectric properties as a whole were not sufficient.

[0009] Electrolytic copper foil is mainly used as the conductive metal layer of the laminate for printed wiring boards. The copper foil is usually subjected to a surface roughening treatment for depositing metal particles having a size of about 5 to 20 μm on a surface to be adhered to the insulating base material by a plating method. The adhesion strength of the copper foil to the insulating base material is increased by making the deposited metal particles bite into the insulating base material. However, when the conventional roughened electrolytic copper foil is used, the dielectric loss of the electrolytic copper foil increases even if the dielectric properties of the insulating substrate are improved, so that the performance of the insulating substrate is maximized. I couldn't show it. Also, as the propagation frequency increases, the current flows only near the surface of the copper foil, and particularly when high-frequency characteristics at 5 GHz or more are required, it is described in JP-A-60-248344. In addition, a rolled copper foil with little irregularities on the surface was used and bonded to an insulating substrate via an adhesive. However, the insulating base material made of the SPS resin composition has excellent solvent resistance as described above, but has poor surface activity, and has no sufficient adhesive for laminating the rolled copper foil. Adhesion was not obtained.

[0010] In recent years, with the trend of miniaturization and weight reduction of electric and electronic devices, laminated boards for multilayer printed wiring boards, which have been increased in density by being multi-layered, have also been used. However, in order to multilayer an interior substrate in which a wiring pattern is formed on an insulating base material composed of an SPS resin composition and a reinforcing material via an adhesive layer composed of the SPS resin composition and the reinforcing material, the SPS resin composition The temperature must be equal to or higher than the melting point (270 ° C.) of the product. In such a case, the wiring pattern formed on the interior substrate may be displaced or distorted. In addition, when the adhesive layer is made of a thermosetting resin, a sufficient adhesive force cannot be obtained, resulting in a delamination phenomenon.

That is, an object of the present invention is to use an SPS resin composition as a resin material of an insulating base material of a laminated board for a printed wiring board, wherein the resin material is present at an interface between the SPS resin composition and a woven fabric. Laminated board for printed wiring boards with extremely few residual air bubbles, having sufficient mechanical strength as a laminated board for printed wiring boards, and having good mechanical efficiency and good production efficiency, having sufficient mechanical strength and excellent dielectric properties For printed wiring boards, laminates for printed wiring boards having good adhesion between copper foil and insulating substrate, laminated boards for multilayer printed wiring boards having interlayer adhesion strength that can withstand actual use, and production thereof It is to provide a method.

[0012]

According to a first aspect of the present invention, there is provided a laminate for a printed wiring board, comprising: a resin composition mainly composed of a polystyrene resin having a syndiotactic structure as a main material; and a woven fabric. In a laminate for a printed wiring board provided with a conductive metal layer on both or part of one or both surfaces, the woven fabric surface is previously treated with a resin composition having compatibility with the polystyrene resin. It is characterized by. The laminate for a printed wiring board according to claim 2 is a resin composition mainly composed of a polystyrene resin having a syndiotactic structure as a main material, and a general formula aA _X O _Y · bB.
₂ O ₃ (a and b are each a number of 1 to 9, A is a metal element having 1 to 3 valences, X and Y are X = 2, Y = 1, X = Y = 1 or X = 2, Y = 3) or the general formula pM _V O _w · qSiO _2.
rH ₂ O (p, q, r are 1 ≦ p ≦ 3, 1 ≦ q ≦ 3, 0
Real number of ≦ r ≦ 10, M is a trivalent metal element, V, W
Is V = 2, W = 1, V = W = 1 or V = 2, W = 3)
In a laminate for a printed wiring board provided with a conductive metal layer on both or part of one or both surfaces of an insulating substrate made of a reinforcing material represented by the following, the compounding amount of the reinforcing material is based on the resin composition. , 5 to 60% by weight, characterized in that the surface of the reinforcing material is previously treated with a resin composition having compatibility with the polystyrene resin. According to a third aspect of the present invention, there is provided the laminate for a printed wiring board according to the second aspect, wherein the insulating substrate contains mica in a ratio of 10 to 70% by weight based on the SPS resin composition. It is characterized in that The laminated board for a printed wiring board according to claim 4 is preferably a resin composition mainly composed of a polystyrene resin having a syndiotactic structure as a main material and a part or the whole of one or both surfaces of an insulating substrate made of a woven fabric. In the printed wiring board laminate provided with the conductive metal layer, the thickness ratio of the layer containing the woven fabric and the layer not containing the woven fabric constituting the insulating base material is in the range of 1: 0.25 to 1: 4. And the two layers are arranged substantially symmetrically in the thickness direction. The laminated board for a printed wiring board according to claim 5 is preferably a resin composition mainly composed of a polystyrene-based resin having a syndiotactic structure and a part or the whole of one or both surfaces of an insulating base material composed of a reinforcing material. In the printed wiring board laminate provided with the copper foil layer, the bonding surface of the copper foil layer with the insulating substrate has metal particles having an average particle diameter of 1 μm or less deposited by a plating method, and Average surface roughness (JI) before adhesion of particles
S) is 1 μm or less. The laminated board for a multilayer printed wiring board according to claim 6 has at least a wiring pattern formed on both surfaces of an insulating base material mainly composed of a resin composition mainly composed of a polystyrene resin having a syndiotactic structure and a reinforcing material. A laminated board for a multilayer printed wiring board in which a conductive metal layer is provided on the outer surface of a single interior substrate via an adhesive layer, wherein the adhesive layer is cured at a temperature of 250 ° C. or less from a thermosetting resin and a reinforcing material. It is characterized by becoming.
The method for producing a laminated board for a multilayer printed wiring board according to claim 7,
The method is characterized in that after the adhesive layer is cured at 250 ° C. or lower, the temperature is raised to 270 ° C. or higher, and then cooled.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, an insulating substrate of a laminate for a printed wiring board of the present invention comprises an SPS resin composition and a reinforcing material. As the SPS resin used in the present invention,
For example, polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoate), hydrogenated polymers thereof, and mixtures thereof or Copolymers containing these as main components are exemplified. The SPS resin has a syndiotactic structure, that is, a three-dimensional structure in which phenyl groups and substituted phenyl groups, which are side chains, are alternately located in opposite directions to a main chain formed from carbon-carbon bonds. Must. Specifically, the tacticity is determined by analyzing the tacticity by a carbon 13 nuclear magnetic resonance method ( ¹³ C-NMR method). In the case of pentad), the racemic dyad is usually 75% or more,
It is preferably at least 85% or at least 30%, preferably at least 50% in racemic pentad.

The above poly (alkylstyrene) includes:
As poly (halogenated styrene) such as poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (t-butyl styrene), poly (phenyl styrene), poly (vinyl naphthalene), poly (vinyl styrene), etc. Is poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), etc., and poly (halogenated alkylstyrene) is poly (chloromethylstyrene), poly (alkoxystyrene)
Examples thereof include poly (methoxystyrene) and poly (ethoxystyrene). Further, as the comonomer component of the copolymer containing these structural units, in addition to the monomers of the styrene-based polymer, ethylene, propylene, butene, hexene, olefin monomers such as octene, butadiene, diene monomers such as isopropylene, Examples thereof include polar vinyl monomers such as cyclic olefin monomers, cyclic diene monomers, methyl methacrylate, maleic anhydride, and acrylonitrile. Of these, particularly preferred SPS resins include polystyrene, poly (alkylstyrene), poly (halogenated styrene), hydrogenated polystyrene, and copolymers containing these structural units.

Such an SPS resin is prepared, for example, by using a condensation reaction product of a titanium compound and a trialkylaluminum with water in an inert hydrocarbon solvent or in the absence of a solvent, using a styrene-based monomer (the above-mentioned styrene monomer). (A monomer corresponding to a polymer) can be produced (JP-A-62-187708). Further, poly (halogenated alkylstyrene) is disclosed in
-46912 and these hydrogenated polymers can be obtained by the method described in JP-A-1-178505. The molecular weight of the SPS resin is not particularly limited, but the weight average molecular weight is 2,000 or more, preferably 1
Optimally, those having a molecular weight of 0000 or more, especially 50,000 or more. Also, there is no limitation on the molecular weight distribution.

Various additives such as a flame retardant, a flame retardant auxiliary, a softening agent, and a processing aid can be added to the SPS resin as needed. However, the dielectric properties of the SPS resin should not be impaired. It is desirable that the amount be within 15 parts by weight based on 100 parts by weight of the SPS resin. Further, in order to improve mechanical properties, particularly impact resistance, a thermoplastic resin compatible with the SPS resin, for example, a styrene polymer having an atactic structure,
A styrene-based polymer having an isotactic structure, polyphenylene ether, styrene-butadiene-styrene copolymer (SBS), styrene-ethylene-butylene-styrene copolymer (SEBS), or the like may be added to the SPS resin.

An insulating substrate composed of only an SPS resin composition has insufficient mechanical strength, cannot match thermal expansion with a conductive metal, and may be deformed or peeled off due to a temperature change. Then, the reinforcing material is compounded to form an insulating base material. Glass fiber, carbon fiber, boron,
Whisker of silica, silicon carbide, etc., alumina fiber, ceramic fiber (gypsum fiber, potassium titanate fiber, magnesium sulfate fiber, magnesium oxide fiber, etc.), organic synthetic fiber (wholly aromatic polyamide fiber, aramid fiber, polyimide fiber, fluororesin) Fiber, etc.), and glass fiber is preferred in terms of price and mechanical strength. These fibers may be used alone or in combination of two or more.
Examples of the shape of the reinforcing material include non-woven fabrics such as chopped strands, chopped fibers, and continuous fibers, woven fabrics, swirled laminates, swirled laminates obtained by needle punching, powders, and milled fibers. Regarding the weaving method of the fibers constituting the reinforcing material, for example, a twist yarn obtained by combining several long fibers, a plain weave,
It may be woven by an appropriate method such as a twill weave or a plain weave, but plain weave is preferable in that surface smoothness is easily obtained.

However, in the first and fourth aspects of the invention,
Use woven fabric as reinforcement. Further, in the invention according to claims 2 and 3, as a reinforcing material, a general formula aA _X O _Y · bB is used.
₂ O ₃ (a and b are each a number of 1 to 9, A is a metal element having 1 to 3 valences, X and Y are X = 2, Y = 1, X = Y = 1 or X = 2, Y = 3) or the general formula pM _V O _w · qSiO _2.
rH ₂ O (p, q, r are 1 ≦ p ≦ 3, 1 ≦ q ≦ 3, 0
Real number of ≦ r ≦ 10, M is a trivalent metal element, V, W
Is V = 2, W = 1, V = W = 1 or V = 2, W = 3)
Is used. By using these compositions, it is possible to improve the mechanical strength while suppressing the increase in the dielectric constant of the printed wiring board laminate,
Production efficiency can be increased. The above A is M
g, Ca, Cr, Mn, Fe, Co, Ni, Cu, Z
n, Al, Ga, Sr, Y, Zr, Nb, Mo, Pb,
Ba, W, Li and the like can be mentioned. Among them, aluminum borate whiskers in which A is Al, magnesium borate whiskers in which A is Mg, and nickel borate whiskers in which A is Ni are preferable. As aluminum borate whiskers, 9 is more preferable.
_{Al 2 O 3 · 2B 2 O} 3, 2Al 2 O 3 · B 2 O 3 is exemplified.

The aluminum borate whiskers are white needle-like crystals. For example, at least one aluminum supply component selected from aluminum hydroxide or aluminum inorganic salt, and boron oxide, oxyacid or alkali metal salt At least one boron supply component selected from the group consisting of a sulfate, a chloride or a carbonate of an alkali metal, in the presence of at least one fluxing agent selected from the group consisting of It can be easily produced by heating and reacting and growing at a firing temperature in the range. Aluminum borate whisker represented by the _{9Al 2 O 3 · 2B 2 O} 3 is a true specific gravity from 2.93 to 2.9
5. Melting point is 1,420 to 1,460 ° C and firing temperature is 9
Those manufactured at 00 to 1,200 ° C are preferred. Also,
2Al aluminum borate whisker represented by ₂ O ₃ · B ₂ O ₃ is a true specific gravity from 2.92 to 2.94, a melting point 1,0
30 to 1,070 ° C, and a firing temperature of 600 to 1,000
Those produced at 0 ° C. are preferred. Currently available aluminum borate whiskers include, for example, 9Al
"Arbolex G" represented by ₂ O ₃ · 2B ₂ O ₃
(Trade name, manufactured by Shikoku Chemicals). The average fiber diameter of this is 0.5-1 μm, the average fiber length is 10-30 μm
m. If necessary, the above 9Al ₂ O ₃ .2B
The ₂ O ₃ in an oxidizing atmosphere or a reducing atmosphere, 1,200
By heating at a temperature of １，1,400 ° C., a fiber from which a part of the boric acid component has been eliminated can also be used.

As the magnesium borate whisker,
Those represented by _{2Mg 2 O 3 · B 2 O} 3 is exemplified.
The whiskers are white needle-like crystals, for example, at least one magnesium supply component selected from oxides, hydroxides and inorganic acid salts of magnesium, and oxides of boron, oxygen acids and alkali metal salts. At least one boron supply component selected from the group consisting of sodium chloride and potassium halide, preferably in the presence of at least one flux selected from sodium halide and potassium halide.
It can be easily produced by heating to a firing temperature in the range of 00 ° C. to cause reaction and growth. In addition, 2Mg ₂
The magnesium borate whisker represented by O ₃ · B ₂ O ₃ has a true specific gravity of 2.90 to 2.92 and a melting point of 1,320 to
1,360 ° C is preferred.

The above aluminum borate whiskers and magnesium borate whiskers have an average fiber diameter of 0.05.
-5 μm and an average fiber length of 2-100 μm can be manufactured, and any of them can be used. However, the average fiber diameter is 0.1-2 μm and the average fiber length is 10-5
Those having a thickness of 0 μm are preferred.

The general formula pM _V O used in the invention of claim 2
_w · qSiO ₂ · rH ₂ O (p, q, r are 1 ≦ p ≦
3, 1 ≦ q ≦ 3, real number of 0 ≦ r ≦ 10, M is a metal element having 1 to 3 valences, V and W are V = 2, W = 1, V = W = 1 or V = 2, W = 3), for example,
CaO.SiO ₂ (Walathnite), 6CaO.6Si
O ₂ · H ₂ O (Zonotorite), 3Al ₂ O3.2Si
O ₂ (mullite), 2ZnO · SiO ₂ (zinc _{silicate), 2MgO 3 · SiO 2 ·} 3.5H 2 O ( sepiolite) include _{3MgO · 2SiO 2 · 2H 2 O} ( chrysotile). Among them, particularly preferable ones are CaO.SiO ₂ (Walathnite), 6CaO.
6SiO is a ₂ · H ₂ O (xonotlite). Whalathnite is a white needle-like crystal produced naturally, and it can be used as it is, crushed or classified, irrespective of the form of fiber or lump, or it may be synthesized. These reinforcing materials have a difference in aspect ratio depending on the pulverizing method and the place of production. In general, β-type wallasnite having a large aspect ratio is desirable from the viewpoint of reinforcing performance. In order to improve the mechanical properties and thermal properties, a component having an aspect ratio of 6 or more contains 60% by weight or more, preferably 80% by weight or more, and a component having a fiber diameter of 5 μm or less contains 80% by weight. As described above, it is preferable to use a fine and long-shaped wollastonite having a content of preferably 95% by weight or more. Some of the currently marketed wollastonite satisfy the above-mentioned standards, and have an average fiber diameter of 2.0 μm, an average fiber length of 25 μm, and a component having a fiber diameter of 5 μm or less.
Since the component having an aspect ratio of 6 or more is 5% by weight or more and the component having an aspect ratio of 6 or more is 90% by weight or more, the reinforcing performance and the surface smoothness are excellent. On the other hand, zonotolite has a chemical composition of 6CaO.6SiO.
_2. A fibrous calcium silicate represented by ₂ · H ₂ O,
Those having an average fiber diameter of 0.5 to 1 μm, an average fiber length of 2 to 5 μm, and an aspect ratio of 2 to 15 are synthesized.

The mixing ratio of the reinforcing material to the SPS resin composition is such that the reinforcing material 2 is added to 100 parts by weight of the SPS resin composition.
The amount is preferably 0 to 400 parts by weight, particularly preferably 50 to 100 parts by weight. If the amount is less than 20 parts by weight, sufficient mechanical strength cannot be obtained, and the rigidity when heat is applied is reduced.
If the amount exceeds the weight part, the SPS resin composition cannot cover the reinforcing material sufficiently, so that voids are generated. As a result, the mechanical strength is impaired and the bending strength is so small that it cannot be measured. This is because it is significantly inferior to the above. However, in the invention of claims 2 and 3, the mixing ratio of the reinforcing material is 5 to 60% by weight based on the SPS resin composition.
Range. If it is outside this range, the mechanical strength becomes insufficient.

According to the third aspect of the present invention, mica is further added as a constituent material of the insulating substrate. Since mica has a very small dielectric loss tangent in the high-frequency band, even if it is mixed with SPS resin with a small dielectric tangent, the decrease in dielectric properties is minimal, and the warpage and dimensions seen when a reinforcing material is mixed with the SPS resin composition Greatly improves stability. The type of mica is not particularly limited, but natural muscovite, natural phlogopite, synthetic phlogopite, synthetic silica tetrasilicic mica and the like are preferable. The particle size, thickness, and aspect ratio of mica are not particularly limited, but the aspect ratio is preferably 10 or more, and more preferably 15 or more, in order to increase the dimensional stability of the printed wiring board laminate. As the amount of mica, the content of mica in the SPS resin composition is 10 to 7
The content is desirably 0% by weight, particularly 15 to 50% by weight. If it exceeds 70% by weight, it is difficult to form a laminate for a printed wiring board, and if it is less than 10% by weight, the effect of improving dimensional stability and warpage becomes insufficient.

The reinforcing material and mica are desirably treated with various coupling agents such as a silane coupling agent and a titanate coupling agent in order to improve the wetting with the SPS resin composition. In the inventions of claims 1 to 3, this treatment is performed before the treatment with the second resin composition described later. Specific examples of the silane coupling agent include:
Triethoxysilane, pinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (1,1-epoxycyclohexyl) ethyltrimethoxysilane, N-β -(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
γ-aminopropyl-tris (2-methoxy-ethoxy) silane, N-methyl-γ-aminopropyltrimethoxysilane, N-pinylbenzyl-γ-aminopropyltriethoxysilane, triaminopropyltrimethoxysilane, 3-ureidopropyl Trimethoxysilane, 3
-(4,5-dihydroimidazole) propyltriethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) amide, N, N-bis (trimethylsilyl) urea and the like. Among these, preferred are γ-aminopropyltrimethoxysilane, N-β
Aminosilanes such as-(aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; and epoxysilanes.

Specific examples of the titanate coupling agent include isopropyl triisostearoyl titanate,
Isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (1,1-
Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyliso Examples include stearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-amidoethyl, aminoethyl) titanate, dicumyl phenyloxy acetate titanate, and diisostearoyl ethylene titanate. Preferred among these is isopropyl tri (N-amidoethyl-aminoethyl) titanate.

In order to treat the surface of the reinforcing material with the above-mentioned coupling agent, a conventional method may be used. For example, a method such as a sizing treatment in which an organic solvent solution or suspension of a coupling agent is applied as a sizing agent is exemplified.

In the first to third aspects of the present invention, the surface of the reinforcing material is treated in advance with a solution obtained by diluting a resin composition having compatibility with the SPS resin (referred to as a second resin composition) with a solvent. This improves the wetting with the SPS resin composition,
As a result, residual bubbles on the insulating substrate are extremely reduced.
Moreover, the mechanical strength of the laminated board for printed wiring boards can be improved. The degree of compatibility of the second resin composition with the SPS resin was determined by comparing the SPS resin and the second resin composition with one another:
When the mixture is extruded through a T-die having a lip of 0.5 mm by a co-axial twin screw extruder having an L / d of 20 or more, the mixture is taken up to a thickness of 0.2 mm. The sheeting can be performed without causing defects due to incompatibility. Examples of the second resin composition include SPS resin, styrene-ethylene-butylene-styrene copolymer (SEBS), polyphenylene ether (PPE), epoxy resin, and modified products thereof. SPS resin and PP with excellent properties
It is preferable that E is a main component. These alone or 2
More than one kind may be used in combination, and various additives such as a crosslinking agent, an antioxidant, an ultraviolet absorber, and a reinforcing material may be added. Further, the solvent for diluting the second resin composition may be a general-purpose solvent such as toluene, xylene, MEK, MIBK, ethyl acetate, butyl acetate, n-hexane, cyclohexane, cyclohexanone, and naphtha. The solution concentration of the second resin composition may be very thin because the purpose is to treat the surface of the reinforcing material. Specifically, it can be calculated from the thickness of the reinforcing material, the solution holding amount of the reinforcing material, and the specific surface area, and about 0.5 to 10% is appropriate. For example, wire diameter 10 [mu] m, using a reinforcing material having a basis weight of 210g / cm ^2, a solution holding amount of this product is 50 g, if the film thickness of the reinforcing material to be surface treated was set to 0.05 .mu.m, 1 m per ² second If the required amount of the resin composition is 1.7 cm ³ and the specific gravity is 1, the concentration at this time is 1.7 g / 50 g and 3.4%.

To treat the surface of the reinforcing material with the second resin composition, the second resin composition is diluted with a solvent to form a solution,
The solution may be applied to a reinforcing material by a spraying method, a dipping method, or the like using a usual coating device, a stirring device, or a dipping device, and dried. The solution viscosity of the second resin composition is not particularly limited, and may be a solution viscosity suitable for a coating device, a stirring device, and a dipping device. For example, when applying using a stirrer, it is possible to select from 10 poise or less,
In order to perform a uniform surface treatment, it is preferable to adjust the surface treatment so that it is 5 poise or less, preferably 1 poise or less.

In order to form the insulating base material by combining the SPS resin composition and the reinforcing material, a conventional forming method may be used. For example, a method in which a reinforcing material is mixed with a molten SPS resin composition to form a composite, a dry blending of the SPS resin composition, pelletizing by a usual method, and then forming a sheet by an extrusion molding method, The reinforcing material is overlaid, pressurized by a press while heating to a temperature equal to or higher than the melting point of the SPS resin, and then cooled to form a composite. The raw material containing the SPS resin composition is formed into a sheet by a T-die extrusion method or the like. While extruding, a method of heating, compressing and cooling with a roll and a roll or a double head press or a single press to form a composite is given. In the method of mixing the molten SPS resin composition with the reinforcing material to form a composite, there is no particular limitation on mixing both, and a conventional method can be widely used. For example, a mixing mixer or a single-screw or twin-screw extruder having a heating function and a mixing function, particularly, using a twin-screw extruder, supplying the SPS resin composition from the main hopper, during melt kneading It is desirable to add a reinforcing material to the resin and knead it further. The above mixture may be formed into an arbitrary molded product immediately after its production, or may be once formed into pellets. Further, in the method of combining the two by hot pressing, the temperature of the press machine needs to be heated to a temperature higher than the melting point of the SPS resin, that is, 270 ° C. or higher, and the time required for the temperature rise of the work is required. 280 ° C. or higher, more preferably 290 ° C.
It is preferable that heating is performed as described above. However, if the temperature is too high, the SPS resin is liable to be decomposed.
The temperature is preferably set to 0 ° C. or lower. The pressurizing time after the temperature reaches the melting point or higher depends on the type of reinforcing material and pressure,
For example, when a # 7628 type glass cloth is used and the pressure is about 40 kgf / cm ² , a sufficient impregnation state can be obtained in about 2 to 3 minutes.

In the fourth aspect of the present invention, the layer of the insulating base material not containing the woven fabric may be a layer made of the above-mentioned SPS resin composition, and may be made of a composition containing various reinforcing fillers. Layer. The shape of the reinforcing filler is not particularly limited, and may be any of fibrous, granular, and powdery. Examples of the fibrous material include glass fiber, carbon fiber, organic synthetic fiber, aluminum borate whisker, nickel borate whisker, calcium carbonate whisker, ceramic fiber, metal fiber, and natural plant fiber. In addition, talc, carbon black, graphite, titanium dioxide,
Examples include silica, 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, and glass beads. Among these, glass beads, glass fibers, mica, and aluminum borate whiskers are particularly preferable. These reinforcing fillers can be used alone or in combination of two or more. Further, it is preferable that these reinforcing fillers are surface-treated with a coupling agent described later or a resin compatible with the SPS resin. The method for mixing the SPS resin composition and the reinforcing filler is not particularly limited, and a generally known method may be used, but while the SPS resin composition is melt-kneaded using a twin-screw extruder, The optimal method is to supply and knead a predetermined amount of filler and form a sheet from a T-die.

According to the fourth aspect of the present invention, the thickness ratio of the layer containing the woven fabric to the layer not containing the woven fabric is in the range of 1: 0.25 to 1: 4, preferably 1: 3 to 1: 1/3. To By doing so, it is possible to obtain a laminate for a printed wiring board having sufficient mechanical strength and excellent dielectric properties. The combination of the layer including the woven fabric and the layer not including the woven fabric is not limited as long as they are arranged substantially symmetrically in the thickness direction. For example, a layer not containing a woven fabric may be used as an intermediate layer with an emphasis on mechanical strength and dielectric constant, and a layer containing a woven fabric may be arranged on both surfaces thereof, or to obtain a surface smoothness of an insulating base material. Alternatively, a layer containing no woven fabric may be provided on the surface. For the thickness of the layer containing the woven fabric,
When the thickness of the layer containing no woven fabric is less than 20%, SP
The effect of the excellent dielectric properties of the S-resin composition is reduced, and if it exceeds 80%, the reinforcing effect of the woven fabric is reduced, so that sufficient mechanical strength cannot be obtained as a laminate for a printed wiring board. . The method for laminating the layer containing the woven fabric and the layer not containing the woven fabric is not particularly limited, and a conventionally known method can be arbitrarily selected. For example, a layer including a woven fabric and a layer not including a layer including a woven fabric and a layer not including a layer including a woven fabric and a layer not including the woven fabric by extrusion molding may be inserted between the pair of metal belts by heating and melting. There is a method of performing hot press molding by overlapping.

The laminated board for a printed wiring board of the present invention has a
A conductive metal layer made of a metal foil such as copper, nickel, aluminum, tin, gold, silver, or zinc is provided on both surfaces or one surface of an insulating substrate made of an S resin composition and a reinforcing material. The conductive metal layer may be provided on the entire surface of the insulating base material, or may be provided only on necessary portions. As a method of forming the conductive metal layer on the surface of the insulating base material, a method of bonding a roughened metal foil by a hot press, a method of inserting a metal foil in a mold in advance and performing an injection molding, and a method of plating. , Vacuum deposition, and sputtering. In particular, in the case of a method in which a metal foil is bonded by a hot press, it can be performed simultaneously with the step of impregnating and compounding the reinforcing material with the SPS resin composition, and further, there is no need to use a separator in the step, and one step Impregnated with,
Since the lamination is completed, the production efficiency becomes very good.
For example, in a method of bonding a metal foil to an insulating substrate using a heating press, the adhesive is developed by melting the insulating substrate, so that the temperature of the press is equal to or higher than the melting point of the SPS resin composition. That is, it is necessary that the resin is heated to 270 ° C. or higher. However, if the temperature is too high, there is a possibility that a resin may flow too much and a desired thickness may not be obtained. Therefore, considering the time required for the temperature rise of the work, the temperature of the press machine is 280-370 ° C. or more,
Preferably, it is good to heat to 290-320 ° C. The pressurizing time after the temperature reaches the melting point or more is shorter than the conventional one because it is not necessary to impregnate the reinforcing material with the resin material as in the past, and the final metal The lamination of the foil is completed. Pressurization is 5kgf / cm ²
It becomes poor adhesion is less than, since excessively flow to higher than 80 kgf / cm ^2, it is in the range of 5~80kgf / cm ^2. Also, when cooling the obtained one,
After quenching, the crystallinity of the SPS resin becomes poor, so that it is once held at 130 to 170 ° C. for 5 seconds or more in order to more efficiently take a syndiotactic structure.
Cooling at room temperature is desirable.

According to a fifth aspect of the present invention, a surface roughening treatment for depositing metal particles having an average particle size of 1 μm or less on a bonding surface of the copper foil layer, which is a conductive metal layer, with the insulating base material by a plating method. Apply. When the average particle size exceeds 1 μm, when a high-frequency circuit of several GHz or more is formed, transmission loss rapidly deteriorates. On the other hand, when the average particle size is too small, a sufficient anchor effect cannot be obtained and the peel strength is low. The average particle size is 0.1μ
m or more. Further, in the invention of claim 5, the average surface roughness (JI) of the surface of the copper foil layer subjected to the surface roughening treatment is determined.
S) needs to be 1 μm or less. This is because, when the average surface roughness exceeds 1 μm, during the surface roughening treatment by the plating method, the current concentrates on the projection due to the lightning rod effect, and
This is because it is difficult to form the following metal particles and the transmission loss increases. In order to manufacture a copper foil constituting such a copper foil layer, a roughened surface, that is, when a copper foil is manufactured by an electrolytic method, instead of performing a surface roughening treatment on a surface on the electrolyte side, a gloss is applied. The surface, that is, the surface on the electrode roll side may be subjected to a roughening treatment. This is because, in the case of a normal copper foil, crystals grow when the copper foil is generated, and 5 to 10
Protrusions at μm intervals are formed, but when this roughened surface is subjected to surface roughening treatment by plating, metal particles concentrate on the apexes of the protrusions due to the lightning rod effect during plating, while copper foil is generated. This is because, when the surface of the glossy surface on which the crystal at the time of the crystal growth is still in a small stage of about 1 to 2 μm is subjected to the roughening treatment, the metal particles are uniformly formed on the entire treated surface.

According to a sixth aspect of the present invention, there is provided a laminate for a multilayer printed wiring board, wherein a desired wiring pattern is formed of the conductive metal on both surfaces of an insulating substrate. It is provided with a metal layer. This adhesive layer is composed of a thermosetting resin that cures at 250 ° C. or lower and the above-described reinforcing material. Curing temperature of thermosetting resin is 250
If the temperature exceeds ℃, the SPS resin constituting the interior substrate is softened, and there is a risk that the wiring pattern may be shifted or distorted. On the other hand, if the curing starts at an extremely low temperature, there is a danger that the pot life will be shortened or the curing will start during the work. It is better to choose. As the adhesive layer, for example, epoxy resin, phenol resin,
An example is one in which a reinforcing material such as a glass cloth is immersed and impregnated in a solution of an uncured material such as a thermosetting modified polyphenylene ether or BT resin, dried and B-staged through a heating furnace. The ratio of the reinforcing material to the thermosetting resin is 2
0 to 80 vol%.

According to a sixth aspect of the present invention, there is provided a laminate for a multilayer printed wiring board, wherein an adhesive layer is applied to an outer surface of one internal substrate or a plurality of internal substrates laminated via an adhesive layer, and a conductive metal layer is formed thereon. Can be obtained by bonding together. For example, when an adhesive layer is applied to the outer surface of one interior substrate and a conductive metal layer is laminated thereon, a four-layer laminate for a multilayer printed wiring board is obtained, and a conductive metal layer is laminated on both outer surfaces. Alternatively, when two interior substrates are laminated via an adhesive layer, and a conductive metal layer is laminated on both outer surfaces, a six-layer laminate for a multilayer printed wiring board is obtained. Similarly, the number of layers of the wiring pattern can be arbitrarily set by increasing the number of layers of the interior substrate. When manufacturing the laminated board for a multilayer printed wiring board according to claim 6, when the conductive metal layers are bonded to each other through the adhesive layer between the internal substrates or the internal substrate, the temperature of the SPS resin composition constituting the adhesive layer is reduced. First, the resin composition is cured at 250 ° C. or lower, and then heated to 270 ° C. or higher to melt the resin composition,
Then, it cools. In this case, first, 250 ° C.
In the following, the adhesive layer is cured while the wiring pattern of the interior substrate is fixed to the insulating substrate.
Even when the temperature rises to ℃ or more, the wiring pattern is fixed to the adhesive layer, so even if the SPS resin composition is melted, the wiring pattern is not shifted or distorted, and the multilayer printed wiring has high interlayer adhesion strength. A board laminate is obtained.

[0037]

Next, examples of the present invention and comparative examples will be described. Note that the present invention is not limited to the following embodiments.

(Example 1) Glass cloth "# 7628" treated with mercaptosilane-based coupling agent "KBM803" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a woven fabric
(Asahi Schwebel, product name)
0.7% solution of resin composition "XAREC S-100" (trade name, manufactured by Idemitsu Petrochemical Co., Ltd.) (solvent is xylene: MI)
BK = 9: 1 mixed solvent), passed through a pinch roll, dried through a hot air drying oven at 180 ° C., and this process was repeated once again, and the resin amount was 1 g / g.
m ² of treated woven fabric was obtained. Then, two sheets of the SPS resin composition "XAREC S-100" which have been sheeted to a thickness of 0.06 mm by T-die extrusion molding in advance.
(See above) One sheet of the treated woven fabric was sandwiched between sheets, pressed at 300 ° C. and 40 kgf / cm ² for 5 minutes, and then cooled to obtain a prepreg. The three prepregs are superimposed, and an electric field copper foil (type JTC manufactured by Japan Energy Co., Ltd.) having a thickness of 18 μm is superimposed on the upper and lower surfaces so that the roughened surface is on the inner side.
After pressing at 0 kgf / cm ² for 5 minutes (3 minutes after the internal temperature reaches 270 ° C., which is the melting point of the SPS resin), crystallization treatment was performed at 150 ° C. and 50 kgf / cm ² for 1 minute. A laminate for a printed wiring board of the present invention having a thickness of 0.64 mm was obtained.

Example 2 As a woven fabric, an aminosilane-based coupling agent “KBM602” (manufactured by Shin-Etsu Chemical Co., Ltd.)
A glass cloth “# 7628” (trade name) treated with a 3% solution of a thermosetting modified PPE resin (manufactured by Asahi Kasei Corporation, density 1.08 g / cm ³ ) (solvent is xylene: MIBK = (A 9: 1 mixed solvent was used), passed through a pinch roll, dried and semi-cured through a 180 ° C. hot air drying oven to obtain a treated woven fabric having a resin amount of 2 g / m ² . Then, one sheet of the woven fabric was sandwiched between two sheets of the SPS resin composition “XAREC S-100” (described above) which had been sheeted to a thickness of 0.06 mm by T-die extrusion in advance. One stack is made, and three stacks are stacked, and the top and bottom surfaces are 18 μm thick.
The electric field copper foil (supra), roughening treated surface superposed such that the inner, 300 ° C., was pressed for 5 minutes at a ^{40kgf / cm 2, 150 ℃,} 50kgf / cm 2 in 1 minute A crystallization treatment was performed to obtain a laminate for a printed wiring board of the present invention having a total thickness of 0.64 mm.

(Comparative Example 1)
Two SPs sheeted to a thickness of 0.06mm
An aminosilane-based coupling agent “KBM60” is placed between sheets of the S resin composition “XAREC S-100” (described above).
Glass cloth "# 7628" treated in "2" (above)
One sheet of the above was sandwiched, pressed at 300 ° C. and 40 kgf / cm ² for 5 minutes, and then cooled to obtain a prepreg. The three prepregs are superimposed, and an electric field copper foil having a thickness of 18 μm (described above) is superimposed on the upper and lower surfaces so that the roughened surface is on the inner side, 290 ° C., 30 kgf / cm
After pressing under the conditions of ² for 5 minutes (3 minutes after the internal temperature reaches 270 ° C., the melting point of the SPS resin),
Crystallization was performed at 50 ° C. and 50 kgf / cm ² for 1 minute to obtain a laminate for a printed wiring board having a total thickness of 0.64 mm.

(Comparative Example 2)
Two SPs sheeted to a thickness of 0.06mm
An aminosilane-based coupling agent “KBM60” is placed between sheets of the S resin composition “XAREC S-100” (described above).
Glass cloth "# 7628" treated in "2" (above)
One stack is sandwiched between the above (described above), and this is set as 3 stacks.
The stack was superimposed, and an electric field copper foil having a thickness of 18 μm (described above) was superimposed on the upper and lower surfaces so that the roughened surface was on the inside, and pressed at 300 ° C. and 40 kgf / cm ² for 5 minutes. Thereafter, crystallization treatment was performed at 150 ° C. and 50 kgf / cm ² for 1 minute to obtain a laminate for printed wiring boards having a total thickness of 0.64 mm.

(Comparative Example 3) The same conditions as in Comparative Example 2, except that the pressing conditions were changed from 5 minutes to 10 minutes,
By the method, a laminate for a printed wiring board having a total thickness of 0.64 mm was obtained.

(Evaluation) Tensile rupture strength measurement and migration resistance test (distance between electrodes: 3 m) of the laminates for printed wiring boards prepared in Examples and Comparative Examples after removing the copper foil.
m, applied voltage DC50V, atmosphere 40 ° C, 90% RH,
240 hours). The test results are shown in Table 1.

[0044]

[Table 1]

(Example 3) As a reinforcing material, aluminum borate whiskers "Alvolex" (trade name, manufactured by Otsuka Chemical Co., Ltd.) treated with aminosilane-based coupling agent "KBM602" (supra) were used, and SEBS was used as the reinforcing material. 20% of "Tuftec M1913" (made by Asahi Kasei Kogyo Co., Ltd.)
A solution (using a mixed solvent of xylene: MIBK = 9: 1 as a solvent) is applied by spraying, stirred with a universal stirrer, dried at room temperature, and then dried through a hot-air drying oven at 180 ° C. to obtain a treated reinforcing material. I got As mica, phlogopite “S-325” (trade name, manufactured by REPCO) treated with aminosilane-based coupling agent “KBM602” (described above) was used, and SEBS “Tuftec M1913” (trade name, manufactured by Asahi Kasei Corporation) 2% solution (solvent xylene: MI)
BK = 9: 1 mixed solvent), spray-coat, stir with a universal stirrer, dry at room temperature,
The resultant was dried through a hot-air drying oven at ℃ to obtain surface-treated mica. Pelletized SPS resin composition "XAREC S-1"
00 "(described above) from the main hopper of the twin-screw kneading extruder, and the treated reinforcing material was added to the resin composition by 3%.
0% by weight and 20% by weight of surface treated mica,
The extruder was fed through a vent port using a side feeder and extruded to obtain a sheet having a thickness of 0.6 mm from a T-die.
One sheet of 35 μm electric field copper foil (described above) was placed on each side of one sheet of this sheet, and this was charged into a compression molding die.
0 ° C., was pressed for one minute under the conditions of 20kgf / cm ^2, 150 ℃, by performing 1 minute crystallization treatment at 20 kgf / cm ^2, to obtain a printed wiring board laminates of the present invention. The copper foil was removed by etching, and the relative dielectric constant was measured to be 2.7 (1 GHz). Further, the flexural modulus was 17.2 kgf / mm ² and the warpage was 0.17%.

Example 4 In the same manner as in Example 3, pelletized SPS resin composition "XAREC S-100" (described above) was charged from the main hopper of a twin-screw kneading extruder, and the treated reinforcing material was added. An extruder was used so that 40% by weight of the resin composition and 15% by weight of a surface-treated mica similarly prepared using surface-treated muscovite “M-325” (trade name, manufactured by REPCO). Extruded from the vent using a side feeder and extruded, 0.6 mm thick from the T-die
Sheet was obtained. One sheet of 18 μm electric field copper foil (described above) was placed on both sides of one sheet of this sheet, and the sheets were charged into a compression molding die, and were placed under the conditions of 300 ° C. and 20 kgf / cm ^2.
Minutes after pressing, 0.99 ° C., at 20 kgf / cm ² 1
The crystallization treatment was performed for one minute to obtain a laminate for a printed wiring board of the present invention. When the copper foil was removed by etching and the relative dielectric constant was measured, it was 2.9 (1 GHz).
Met. The flexural modulus is 18.0 kgf / mm
^{2. The} warpage was 0.19%.

Example 5 As a reinforcing material, needle-shaped wallathnite "FPW-400" treated with an aminosilane-based coupling agent "KBM602" (described above).
(Made by Kinsei Matek Co., Ltd.) and SE
A 2% solution of BS "ToughTech M1913" (described above) (using a mixed solvent of xylene: MIBK = 9: 1) is applied by spraying, stirred with a universal stirrer, dried at room temperature, and then dried at 180 ° C. And dried through a hot-air drying oven to obtain a treated reinforcing material. In the same manner as in Example 3, pellet S
The PS resin composition “XAREC S-100” (described above) was charged from the main hopper of the twin-screw kneading extruder, and the treated reinforcing material was 40% by weight based on the resin composition, and the surface used in Example 4 was used. The treated mica was introduced from the vent of the extruder using a side feeder so as to be 15% by weight and extruded to obtain a sheet having a thickness of 0.6 mm from the T-die. An 18 μm electric field copper foil (described above) was placed on each side of one sheet of this
The sheets are arranged one by one, and this is charged into a compression molding die.
After pressing for 1 minute at 20 ° C and 20 kgf / cm ² ,
By subjecting the crystallization treatment at 150 ° C. and 20 kgf / cm ² for 1 minute, a laminate for a printed wiring board of the present invention was obtained. This copper foil is removed by etching,
When the relative dielectric constant was measured, it was 2.9 (1 GHz). The flexural modulus was 16.2 kgf / mm ² and the warpage was 0.19%.

Comparative Example 4 SPS resin composition "XARE"
"CS-100" (described above) was formed from a twin-screw extruder through a T-die to form a sheet having a thickness of 0.07 mm. A glass cloth “# 7628” (described above) is sandwiched between the two sheets, pressed at 290 ° C. and 30 kgf / cm ² for 5 minutes, and cooled at room temperature for 10 minutes to obtain a thickness of 0.1 mm. 2 was obtained. Four prepregs are superimposed, an 18 μm-thick electric field copper foil (described above) is superimposed on the upper and lower surfaces, and pressed at 290 ° C. and 30 kgf / cm ² for 5 minutes. For 30 minutes, and further cooled at room temperature for 10 minutes to obtain a laminate for a printed wiring board. The copper foil was removed by etching, and the relative dielectric constant was measured.
GHz). The flexural modulus is 25.4 kgf.
/ Mm ² , and the warpage was 0.17%.

(Comparative Example 5) Glass fiber (wire diameter 9 μm, length 5 mm, made of E glass) treated with an aminosilane-based coupling agent “KBM602” (described above) was used as a reinforcing material, and SEBS “Toughtech” was used. Spray and apply 2% solution of M1913 ”(supra) (solvent uses a mixed solvent of xylene: MIBK = 9: 1), stir with a universal stirrer, dry at room temperature, and then dry with hot air at 180 ° C. It was dried through an oven to obtain a treated reinforcing material. As in Example 3, the pelleted SPS resin composition “XAREC S-
100 "(described above), which was charged from the main hopper of the twin-screw kneading extruder. The treated reinforcing material was 40% by weight based on the resin composition, and the surface-treated mica used in Example 4 was 15%. The mixture was extruded from the vent opening of the extruder using a side feeder and extruded so as to obtain a sheet having a thickness of 0.6 mm from the T-die. One on both sides of this sheet
An 8 μm electric field copper foil (described above) is arranged one by one, and this is charged into a compression molding die, and is heated at 300 ° C. and 20 kgf / cm ^2.
After pressing for 1 minute under the conditions of
By performing crystallization treatment at 1 cm ² for 1 minute, a laminate for a printed wiring board was obtained. The copper foil was removed by etching and the relative dielectric constant was measured.
(1 GHz). The flexural modulus is 17.4k
gf / mm ² and warpage were 0.41%.

(Example 6) By T-die extrusion molding,
Two SPs sheeted to a thickness of 0.06mm
Glass cloth treated with a mercaptosilane-based coupling agent "KBM803" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) between sheets of S resin composition "XAREC P-86" (trade name, manufactured by Idemitsu Petrochemical Co., Ltd.) "# 7628" (see above)
Was pressed at 300 ° C. and 40 kgf / cm ² for 5 minutes, and then cooled to obtain a prepreg.
A 0.20 mm thick SPS is placed between the two prepregs.
A sheet of the resin composition “XAREC P-86” (described above) is sandwiched between sheets, and an electric field copper foil having a thickness of 18 μm (described above) is superimposed on the upper and lower surfaces so that the roughened surface is on the inside. ,
5 minutes at 290 ° C. and 30 kgf / cm ² (3 minutes after the internal temperature reaches 270 ° C., the melting point of the SPS resin).
After pressing, a crystallization treatment was performed at 150 ° C. and 50 kgf / cm ² for 1 minute, and the total thickness was 0.64 mm, and the ratio of the thickness of the layer including the woven fabric to the layer not including the woven fabric was 1: 0.5. A laminate for a printed wiring board of the present invention was obtained. The copper foil was removed by etching, and the relative dielectric constant was measured. As a result, it was 2.7 (1 GHz). Further, the flexural modulus was 21.7 kgf / mm ² .

(Example 7) By T-die extrusion molding,
An aminosilane-based coupling agent “KBM60” was placed between two sheets of the SPS resin composition “XAREC P-86” (described above) sheeted to a thickness of 0.06 mm.
Glass cloth "# 7628" treated in "2" (above)
300 ° C, 40kgf / cm ²
After pressing for 5 minutes under the conditions described above, cooling was performed to obtain a prepreg. As the fibrous filler, an aluminum borate whisker “Albolex” (described above) treated with an aminosilane-based coupling agent “KBM602” (described above) was used.
SEBS "ToughTech M1913" (mentioned above)
A 0% solution (solvent is a mixed solvent of xylene: MIBK = 9: 1) is applied by spraying, followed by high-speed stirring with a universal stirrer,
Drying was performed at room temperature and then through a hot air drying oven at 180 ° C. to obtain a surface-treated fibrous filler. SPS resin composition “XAR” previously pelletized by extrusion molding
ECS-100 ”(supra) was charged from the resin input hopper of the twin-screw kneading extruder, and the side of the extruder was vented so that the ratio of the surface-treated fibrous filler was 40% by weight. It was charged using a feeder, and passed through a T-die to obtain a filler-containing sheet having a thickness of 0.20 mm. Between the two prepregs, one sheet with the filler is sandwiched,
On the upper and lower surfaces, an 18 μm-thick surface-roughened electric field copper foil (described above) is overlapped so that the roughened surface is on the inner side, and at 290 ° C. and 30 kgf / cm ² for 5 minutes (internal). After the temperature reaches 270 ° C., the melting point of the SPS resin, it is pressed for 3 minutes) and then pressed at 150 ° C. and 50 kgf / cm.
² for 1 minute to obtain a laminate for a printed wiring board of the present invention having a total thickness of 0.64 mm and a thickness ratio of a layer containing a woven fabric to a layer not containing a woven fabric of 1: 0.5. Was. The copper foil was removed by etching, and the relative dielectric constant was measured to be 2.9 (1 GHz). Further, the flexural modulus was 25.6 kgf / mm ² .

(Example 8) Using a prepreg and a sheet containing a filler obtained in the same manner as in Example 7, a sheet containing a filler having a thickness of 0.20 mm is superimposed on both sides of one prepreg one by one. Further, after the prepregs are stacked one by one on the upper and lower surfaces, a thickness of 18 μm
The surface-roughened copper foil (described above) is overlaid so that the roughened surface is on the inside, at 290 ° C. and 30 kgf /
After pressing for 5 minutes under the condition of cm ² (for 3 minutes after the internal temperature reaches 270 ° C. which is the melting point of the SPS resin),
The printed wiring of the present invention is subjected to crystallization treatment at 50 ° C. and 50 kgf / cm ² for 1 minute, and has a total thickness of 1.04 mm and a thickness ratio of a layer containing a woven fabric to a layer not containing the woven fabric of 1: 2/3. A plate laminate was obtained. The copper foil was removed by etching and the relative dielectric constant was measured to be 3.1 (1 GH).
z). The flexural modulus is 25.1 kgf / m.
m ² .

Example 9 Sheets containing fillers having a thickness of 0.1 mm and 0.05 mm were produced by the same method and material as in Example 7. Sheet 1 with filler of thickness 0.1mm
The same prepreg as in Example 7 was superimposed on both sides of the sheet, and a 0.05 mm-filled sheet was superimposed on the upper and lower surfaces, and the upper and lower surfaces were roughened on one side with a thickness of 18 μm. The electric field copper foil (described above) is overlaid so that the roughened surface is on the inside, 290 ° C., 30 kgf / cm ²
5 minutes under the conditions of (the internal temperature is the melting point of the SPS resin 2
3 minutes after reaching 70 ° C)
The printed wiring board according to the present invention, which is subjected to crystallization treatment at 50 ° C. and 50 kgf / cm ² for 1 minute, and has a total thickness of 0.64 mm and a thickness ratio of a layer containing a woven fabric to a layer not containing the woven fabric of 1: 0.5. To obtain a laminate. The copper foil was removed by etching, and the relative dielectric constant was measured to be 2.9 (1 GHz). Further, the flexural modulus was 23.2 kgf / mm ² .

Comparative Example 6 SPS resin composition "XARE"
“CP-86” (supra) was charged into a twin-screw extruder, and a sheet having a thickness of 0.07 mm was formed through a T-die. A glass cloth “# 7628” (described above) is sandwiched between the two sheets, pressed at 290 ° C. and 30 kgf / cm ² for 5 minutes, and then cooled at room temperature for 10 minutes to obtain a thickness of 0.1 mm. 2
mm prepreg was obtained. Four prepregs are superimposed, and an electric field copper foil having a thickness of 18 μm is formed on the upper and lower surfaces thereof (described above)
Are overlapped so that the roughened surface is on the inside, and 29
After pressing at 0 ° C. and 30 kgf / cm ² for 5 minutes (3 minutes after the internal temperature reaches 270 ° C., which is the melting point of the SPS resin), it is cooled at 140 ° C. for 30 minutes, and further cooled at room temperature for 10 minutes. Thus, a laminate for a printed wiring board was obtained. This copper foil is removed by etching,
The relative dielectric constant was measured and found to be 3.4 (1 GHz). Further, the flexural modulus was 25.4 kgf / mm ² .

(Comparative Example 7) Three sheets of a 0.20 mm thick SPS resin composition "XAREC P-86" (described above) were superposed on each other, and an electric field copper foil having a thickness of 18 µm was formed on the upper and lower surfaces thereof (described above). ) Are superimposed on each other so that the roughened surface is on the inside, and pressed at 290 ° C. and 30 kgf / cm ² for 5 minutes (3 minutes after the internal temperature reaches 270 ° C., the melting point of the SPS resin). And then pressurized at 140 ° C for 30
After cooling for 10 minutes and further at room temperature for 10 minutes, a laminate for a printed wiring board was obtained. The copper foil was removed by etching, and the relative dielectric constant was measured.
(1 GHz). The flexural modulus is 5.0 kg.
f / mm ² .

Example 10 Two sheets of SPS resin composition "XAREC S-100" previously sheeted to a thickness of 0.06 mm by T-die extrusion (see above).
Glass cloth treated with a mercaptosilane-based coupling agent “KBM803” (described above)
7628 "(supra), 300 ° C, 40kg
After pressing for 5 minutes under the condition of f / cm ² , it was cooled to obtain a prepreg. Three prepregs were stacked, and the upper and lower surfaces were subjected to a surface roughening treatment to deposit copper particles having an average surface roughness of 0.5 μm and an average particle size of 0.7 μm on the glossy side by plating. The above-mentioned 18 μm-thick electric field copper foil (described above) is overlapped with the roughened surface facing inward at 290 ° C. and 30 kgf / cm ² for 5 minutes (the internal temperature is the melting point of the SPS resin. After pressing for 3 minutes after reaching 270 ° C), press at 150 ° C, 50kgf / cm
² for 1 minute to obtain a laminate for a printed wiring board of the present invention having a total thickness of 0.64 mm. When the copper foil peel strength of this product was measured, it was 1.17 kgf / cm. The dielectric loss tangent in the thickness direction at 10 GHz was 0.0038 when measured by a method in the _TM0m0 mode using a disk resonator.

Comparative Example 8 The copper foil of Example 10 was subjected to a surface roughening treatment on the roughened surface having an average surface roughness of 8 μm to precipitate copper particles having an average particle size of 12 μm. A laminated board for a printed wiring board was produced in the same manner as in Example 10 except that the above conditions were satisfied. When the copper foil peel strength of this product was measured, it was 0.96 kgf / cm. Also, 1
The dielectric loss tangent in the thickness direction at 0 _GHz was measured by a method using a TM _0m0 mode using a disc resonator.
0.0088.

Comparative Example 9 A laminated board for a printed wiring board was prepared in the same manner as in Example 10 except that the copper foil in Example 10 was a rolled copper foil having an epoxy resin adhesive applied to one surface. Produced. When the copper foil peel strength of this product was measured, it was 0.12 kgf / cm. Also, 1
The dielectric loss tangent in the thickness direction at 0 _GHz was measured by a method using a TM _0m0 mode using a disc resonator.
0.0035.

Example 11 One glass cloth “# 7628” (described above) treated with a mercaptosilane-based coupling agent “KBM803” (described above) was previously subjected to T-die extrusion molding to a thickness of 0.06 mm. SPS resin composition "XAREC S-100" sheeted in Japan
(Before) sandwiched between sheets, 18μm thick on the upper and lower surfaces
Laminated electric field copper foil (described above) is superimposed, and 30
After pressing at 0 ° C. and 40 kgf / cm ² for 5 minutes, it was cooled. Then, unnecessary portions of the copper foil are removed by etching, and both sides have a line width of 0.1 mm and a pitch of 0.2 mm.
Was formed so as to intersect the opposite surface at an angle of 90 ° to obtain an interior substrate. A thermosetting PPE-glass prepreg “TLP-596 DK” (trade name, manufactured by Toshiba Chemical Co., Ltd.) was provided as an adhesive layer on both surfaces of the interior substrate, and the upper and lower surfaces were roughened on one side with a thickness of 18 μm. The electric field copper foil (described above) is overlaid so that the roughened surface is on the inside, and the hot plate set temperature is 180 ° C. and the pressure is 7 kgf.
/ Cm ² for 10 minutes, after which the pressure is increased to 20 kgf / cm
² and pressed for 2 hours.
After pressing at 0 kgf / cm ² for 2 minutes, the mixture was cooled to obtain a laminate for a multilayer (four-layer) printed wiring board of the present invention. The copper foil on the outermost surface is completely removed by etching, and X
When the interior pattern was observed with the line, no defect such as displacement or distortion was observed in the pattern.

(Comparative Example 10) A thermosetting PPE-glass prepreg “TLP-596 DK” (described above) was disposed as an adhesive layer using the same interior substrate as in Example 11, and the upper and lower surfaces were thick. An electric field copper foil having a surface roughness of 18 μm (described above) is superimposed such that the roughened surface is on the inside,
Hot plate set temperature 180 ° C., a pressure 7 kgf / cm ² for 10 minutes, and then raised the pressure to 20 kgf / cm ² 2
After pressing for a time, cooling was performed to obtain a multilayer (four-layer) printed wiring board. When the copper foil on the outermost surface was completely removed by etching, and the interior pattern was observed with X-rays, no problems such as misalignment or distortion in the pattern were observed. However, when the peel strength between the adhesive layer and the interior substrate was measured, it was 300 g / cm, which was not usable.

(Comparative Example 11) A thermosetting PPE-glass prepreg “TLP-596 DK” (described above) was disposed as an adhesive layer using the same interior substrate as in Example 11, and the upper and lower surfaces were thick. An electric field copper foil having a surface roughness of 18 μm (described above) is superimposed such that the roughened surface is on the inside,
After pressing at a hot plate set temperature of 280 ° C. and a pressure of 20 kgf / cm ² for 2 minutes, the resultant was cooled to obtain a multilayer (four-layer) printed wiring board laminate. When the copper foil on the outermost surface was completely removed by etching and the interior pattern was observed with X-rays, the pattern was displaced and distorted almost over the entire surface.
Disconnection was observed on both sides. Further, when an attempt was made to measure the peel strength between the adhesive layer and the interior substrate, the adhesion was strong and the base material of the adhesive layer was broken, so that accurate measurement could not be performed.

[0062]

According to the first aspect of the present invention, the woven fabric is made of SPS.
By performing a surface treatment with a resin that is compatible with the resin composition, the affinity between the two is improved, and as a result, the impregnation of the SPS resin composition between the fibers constituting the woven fabric proceeds rapidly, so that the production time And the production cost can be reduced, the residual bubbles existing at the interface between the SPS resin composition and the woven fabric are extremely small, the mechanical strength is excellent, and the long-term environmental reliability represented by migration resistance is excellent. A high laminate for printed wiring boards can be obtained. According to the invention of claim 2, using a reinforcing material exemplified by aluminum borate whiskers,
By treating this, the mechanical strength can be improved while suppressing the increase in the dielectric constant, and the production efficiency can be increased. According to the third aspect of the invention, in addition to the effect of the second aspect of the present invention, it is possible to reduce the warpage generated in the printed wiring board laminate, and to enhance the dimensional stability. According to the fourth aspect of the present invention, a laminated board for a printed wiring board having sufficient mechanical strength, excellent dielectric characteristics, and high-frequency characteristics can be obtained. According to the fifth aspect of the present invention, a laminate for a printed wiring board having a sufficient adhesive strength between the insulating base material and the copper foil can be obtained without impairing the performance of the SPS resin.
According to the invention of claim 6, a laminate for a multilayer printed wiring board having a sufficient interlayer adhesive strength can be obtained, which can contribute to miniaturization and weight reduction of equipment. According to the invention of claim 7, the laminated board for a multilayer printed wiring board according to claim 6 can be manufactured without the wiring pattern coming off or being distorted. Further, in any of the first to sixth aspects of the present invention, since the SPS resin composition is used as the resin material, the resin composition has excellent heat resistance and dielectric properties, and has high frequency characteristics such as high-speed operation and small communication equipment. Even when used for required applications, heat generation and noise can be reduced. Further, since the price is lower than that of the conventional PTFE or BT resin substrate, the product cost can be reduced.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hiroshi Ohara 1-406-1, Yoshino-cho, Omiya-shi, Saitama Shin-Etsu Polymer Co., Ltd. Product Research Laboratories

Claims (7)

[Claims] 1. A conductive metal layer is provided on both or one or both surfaces of an insulating substrate composed of a woven fabric and a resin composition mainly composed of a polystyrene resin having a syndiotactic structure as a main material. A laminate for a printed wiring board, wherein the surface of the woven fabric is previously treated with a resin composition having compatibility with the polystyrene resin. 2. A resin composition mainly comprising a polystyrene resin having a syndiotactic structure as a main material, and a general formula aA _X O _Y .bB ₂ O ₃ (where a and b are 1 to 9 respectively)
A is a trivalent metal element, X and Y are X = 2, Y
= 1, X = Y = 1 or X = 2, Y = 3) or the general formula pM
_{V O w · qSiO 2 · rH} 2 O (p, q, r is, 1 ≦ p
≦ 3, 1 ≦ q ≦ 3, 0 ≦ r ≦ 10, M is a 1-3 valent metal element, V and W are V = 2, W = 1, V = W = 1 or V = 2, W = 3) In a laminated board for a printed wiring board provided with a conductive metal layer on both or one or both surfaces of an insulating base material comprising a reinforcing material represented by W), the amount of the reinforcing material is not more than the resin composition 2. The composition according to claim 1, wherein the reinforcing material has a ratio of 5 to 60% by weight with respect to the material, and the surface of the reinforcing material is previously treated with a resin composition having compatibility with the polystyrene resin. 3. For printed wiring boards. 3. The printed wiring board laminate according to claim 2, wherein the insulating base material contains mica in an amount of 10 to 70% by weight based on the resin composition. 4. An electrically conductive metal layer is provided on both or one or both surfaces of an insulating substrate composed of a woven fabric and a resin composition mainly composed of a polystyrene resin having a syndiotactic structure as a main material. In the printed wiring board laminate, the thickness ratio of the layer containing the woven fabric and the layer not containing the woven fabric constituting the insulating base material is in the range of 1: 0.25 to 1: 4,
A laminate for a printed wiring board, wherein the two layers are arranged substantially symmetrically in the thickness direction. 5. A print in which a copper foil layer is provided on both or one or both surfaces of an insulating base material comprising a resin composition mainly composed of a polystyrene resin having a syndiotactic structure as a main material and a reinforcing material. In the laminate for a wiring board, the bonding surface of the copper foil layer with the insulating substrate has metal particles having an average particle diameter of 1 μm or less deposited by a plating method, and is bonded before the metal particles are deposited. Average surface roughness of 1μ
m or less. 6. An outer surface of at least one interior substrate in which wiring patterns are formed on both surfaces of an insulating base material mainly composed of a resin composition mainly composed of a polystyrene resin having a syndiotactic structure and a reinforcing material. A multilayer board for a multilayer printed wiring board provided with a conductive metal layer via an adhesive layer, wherein the adhesive layer comprises a thermosetting resin which cures at 250 ° C. or lower and a reinforcing material. Laminates for wiring boards. 7. After curing the adhesive layer at 250 ° C. or less,
The method for producing a laminated board for a multilayer printed wiring board according to claim 6, wherein the temperature is raised to 270 ° C or higher and then cooled.