JPH0641418A - Poly@(3754/24)phenylene oxide) resin composition and metal-clad laminate made by using the same - Google Patents

Abstract

PURPOSE:To improve the adhesion properties of a conventional poly(phenylene oxide) resin composition without substantially impairing the other properties. CONSTITUTION:The composition comprises a poly(phenylene oxide), a prepolymer of at least either of triallyl isocyanurate and triallyl cyanurate, a crosslinked polymer, a crosslinkable monomer, and a coupling agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyphenylene oxide resin composition and a metal foil-clad laminate using the same.

[0002]

2. Description of the Related Art Recently, polyphenylene oxide (hereinafter appropriately abbreviated as "PPO") has attracted attention because of its excellent high frequency characteristics. Casting or molding of PPO is carried out, and in this case, polystyrene (hereinafter abbreviated as "PS") and / or styrene butadiene copolymer is used to improve solubility and moldability. (Hereafter, abbreviated as "SBS")
May be used in addition to the formulation. However, even in a resin composition having such a composition, it is necessary to improve heat resistance and other physical properties depending on the application. To meet this demand, PPO is mixed with triallyl isocyanurate (hereinafter, abbreviated as “TAIC”) or triallyl cyanurate (hereinafter, abbreviated as “TAC”) as a resin composition. We are trying to obtain a resin molded product with excellent heat resistance. Furthermore, TAIC monomer and TAC
In order to prevent bleeding due to a monomer, TAIC or TAC is partly or wholly converted into a prepolymer and compounded.

[0003]

However, the conventional polyphenylene oxide resin composition has a problem that the adhesiveness is still insufficient. Therefore, for example, when a metal foil-clad laminate used for a printed wiring board is produced by using a conventional polyphenylene oxide resin composition, the adhesion of the metal foil is insufficient. Usually, a sheet or prepreg is prepared using a conventional polyphenylene oxide resin composition, and a metal foil-clad laminate is obtained by laminating and integrating a metal foil on this, but the adhesion of the metal foil is insufficient. If so, the metal foil for the circuit is easily peeled off during or after the manufacturing process of the printed wiring board, which is a problem.

In view of the above circumstances, the present invention aims to improve the adhesiveness without substantially deteriorating other properties of the conventional polyphenylene oxide resin composition, and at the same time, to provide a polyphenylene oxide resin composition. An object of the present invention is to improve the adhesion of metal foil to a metal foil-clad laminate using a product.

[0005]

In order to solve the above problems, in the polyphenylene oxide resin composition according to the present invention, a polyphenylene oxide, a triallyl isocyanurate and / or a triallyl cyanurate prepolymer, a crosslinkable polymer, and a crosslinker are used. Sex monomer, and
In the metal foil-clad laminate according to the present invention, a sheet and / or a prepreg and a metal foil are integrally laminated by using the polyphenylene oxide resin composition. I am trying to take the structure that is made into.

The present invention will be specifically described below. The PPO used in the present invention has, for example, the following general formula:

[0007]

[Chemical 1]

[Where R is hydrogen or 1 to 3 carbon atoms]
Represents a hydrocarbon group, and each R may be the same or different. ], As an example thereof, poly (2,6-dimethyl-1,4-phenylene oxide), poly (3,5-dimethyl-1,4-phenylene oxide), etc. are exemplified. Can be done.

The molecular weight is not particularly limited, but for example, the weight average molecular weight (Mw) is about 50,000.
A polymer having a molecular weight distribution Mw / Mn = 4.2 (Mn is a number average molecular weight) of about 0 is preferably used. Such PPOs, such as poly (2,6-dimethyl-1,4-
In the case of phenylene oxide), 2,6-xylenol can be obtained by oxidative coupling reaction with a gas containing oxygen and methanol in the presence of a catalyst. Here, as the catalyst, a copper (I) compound, N
(Without dash), N (with dash) -the-tert
-Butylethylenediamine, butyldimethylamine and hydrogen bromide can be included. In addition, methanol is
Based on this, 2 to 15% by weight of water can be added to the reaction mixture system so that the total of methanol and water becomes a polymerization solvent of 5 to 25% by weight.

The triallyl isocyanurate (TAI) in the polyphenylene oxide resin composition of the present invention is
The prepolymer of C) or triallyl cyanurate (TAC) can be produced by a solution polymerization method or a bulk polymerization method. The solution polymerization method is milder in reaction than the bulk polymerization method, and the molecular weight can be easily adjusted. In this method, a triallyl isocyanurate monomer and / or a triallyl cyanurate monomer is dissolved in a solvent, a radical initiator is mixed and reacted with stirring until an appropriate molecular weight is obtained, and heating is performed if necessary. It can be carried out. At that time, it is preferable to carry out the reaction using a reflux apparatus and in an atmosphere in which oxygen does not exist.

The reaction atmosphere may be, for example, a nitrogen atmosphere. Further, as the solvent, benzene, toluene, xylene, methanol, ethanol, acetone, methyl ethyl ketone, heptane, carbon tetrachloride, dichloromethane, trichloroethylene, etc. can be used. As the radical initiator, any appropriate one can be used including conventionally known ones, and examples thereof include benzoyl peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane and t-.
Butyl peroxy benzoate, dicumyl peroxide, etc. can be illustrated.

For example, the above-mentioned triallyl isocyanurate prepolymer can be produced as follows. (Example 1): triallyl isocyanurate monomer 280
Benzoyl peroxide 11 g, benzene 1087 g
g, and using a stirrer and a reactor equipped with a reflux condenser,
The reaction is carried out for 6 hours while boiling under a nitrogen atmosphere. After recovering benzene under reduced pressure, methanol is added to recover the polymer, which is dried under reduced pressure. 139 g of polymer are obtained. The number average molecular weight is about 10,000. (Example 2): triallyl isocyanurate monomer 225
Dicumyl peroxide (10 g) and toluene (527 g) were added to g to obtain a polymer in the same manner as in Example 1. The number average molecular weight is about 4,000.

For example, the number average molecular weight of the triallyl isocyanurate or the prepolymer of triallyl cyanurate which can be produced as described above is 10,000.
It is preferably 0 or less. Since the triallyl isocyanurate and the triallyl cyanurate have an isomer relationship in terms of chemical structure and show almost the same reactivity and polymer characteristics, either one or both can be used. .

The crosslinkable polymer in the polyphenylene oxide resin composition of the present invention is not particularly limited, but for example, 1,2-polybutadiene, 1,4-polybutadiene, styrene butadiene copolymer, modified 1 , 2-polybutadiene (male modified, acryl modified, epoxy modified), rubbers and the like, each of which may be used alone or in combination of two or more. The polymer state may be elastomer or rubber.
Further, polystyrene may be used within a range that does not hinder the achievement of the object of the present invention.

Examples of the crosslinkable monomer include ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, acrylates such as silicon acrylates, triallyl cyanurate and triallyl. Examples include polyfunctional monomers such as isocyanurate, ethylene glycol dimethacrylate, divinylbenzene and diallyl phthalate, monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene and paramethylstyrene, and polyfunctional epoxies. Alternatively, two or more may be used together, but the invention is not particularly limited to these.

The blending of crosslinkable polymers and monomers improves film-forming properties, crosslinkability, adhesion, heat resistance and dielectric properties. Then, examples of the coupling agent which is a feature of the compound of the polyphenylene oxide resin composition of the present invention include a silane coupling agent and a titanate coupling agent.

Examples of silane coupling agents include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimechitosisilane, γ-methacryloxypropyltrimethoxysilane and β- (3,4 epoxycyclohexyl). ) Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, There are N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like.

Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate) titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl Isostearoyl titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl isostearoyl dia Riruchitaneto, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenylalanine titanate, tetraisopropyl bis (dioctyl phosphite) titanate.

These coupling agents may be used alone or in combination of two or more. A prepolymer of TAIC and / or TAC as described above,
Crosslinkable polymer, crosslinkable monomer, coupling agent in PPO
When compounded in, the initiator may also be compounded.

As the initiator, the following two types can be selected depending on whether the resin composition is an ultraviolet curing type or a thermosetting type, but is not limited to these. UV curable photoinitiators (ie,
As those that generate radicals by UV irradiation),
Benzoin, allyldiazonium fluoroborate, benzyl methyl ketal, 2,2-diethoxyacetophenone, benzoyl isobutyl ether, p-tert-butyltrichloroacetophenone, benzyl (o-ethoxycarbonyl) -α-monooxime, biacetyl, acetophenone, benzophenone, Michler's ketone, tetramethylthiuram sulfide, azobisisobutyronitrile, etc. can be used.

Further, as the thermosetting type initiator (that is, one which generates a radical by heat), dicumyl peroxide, tert-butyl cumyl peroxide, di-
tert-butyl peroxide, 2,5-dimethyl-2,
5-di- (tert-butylperoxy) hexyne-3,
2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexane, α (without dash), α (with dash) -bis (tert-butylperoxy-m-isopropyl) benzene [1,4 (Or 1,3) -bis (tert-
Butylperoxyisopropyl) benzene] and the like, 1-hydroxycyclohexylphenyl edone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl)
2-hydroxy-2-methylpropan-1-one, 2
-Chlorothioxanthone, methylbenzoyl formate, 4,4-bisdimethylaminobenzophenone (Michler's ketone), benzoin methyl ether, methyl-o
-Benzoyl benzoate, α-acyloxime ester, biscumyl of NOF CORPORATION, etc. may be used alone or in combination of two or more, but are not limited thereto.

PPO, TAIC and / or TA in the polyphenylene oxide resin composition of the present invention
The compounding ratio of the prepolymer of C, the crosslinkable polymer, the crosslinkable monomer, the coupling agent, and the reaction initiator (100% by weight based on the total polyphenylene oxide resin composition) is usually P.
5 to 95% by weight of PO, TAIC and / or TAC
1 to 90% by weight of the prepolymer and 1 to 9 of the crosslinkable polymer
0% by weight, 1 to 90% by weight of crosslinkable monomer, 0.1 to 10% by weight of coupling agent, and 0.1 to 10% of reaction initiator.
Keep in the range of% by weight.

The compounding components used in the polyphenylene oxide resin composition of the present invention as described above can be usually obtained by dissolving them in a solvent, mixing them, and then removing the solvent. Examples of the solvent in this case include halogenated hydrocarbons such as trichloroethylene, trichloroethane, chloroform and methylene chloride, aromatic hydrocarbons such as chlorobenzene, benzene, toluene and xylene, acetone and carbon tetrachloride. Trichloroethylene is particularly preferable, These may be used alone or in combination of two or more, but are not limited thereto. Note that the mixing may be performed by another method.

The obtained polyphenylene oxide resin composition can be used for producing a metal foil-clad laminate and can be molded into various other molded products. In the production of a laminate, the above composition can be molded into a sheet or prepreg and used. The sheet can be manufactured, for example, by the casting method as follows.

In the casting method, a solution of a polyphenylene oxide resin composition mixed by being dissolved in a solvent,
In this method, a thin layer is formed by casting or coating and then the solvent is removed to obtain a cured product. According to the casting method, a cured product can be obtained at a low temperature without using the costly calendar method. More specifically explaining this casting method, a solution of a flame-retardant polyphenylene oxide resin composition mixed in a solvent is mixed on a mirror-finished iron plate or a carrier film for casting, for example, 5 to 700 ( Preferably, the sheet is obtained by casting (or coating) to a thickness of 5 to 500) μm and sufficiently drying to remove the solvent.

The carrier film for casting is not particularly limited, but polyethylene terephthalate (hereinafter abbreviated as "PET") film, polyethylene film, polypropylene film, polyester film, polyimide film and the like which are insoluble in the above solvent are usable. Those which are preferably subjected to a release treatment are preferable.

Drying is performed by air drying or hot air drying. In this case, the upper limit of the temperature range is preferably lower than the boiling point of the solvent or lower than the heat resistant temperature of the casting carrier film (when drying is performed on the casting carrier film). The lower limit is determined by the drying time and processability. For example, when using trichlorethylene as a solvent and a PET film as a carrier film for casting, the range from room temperature to 80 ° C is preferable, and the temperature within this range is preferable. By increasing the value, the drying time can be shortened.

The prepreg can be manufactured as follows. That is, the cured product or the raw material blending component thereof is completely dissolved in the above solvent at a ratio of, for example, 5 to 50% by weight to obtain a solution of the polyphenylene oxide resin composition of the present invention as a base material. The thermosetting resin composition is impregnated and adhered to the base material by dipping (dipping). In this case, it suffices to remove the solvent by drying or the like, or it may be semi-cured to the B stage. The resin content of the prepreg thus prepared is not particularly limited, but is preferably 30 to 60% by weight. The base material is a cloth-like material such as glass cloth, aramid cloth, polyester cloth, or nylon cloth that can be impregnated with resin, a mat-like material made of these materials and / or a fibrous material such as a nonwoven fabric, paper such as kraft paper, linter paper, etc. Are used, but are not limited thereto. When the prepreg is manufactured in this manner, the resin does not have to be melted, and therefore it can be performed at a relatively low temperature more easily.

The required number of such prepregs or sheets are laminated and integrated with a metal foil to form a metal foil-clad laminate. In this case, the metal foil is used in ordinary printed wiring board manufacturing. Appropriate materials such as copper foil and aluminum foil are used. A metal foil is arranged on the outer side (both outer sides or one outer side) of the required number of prepregs and / or sheets, and laminated and clamped under heating at a required temperature and pressure. If the metal foils are placed on both outsides, the both sides will be metal foil-clad, and if the metal foils are placed on only one outside, the one-sided metal foil will be cladded.

The adhesion between the metal foil and the sheet or prepreg or between the sheet and / or prepreg uses heat fusion of resin. Therefore, the lamination pressing temperature is set to be equal to or higher than the glass transition temperature of the resin. Further, an adhesive may be used to bond the metal foil and the sheet or prepreg or the sheet and / or prepreg. By this fusion, strong adhesion can be obtained, but if the crosslinking reaction by the radical initiator is performed by heating at this time, even stronger adhesion can be obtained. As the cross-linking reaction, thermal cross-linking, photo-crosslinking by ultraviolet irradiation, etc. can be performed,
When thermal crosslinking or photocrosslinking cannot be performed, radiation crosslinking may be performed. Further, the crosslinking by irradiation with radiation may be performed after the thermal crosslinking or the photocrosslinking.

[0031]

Since the polyphenylene oxide resin composition according to the present invention has the above-described composition, it has good heat resistance and significantly improved adhesiveness (this is due to the composition of the coupling agent) as compared with the prior art. is doing. Of course, since it is a polyphenylene oxide resin composition, it goes without saying that it has good high frequency dielectric characteristics.

Since the metal foil-clad laminate using the polyphenylene oxide resin composition of the present invention has good adhesiveness of the resin composition, the adhesion of the metal foil is improved, and, of course, heat resistance is also good, so that high precision processing is possible. The printed wiring board suitable for high-speed signal processing can be manufactured.

[0033]

EXAMPLES Next, specific examples of the present invention will be described. -Example 1- (A) First, a polyphenylene oxide resin composition was prepared as follows.

In a reactor equipped with a pressure reducing device, 30 parts by weight of polyphenylene oxide (GE PPO), 5 parts by weight of triallyl cyanurate prepolymer, 60 parts by weight of triallyl cyanurate (TAIC manufactured by Nippon Kasei Co., Ltd.), styrene putadiene copolymer ( Asahi Kasei Corp. Sorprene T40
6) 5 parts by weight, 3 parts by weight of dicumyl peroxide (DCP manufactured by NOF CORPORATION) as an initiator, 1 part by weight of coupling agent: vinyltris (β-methoxyethoxy) silane, and further trichloroethylene (Triklene manufactured by Toagosei Co., Ltd.) ) Was added, and the mixture was sufficiently stirred until a uniform solution was obtained, and defoamed to obtain a polyphenylene oxide resin composition.

(B) Using the above resin composition, a metal foil-clad laminate was prepared as follows. The polyphenylene oxide resin composition obtained in (A) was impregnated into a glass cloth using an impregnating device, and dried at 100 ° C. for 5 minutes to remove trichlene to prepare a prepreg having a resin content of 60%.

Four prepregs obtained were superposed, electrolytic copper foils (thickness 18 μm) were arranged on both outer sides (upper and lower sides), and the temperature was 200 ° C., the pressure was 30 kg / cm ² , and the pressure was 90 minutes. By laminating and integrating them, a double-sided metal foil-clad laminate having copper foils (metal foils) 2 bonded to both surfaces of four prepregs 1 was obtained as shown in FIG. -Examples 2 to 5, Comparative Example 1-A resin composition was prepared in the same manner as in Example 1 except that the composition of each component in the polyphenylene oxide-based resin composition was as shown in Table 1. A double-sided metal foil-clad laminate was prepared.

With respect to the double-sided metal foil-clad laminates obtained in Examples and Comparative Examples, the dielectric constant, dielectric loss tangent, solder heat resistance, copper foil peeling strength, and bleeding property were measured. Table 2 shows the measurement results.
Shown in.

[0038]

[Table 1]

[0039]

[Table 2]

Comparing the characteristic measurement data of the example and the comparative example shows that the adhesive force (adhesiveness with the resin composition) of the metal foil can be improved without deteriorating the dielectric property, heat resistance and bleeding property. .

[0041]

Since the polyphenylene oxide resin composition of the present invention has the composition as described above, the adhesive property is improved without deteriorating the dielectric properties, heat resistance, bleeding property, etc. Even in the metal foil-clad laminate using this resin composition, the adhesion of the metal foil is improved without deteriorating the dielectric properties, heat resistance, bleeding property, etc. Therefore, the present invention is very useful. is there.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a metal foil-clad laminate obtained in an example.

[Explanation of symbols]

 1 Prepreg 2 Copper foil (metal foil)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C08L 9/00 LBR 8218-4J H01B 3/42 G 9059-5G (72) Inventor Tokio Yoshimitsu Osaka Inside the company, Matsushita Electric Works Co., Ltd.

Claims (5)

[Claims] 1. A polyphenylene oxide resin composition comprising a prepolymer of polyphenylene oxide, triallyl isocyanurate and / or triallyl cyanurate, a crosslinkable polymer, a crosslinkable monomer, and a coupling agent. 2. The polyphenylene oxide resin composition according to claim 1, wherein the coupling agent is at least one of a silane coupling agent and a titanate coupling agent. 3. The crosslinkable polymer is at least one selected from the group consisting of 1,2-polybutadiene, 1,4-polybutadiene, styrene butadiene copolymer, modified 1,2-polybutadiene and rubbers. Item 3. The polyphenylene oxide resin composition according to Item 1 or 2. 4. The crosslinkable monomer includes ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicon acrylates, triallyl cyanurate, triallyl isocyanurate, ethylene glycol. 4. At least one selected from the group consisting of dimethacrylate, divinylbenzene, diallylphthalate, vinyltoluene, ethylvinylbenzene, styrene, paramethylstyrene and polyfunctional epoxies. The polyphenylene oxide resin composition described. 5. A metal foil-clad laminate obtained by laminating and integrating a sheet and / or a prepreg and a metal foil using the resin composition according to any one of claims 1 to 4.