JPH0445530B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] This invention relates to a laminate using a polyphenylene oxide resin composition. [Background technology] X band (10GHz) used for satellite communications, etc.
Laminated plates used in the so-called ultra-high frequency range are required to have excellent high frequency properties, particularly excellent dielectric properties. That is, the dielectric constant and dielectric loss must both be constant and preferably low over a wide frequency range, temperature range, and humidity range. Conventionally, poly(4-fluoroethylene), alumina ceramic, cross-linked polyethylene, etc. have been used for such applications, but alumina ceramic has difficulties in processability, circuit formation (copper cladding method), etc. , poly(4-fluorinated ethylene), and cross-linked polyethylene all have low glass transition points, so they have the disadvantage that the dielectric constant and dielectric loss change significantly near practical conditions.Furthermore, their nonpolar nature makes it difficult to form circuits. It has the disadvantage of insufficient adhesive strength with metal foil. Under these circumstances, conventionally it has not been possible to easily obtain a laminate with excellent high frequency properties and heat resistance. [Purpose of the Invention] The present invention was made in view of the above circumstances, and an object of the present invention is to provide a laminate having excellent high frequency characteristics, as well as good heat resistance, peel strength, and electrical properties. There is. [Disclosure of the Invention] In order to achieve the above object, the inventors have made various efforts and decided to use polyphenylene oxide, which itself has excellent electrical properties such as high frequency properties, as the main material, and take advantage of its advantages. In addition, in order to improve various physical properties such as heat resistance and peel strength, we decided to blend triallyl isocyanurate and/or triallyl cyanurate to polyphenylene oxide, and further improved the above physical properties. However, in order to improve film formability, film transparency, etc., we decided to blend a butadiene-based crosslinkable polymer. Therefore, the present invention provides a laminate obtained by curing a resin composition containing polyphenylene oxide, triallyl isocyanurate and/or triallyl cyanurate, a butadiene-based crosslinkable polymer, and an initiator. This is the summary. This invention will be explained in detail below. In this invention, the term laminate includes one in which metal foil is laminated and bonded on both or one side, and one in which there is no metal foil at all. Polyphenylene oxide (also referred to as polyphenylene ether) used in this invention.Hereinafter,
(denoted as "PPO") is, for example, the following general formula, Here, R represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and each R may be the same or different. An example thereof is poly(2,6-dimethyl-1,4-phenylene oxide). Since PPO is not a crosslinking type, crosslinking does not occur alone. Therefore, in this invention, triallyl isocyanurate (hereinafter abbreviated as "TAIC") and/or triallyl cyanurate (hereinafter abbreviated as "TAC") is used as a crosslinking monomer. TAIC and TAC are used because they are compatible with PPO and have good film forming properties, crosslinking properties, heat resistance, and dielectric properties. TAIC and TAC are chemically structurally isomers and have almost the same properties, so similarly, only one of them,
Or you can use both. In addition, for the purpose of improving the physical properties of the laminate and the film forming properties of the resin composition,
A crosslinkable polymer is used. The blending ratio of each component in the resin composition is PPO,
TAIC and/or TAC and PPO in proportion to 100 parts by weight of crosslinkable polymer
It is preferable that the composition contains 50 parts by weight or more and less than 95 parts by weight of TAIC and/or TAC, 5 parts by weight or more and less than 50 parts by weight of TAIC and/or TAC, and the balance being a crosslinkable polymer. The crosslinkable polymer used here is a butadiene-based polymer, such as polybutadiene (for example, 1,2-polybutadiene, 1,4-polybutadiene, malein-modified 1,2-polybutadiene,
(acrylic modified 1,2-polybutadiene, epoxy modified 1,2-polybutadiene, etc.), styrene,
There are butadiene block polymers, etc., which can be used alone or in combination of two or more.
Not limited to these. In addition, an initiator may be used in the resin composition as necessary. As an initiator, a dialkyl peroxide having an effective functional group number of 2, for example, 2,5
-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-
Di(t-butylperoxy)hexane, α, α′-
Bis(t-butylperoxy-m-isopropyl)benzene {1,4(or 1,3)-bis(t
-butylperoxyisopropyl)benzene}, and in addition, benzoin, benzyl, allyldiazonium fluoroborate, benzyl methyl ketal, 2,2-diethoxyacetophenone, benzoyl isobutyl ether, p-
tert-butyltrichloroacetophenone, benzyl (o-ethoxycarbonyl)-α-monoxime, biacetyl, acetophenone, benzophenone, tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, 1-hydroxycyclohexyl phenyl Edon, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-chlorothioxanthone, methylbun Zoylformate, 4,4-bisdimethylaminobenzophenone (Michler's ketone), benzoin methyl ether, methyl-0-benzoylbenzoate, α-acyloxime ester, etc., and the following formula, ``Biscumil'' manufactured by Nippon Oil & Fats Co., Ltd., which is expressed as ``Biscumyl'', is used. The blending ratio of the initiator is not particularly limited, but
The initiator is added in a proportion of 0.1 to 100 parts by weight of PPO and TAIC and/or TAC.
It is preferable to contain 5.0 parts by weight of the initiator, and when using a crosslinkable polymer, the initiator is contained in an amount of 0.1 to 100 parts by weight based on the total of 100 parts by weight of PPO, TAIC and/or TAC, and the crosslinkable polymer.
It is preferable to contain 5.0 parts by weight. A method for obtaining a resin composition from the above raw materials is usually a blending or solution mixing method. For example, the above raw materials are called solvents (also called solvents).
Then, the resin composition is completely dissolved and mixed in a proportion of 5 to 50% by weight. Examples of the solvent include single or mixed solvents selected from halogenated hydrocarbons such as trichloroethylene, trichloroethane, chloroform, methylene chloride, and carbon tetrachloride, and aromatic hydrocarbons such as chlorobenzene, toluene, and xylene. From a solution of the resin composition as described above, a film of the resin composition is made by a casting method,
A resin-impregnated base material impregnated with a resin composition is prepared. To describe the casting method in detail, a solution of the resin composition is cast (sometimes coated) onto a mirror-treated iron plate or a carrier film for casting to a thickness of, for example, 5 to 700 μm, and A film is obtained by drying to remove the solvent. The upper limit of the set temperature during drying is preferably lower than the boiling point of the solvent or lower than the heat-resistant temperature of the carrier film for casting (when drying is performed on the carrier film for casting); The lower limit is determined by drying time, processability, etc. The resin-impregnated base material can be obtained, for example, by impregnating a base material with a solution of the resin composition and drying it. As the base material, glass cloth, glass mat, polyester cloth, polyester mat, aramid fiber cloth, paper, nonwoven fabric, etc. are used. A laminate is obtained by laminating and molding a predetermined number of the above-mentioned film and resin-impregnated base material, either alone or in combination, to a predetermined thickness. Alternatively, a film or resin-impregnated base material and metal foil may be laminated to form a laminate plate with metal foil on both sides or one side, or a predetermined number of films and/or resin-impregnated base materials may be laminated in advance and one side of this laminated plate may be formed. Alternatively, a metal foil-covered laminate can be obtained by overlapping metal foils on both sides and laminating them. As the metal foil, copper foil, aluminum foil, etc. are used. The overall thickness of the laminate obtained in this way is not particularly limited, but it is preferably about 0.2 to 2 mm, and 0.6 to 0.8 mm.
It is more desirable in terms of circuit design. If the resin composition contains an initiator and is thermally cured, the heating temperature and heating time during laminated molding will depend on the reaction temperature of the initiator used, etc. It is good to choose. For example, temperature 150~300℃, pressure 10~150Kg/ ^cm2 , time
It takes about 10 to 90 minutes. The resin is melted by heating during lamination molding, and films are adhered to each other, resin-impregnated base materials to each other, films and resin-impregnated base materials, films and metal foils, and resin-impregnated base materials to metal foils to each other to obtain a laminate. . This fusion bond provides strong adhesion. PPO has excellent adhesive properties, so it does not require an adhesive when laminating and bonding metal foils. If an initiator is blended into the resin composition, radical crosslinking will occur by heating and/or ultraviolet irradiation, and the resin will be cured.
This curing provides stronger adhesion and a stronger laminate. If radiation is then applied, a crosslinking reaction will occur and the resin will harden even if no initiator is added, resulting in even stronger adhesion and a stronger laminate. Even if metal foil is laminated, it has almost no effect on radiation irradiation. In order to take advantage of PPO's excellent heat-adhesive properties, if the metal foil is heat-sealed to the film or resin-impregnated base material in advance and then irradiated with radiation, the adhesive interface can also be crosslinked. Therefore, adhesion with excellent heat resistance can be realized between the film or resin-impregnated base material and the metal foil. The thus obtained laminate does not impair the properties of PPO, has excellent dielectric properties, and also has good heat resistance, peel strength, and electrical properties. It can be easily obtained by the manufacturing operation described above. Next, Examples and Comparative Examples will be described. (Examples 1 and 3) The compounded materials shown in Table 1 were dissolved and mixed in Trichloroethylene (trichloroethylene manufactured by Toagosei Chemical Industry Co., Ltd.) to form a 20% by weight solution of a resin composition. This solution was applied onto a release film to a thickness of 500 μm and dried to obtain a casting film about 100 μm thick. Six sheets of this film (15 sheets in Example 5) were stacked at a temperature of 220°C and a pressure of 50 kg/ ^cm2.
(In Example 5, lamination molding was carried out at 100 kg/cm ² for 30 minutes to obtain a laminate with a thickness of 0.8 mm. ) to prepare a 15% by weight solution of the resin composition.The base materials shown in Table 1 were impregnated with this solution to produce resin-impregnated base materials.Copper foil, Layer several sheets of resin-impregnated base material and copper foil in that order, and heat to 220℃.
℃ (200° C. in Example 6) and a pressure of 50 kg/cm ² for 30 minutes (60 minutes in Example 6) to obtain a 0.8 mm thick laminate. (Comparative Example 1) An attempt was made to obtain a casting film using the formulation shown in Table 1 in the same manner as in Example 1, but an ear-staining film could not be obtained with this resin composition. (Comparative Examples 2 and 3) A laminate with a thickness of 0.8 mm was obtained in the same manner as in Example 2 using the formulations shown in Table 1. In addition, comparative example 3
Since no initiator is added and only heating is performed during lamination molding, there is almost no curing. In Table 1, A is 2,5-dimethyl-2,5(t
-butylperoxy)hexyne-3, B is 2,5
-dimethyl-2,5-di(t-butylperoxy)hexane, C is α-α'-bis(t-butylperoxy-m-isopropyl)benzene, 1,2
-PB each represents 1,2-polybutadiene.

【table】

〔Effect of the invention〕

The laminate according to the present invention includes PPO and
Since it is obtained by curing a resin composition containing TAIC and/or TAC, it has excellent high frequency properties, and has good heat resistance, peel strength, and electrical properties.

Claims (1)

[Scope of Claims] 1. A laminate obtained by curing a resin composition containing polyphenylene oxide, triallyl isocyanurate and/or triallyl cyanurate, a butadiene-based crosslinkable polymer, and an initiator. 2. If the blending ratio of each component in the resin composition is polyphenylene oxide, triallyl isocyanurate and/or triallyl cyanurate, and crosslinkable polymer, the total of the three components
Polyphenylene oxide per 100 parts by weight
50 parts by weight or more and less than 95 parts by weight, 5 parts by weight or more and less than 50 parts by weight of triallyl isocyanurate and/or triallyl cyanurate, the remainder being a crosslinkable polymer, and between the initiator and the above three, the total of the three.
The laminate according to claim 1, wherein the initiator is contained in an amount of 0.1 to 5.0 parts by weight per 100 parts by weight. 3. The laminate according to claim 1 or 2, wherein the resin composition is formed into a casting film, and this film is laminated and molded. 4. The laminate according to claim 1 or 2, wherein the resin composition is impregnated into a base material, and this base material is laminated and molded.