JPS61287959A - Production of cured polyphenylene oxide article - Google Patents

Abstract

PURPOSE:To obtain the titled cured article having excellent resistance to heat and solvents, by impregnating a substrate with a resin compsn. consisting of a polyphenylene oxide, a crosslinkable polymer and/or monomer and a specified initiator, and curing it. CONSTITUTION:100pts.wt. mixture of 50-95pts.wt. polyphenylene oxide (A) [e.g. poly(2,6-dimethyl-1,4-phenylene oxide)] and 50-5pts.wt crosslinkable polymer (e.g. PS) and/or crosslinkable monomer (e.g. triallyl cyanurate) (B) and 0.1-5.0pts.wt. at least one initiator (C) selected from among compds. of formulas I, II and III (wherein R is a hydrocarbon group; R', R'' are each R, H) such as 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane-3 are dissolved in a solvent (e.g. trichloroethylene) in such a proportion as to give a concn. of 5-50wt%, thus obtaining a resin compsn. soln. A substrate is impregnated with the soln. and the resin compsn. is heat-cured at 120-250 deg.C under a pressure of 10-200kg/cm<2> for 30-60min.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing a polyphenylene oxide cured product.

[Background technology]

Polyphenylene oxide (also referred to as polyphenylene ether, hereinafter abbreviated as rPPOJ) has attracted attention in recent years due to its excellent high frequency characteristics. However, P
PO (including those commercially available as modified PPO)
is a thermoplastic resin and could not be said to have sufficient heat resistance, solvent resistance, 2 strength, etc.

[Purpose of the invention]

In view of the above circumstances, this invention has been developed to provide heat resistance, solvent resistance 1.
The object of the present invention is to provide a method for producing a PPO-based cured product with improved strength and the like.

[Disclosure of the invention]

In order to achieve the above object, the present invention provides a method for producing a PPO-based cured product by curing a resin composition containing a PP01 crosslinkable polymer and/or a crosslinkable monomer and an initiator, wherein the initiator is The following structural formula, R'-0-0-R-0-0-R".

(R is a hydrocarbon group, R' and R'' are each a hydrocarbon group or hydrogen, and R' and R'' may be the same (or different)) The gist thereof is a method for producing a PPO-based cured product characterized by at least one selected from the group consisting of:

The present invention will be explained in detail below.

The PPO used in this invention is, for example, represented by the following general formula, and examples thereof include poly(2,
6-dimethyl-1,4-phenylene oxide).

Since PPO is not a crosslinked type, crosslinking does not occur when used alone). Therefore, in the present invention, only one of the crosslinkable polymer and the crosslinkable monomer is used in combination with PPO, or both are used in combination with PPO.

The smell of this invention. Examples of crosslinkable polymers used include styrenic thermoplastic polymers (e.g., polystyrene, styrene-butadiene block copolymer, styrene-isoprene brosoccopolymer, etc.), polybutadiene (e.g., 1,2-polybutadiene, 1.2-polybutadiene, 1. 4
-polybutadiene, maleic-modified polybutadiene, acrylic-modified polybutadiene, epoxy-modified polybutadiene, etc.), rubbers, polyethylene, polyvinyl acetate, polyacrylate, nylon, polyvaramethylstyrene, each singly or in combination of two or more. Although they can be used in combination, they are not particularly limited to these.

The crosslinkable monomers used in this invention include, for example, (1) ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates,
Acrylic acids such as silicone acrylates, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene.

Examples include polyfunctional monomers such as diallyl phthalate, ■monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene, and polyvaramethylstyrene, and ■polyfunctional epoxies, which can be used alone or in combination of two or more. However, it is not particularly limited to these.

As the crosslinking monomer, it is recommended to use triallyl cyanurate (hereinafter abbreviated as rTAcJ) and/or triallyl isocyanurate (hereinafter abbreviated as rTA I C) because it has good compatibility with PPO and has good film-forming properties. It is preferable in terms of crosslinkability, heat resistance, and dielectric properties.

The initiator used in this invention has the following structural formula: R'-0-0-R-0-0-R" ... (I) ... (II) is a hydrocarbon group, R' and R'' are each a hydrocarbon group or hydrogen, and R' and R'' may be the same or different. At least one of the selected types.

The compound represented by formula (I) is, for example, 2,2-bis(t-butylperoxy)octane H3 (CH3) 3C-0-0-C-0-0-C(CHff
) 3■ CTo-CHz-CHz-CHz-CHz-CHzn-
Butyl-4,4-bis(t-butylperoxy)valerate CH.

blindness 2.2-bis(t-butylperoxy)butane CI.

(CH3)3G-0-0-C-0-0-C(CH3)3
zHs 2,5-dimethylhexane-2,5-cybidroba-oxide α,α'-bis(t-butylperoxy-m-isopropyl)benzene (1,4(or 1,3)-bis(1-
butylperoxyisopropyl)benzene) 2,5-dimethyl-2,5-di(t-butylperoxy)hexane 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, etc. There are, but are not limited to:

Examples of the compound represented by formula (II) include, but are not limited to, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane.

The compound represented by formula (III) is, for example, di-t-
Examples include butyl peroxyisophthalate,
It is not limited to this.

Among the above initiators, in particular, the peroxide represented by the formula (1), 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, α, α' -Bis(t-butylperoxy-m-isopropyl)benzene is effective for curing (crosslinking).

For example, the curing process is as follows.

The above-mentioned initiator is, for example, represented by the formula (1), when the 0-o bond is broken by heating, ultraviolet irradiation, radiation, etc., and the 0-0-R-○ −
0-R'→ R'-0・÷・0-R-○・+・O-R″, a radical is generated, R′-○・+・0-R-0・S・O-R 'Now-C-C-
This allows the radical reaction to proceed and improves crosslinking properties.

The blending ratio of the above raw materials is not particularly limited;
50 to 95 parts by weight, and 5 to 50 parts by weight of a crosslinkable polymer and/or a crosslinkable upper layer,
Preferably, the initiator is contained in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the total of PP01, crosslinkable polymer and/or crosslinkable monomer.

Methods for obtaining the resin composition from the above-mentioned raw materials include, for example, methods such as solution mixing and blending in which the above-mentioned raw materials are dissolved in a solvent (also referred to as a solvent), but are not limited to these methods. In addition, at this time, 5 to 50% by weight of the resin composition
Preferably, it is a solution. The obtained resin composition is molded into a plate, film, sheet, etc. and then cured. The molding method may be injection molding, extrusion molding, transfer molding, direct pressure molding, etc. Any method is fine. For example, a prepreg (also referred to as a resin-impregnated base material) is produced by impregnating a base material with a solution of a resin composition using a normal impregnation method, or a film is produced using a casting method, and then cured. Examples of solvents used in the solution mixing method, impregnation method, casting method, etc. include halogenated hydrocarbons such as trichloroethylene, trichloroethane, chloroform, methylene chloride, and carbon tetrachloride; aromatic solvents such as chlorobenzene, benzene, toluene, and xylene. There are group hydrocarbons, and these can be used alone or in a mixture of two or more, but are not limited thereto.

To describe the casting method in detail, a solution obtained by dissolving and mixing the resin composition in a solvent is cast onto a mirror-treated iron plate or a carrier film for casting to a thickness of, for example, 5 to 7'00 μm.
Alternatively, a film is obtained by coating (or coating) and thoroughly drying to remove the solvent. Note that the term "film" here includes what is called a sheet, membrane, tape, etc., and there are no particular limitations on the extent of the surface orthogonal to the thickness direction or the length, and the thickness can also be set in various ways depending on the application. It is possible to do so. The carrier film for casting is not particularly limited, but may be polyethylene terephthalate (hereinafter referred to as rPE).
Those that are insoluble in the above-mentioned solvents, such as TJ) film, polyethylene film, polypropylene film, and polyimide film, are preferable, and those that have been subjected to mold release treatment are preferable. The solution of the resin composition that has been cast (or coated) on a carrier film for casting is subjected to air drying and/or drying with hot air to remove the solvent. The upper limit of the temperature setting 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), and the lower limit is lower than the boiling point of the solvent or lower than the heat resistance temperature of the carrier film for casting. Determined by time and processability, for example,
When trichlorethylene is used as a solvent and a PET film is used as a carrier film for casting, the temperature range is preferably from room temperature to 80°C, and if the temperature is raised within this range, the drying time can be shortened.

The impregnation method involves impregnating a base material with a solution of the resin composition and drying it to obtain a prepreg. Examples of the base material include, but are not limited to, glass cloth, glass cloak polyester cloth, polyester mat aramid fiber cloth, paper, and nonwoven fabric. As described above, according to the casting method and the impregnation method, films and prepregs of the above resin composition can be obtained at low cost and at low temperatures.

Conditions for thermosetting include, for example, a temperature of 12
30-6 at 0-250℃, pressure 10-200kg/cj
It is preferable to perform heat molding for 0 minutes (laminate molding if necessary), and then perform curing (crosslinking) by radical reaction as described above. In the case of the prepreg and/or film, a predetermined number of sheets may be stacked individually or in combination to obtain a predetermined design thickness, and the prepreg and/or film may be thermally cured under the above curing conditions.

The PPO-based cured product obtained in this way does not impair the properties of Pro, has excellent high-frequency properties such as dielectric properties, and has excellent heat resistance, solvent resistance, and strength. It has become a thing. Moreover, if the molded product is irradiated with radiation after molding to perform radiation crosslinking, it will be even more excellent.

Next, Examples and Comparative Examples will be shown.

(Example 1.2) The blended raw materials shown in Table 1 were dissolved and mixed in Trichlorene (trichlorethylene 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 then dried to obtain a casting film with a thickness of about 100 μm. Layer several sheets of this film together at a temperature of 220℃ and a pressure of 100kg/
C4 for 30 minutes to obtain a PPO-based cured product.

(Example 3) The mixed raw materials shown in Table 1 were made into a solution in the same manner as in Example 1, and a glass cloth was impregnated with this solution to produce a prepreg. Layer several sheets of this prepreg and
It was molded for 60 minutes at 0°C and a pressure of 100 kg/crA.
A PO-based cured product was obtained.

(Example 4) The blended raw materials shown in Table 1 were dissolved and mixed in a mixed solvent of Trichloroethylene (trichloroethylene manufactured by Toagosei Kagaku Kogyo Co., Ltd.) and chloroform to form a 20% by weight solution of a resin composition. A casting film was obtained in the same manner as in Example 1 using this solution. Layer several layers of this film,
It was molded for 90 minutes at a temperature of 200° C. and a pressure of 50 ksr/co1 to obtain a PPO-based cured product.

(Examples 5 to 9) Casting films were obtained by using the mixed raw materials shown in Table 1 as a solution in the same manner as in Example 1. Layer several sheets of this film at a temperature of 200℃ and a pressure of 50kg/cn.
The mixture was molded for 30 minutes (90 minutes in Example 7) to obtain a PPO-based cured product.

(Comparative Examples 1 to 3) Same as Example 5 except that the mixed raw materials shown in Table 1 were used as a solution in the same manner as in Example 5 to obtain a casting film, and the molding time was 60 minutes in Comparative Example 3. A PPO-based cured product was obtained.

In addition, in Table 1, SBS and 5BS2 are styrene.
Butadiene block polymer, 1.2-PB is 1.2-
Polybutadiene, DCP is dicumyl peroxide, A
is 2,5-dimethyl-2,5-di(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, D is 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, E is di-t-butylperoxyisophthalate, Hail each. SBS+
is Tsurprene T406 (manufactured by Asahi Kasei Corporation), 5BSz
Toughprene A (manufactured by Asahi Kasei Industries), L, 2-P B
RB-810 (manufactured by Nippon Soda ■) was used.

For each PPO-based cured product (or solidified product) obtained in Examples 1 to 9 and Comparative Examples 1 to 3, room temperature beer, solvent resistance, soldering heat resistance, insulation resistance, dielectric constant, dielectric loss tangent, and glass transition point (Tg) various physical properties were measured. Solvent resistance was examined by immersing the sample in boiling trichlorethylene for 5 minutes and determining whether there was a change in appearance (OUT) or no change (OK).

The measurement results are also shown in Table 1.

As seen from Table 1, PP obtained in Examples 1 to 9
Compared to the cured or solidified products obtained in Comparative Examples 1 to 3, the O-based cured product had the same dielectric constant, high frequency properties of dielectric loss tangent, and insulation resistance, but the temperature of room temperature beer was about the same or higher. It has improved solvent resistance, soldering heat resistance, and Tg. Therefore, when the initiator used in the production method of the present invention is used, the crosslinkability of the resulting PPO-based cured product is improved compared to when other initiators are used or when no initiator is used at all. I understand.

〔Effect of the invention〕

The method for producing a PPO-based cured product according to the present invention cures a resin composition containing a PP01 crosslinkable polymer and/or a crosslinkable monomer, and the above-mentioned initiator, so it has excellent high frequency properties and is heat resistant. A PPO-based cured product with excellent properties, solvent resistance, and strength can be easily obtained.

Claims (4)

[Claims] (1) A method for producing a polyphenylene oxide-based cured product for curing a resin composition containing polyphenylene oxide, a crosslinkable polymer and/or a crosslinkable monomer, and an initiator, wherein the initiator has the following structural formula, R'-O-O-R-O-O-R'', ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R is a hydrocarbon group, R' and R'' are each carbonized is a hydrogen group or hydrogen, and R' and R'' may be the same,
May be different. ) at least one selected from the group consisting of compounds represented by
A method for producing a cured polyphenylene oxide product characterized by being a seed. (2) The method for producing a polyphenylene oxide cured product according to claim 1, wherein curing is performed after impregnating a base material with the resin composition. (3) The method for producing a cured polyphenylene oxide product according to claim 1, wherein the curing is performed after the resin composition is formed into a film by a casting method. (4) The resin composition contains 50 to 95 parts by weight of polyphenylene oxide and 5 parts by weight of crosslinkable polymer and/or crosslinkable monomer out of 100 parts by weight of polyphenylene oxide, crosslinkable polymer and/or crosslinkable monomer. 50 parts by weight, respectively, and 0.1 to 5.0 parts by weight of an initiator based on 100 parts by weight of the total of polyphenylene oxide, crosslinkable polymer and/or crosslinkable monomer. A method for producing a cured polyphenylene oxide product according to any one of Items 1 to 3.