JPS6272748A - Production of cured ppo resin - Google Patents

Abstract

PURPOSE:To produce the titled cured article having excellent heat-resistance and strength, by dissolving and mixing polyphenylene oxide, a crosslinkable polymer and/or crosslinkable monomer and a polymerization initiator in a solvent and curing the mixture. CONSTITUTION:(A) A polyphenylene oxide, (B) a crosslinkable polymer (e.g. styrene-butadiene copolymer) and/or crosslinkable monomer (e.g. triallyl isocyanurate) (preferably a combination of both compounds) and (C) a radical polymerization initiator (e.g. benzoyl peroxide) or a photo-polymerization initia tor (e.g. benzoin which may contain arbitrary sensitizer) are completely dissolved in a solvent (e.g. triclene) at a concentration of 5-50wt%. The amounts of the components A, B and C are 10-90pts.(wt.), 1-50pts. and 0.1-3pts., respec tively. The solution is formed in the form of a film preferably by casting and cured with heat or ultraviolet radiation. The cured film is dried by removing the solvent therefrom to obtain the objective cured article.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention belongs to the technical field of a method for producing a cured polyphenylene oxide (hereinafter referred to as PPO) resin or a method for curing a PPO resin.

[Background Art] PPO resin is commercially available as so-called engineering plastics. However, recent advances in electronic technology have created a demand for engineering resins with even higher performance.

In order to meet the above demands, attempts have been made to improve PPO resins from various viewpoints. One of the specific challenges is to improve the moldability (flowability) of PPO resin, which has traditionally had problems. For example, JP-A-56-122
As disclosed in No. 851, PPO resin is
A method of improving moldability by blending other thermoplastic resins such as (methyl ethylbenzene) has been proposed. However, even if moldability could be improved by blending a thermoplastic resin, the reality was that the heat resistance of the PPO resin and further the strength of the PPO resin had to be sacrificed.

On the other hand, there have been attempts to further improve the heat resistance or strength of PPO resin, for example, a proposal to blend a thermosetting resin into PP○ resin was published in JP-A-57-143320 and JP-A-59-193929. There is a technology disclosed. These are made by blending epoxy resin with PPO resin,
Along with this, a technique for curing PPO, or a technique for blending 1.2 polybutadiene with PPO resin and blending a radical polymerization initiator for polymerization and curing has been disclosed.

However, it is readily understood that imparting curability to PPO, whether by thermosetting resin or other means, would result in the loss of the convenience of thermoplasticity in molding.

In other words, for example, when thermosetting properties are imparted to PPO, it is necessary to complete shaping within a short time until thermosetting, and molding is impossible after curing, which is the case with general thermosetting resins. This is a constraint that can be seen. Those skilled in the art will appreciate that such constraints typically make molding operations inconvenient.

Ultimately, no concrete proposal has yet been made regarding a technology that can maintain or improve the moldability of PPO resin and also improve its heat resistance and strength, and there is a demand for improvement of PPO resin with respect to these characteristics. was.

[Object of the invention] This invention was made in view of the above circumstances,
The purpose of the present invention is to provide a method for producing a cured PPO resin that has excellent heat resistance and strength while ensuring shapeability.

[Disclosure of the Invention] The present invention is characterized in that, in order to obtain a cured PPO resin, a PP01 crosslinkable polymer and/or a crosslinkable monomer and an initiator are dissolved in a solvent as raw materials and mixed, then cured, and then dried. Has characteristics.

The present invention will be explained in detail below.

The PPO used in this invention has the general formula, for example, where R represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and each R may be the same or different. Good too.

For example, poly(2,
6-dimethyl-1,4-phenylene oxide).

Such PPOs are, for example, USP4059568
It can be synthesized by the method disclosed in the specification. Although not particularly limited, for example, it average molecular weight (Mw) is 50,000, molecular weight distribution (Mw/Mn)
=4.2 (Mn is number average molecular weight) is used.

The crosslinkable polymer used in this invention is not particularly limited, but includes, for example, styrene-butadiene copolymer, styrene-butadiene rubber, 1.2-polybutadiene, 1.4-polybutadiene, modified 1.2-polybutadiene (malein-modified , acrylic modified, epoxy modified, etc.).

Furthermore, examples of crosslinkable monomers include triallylisosymanurate and trimethylolpropane triacrylate, but are not particularly limited to these.

Examples of initiators include radical initiators and photoinitiators.

As a radical initiator, Hensil peroxide,
Di-tert-butyl peroxide, 1-hydroxycyclohexylphenyl edone, 2-hyl'roxy2
-Methyl-1-phenyl-propan-1-one, 1-(
4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-chlorothioxanthone,
Examples include methyl benzoyl formate, 4,4-bisdimethylaminobenzophenone (Michler's ketone), benzoin methyl ether, methyl-0-penzoylhenzoate, and α-aziroxime ester.

Photoinitiators include benzoin, benzyl, allyldiazonium fluorophosphate, benzyl methyl ketal, 2
．． 2-jetoxyacetophenone, hendiyl isobutyl ether, p-tert-butyltrichloroacetophenone, benzyl(0-ethoxycarbonyl)-α-monoxime, biacetyl, acetophenone, benzophenone, Michler's ketone, tetramethylthiuram sulfide, azobisisopronitrile, etc. be.

In addition, the said crosslinkable polymer and crosslinkable monomer may be used individually, and may use 2 or more types together. A more favorable effect can be obtained when used together.

The ratio of blending the above raw materials is not particularly limited, but 1 to 5 parts of the crosslinkable polymer and/or crosslinkable monomer are added to 90 parts by weight (hereinafter abbreviated as parts) of the above raw materials.
Preferably, the proportion is 0 parts, and the proportion of the initiator is 0.1 to 3 parts.

In addition, when using a crosslinkable polymer and a crosslinkable monomer together, the ratio of the crosslinkable polymer to the crosslinkable monomer is not particularly limited, but it is preferably 1 part of the crosslinkable monomer to 20 parts of the crosslinkable polymer or less. .

The raw materials in the above formulation are completely dissolved at a ratio of 5 to 50% by weight in a single or mixed solvent selected from chlorine hydrocarbons such as tricrene, chloroform, carbon tetrachloride, and methylene chloride, xylene, toluene, benzene, and acetone. This solution is then subjected to shaping.

The shaping method is not particularly limited, but a so-called casting method is preferable. Furthermore, the shape of the excipient is not limited, and in principle, any shape can be used as long as it can be shaped. However, it is more desirable to have a shape that can be cast using the casting method, and therefore, the most suitable shape is a film or thread.

With such a shape, it is easy to uniformly cure, and it is also easy to remove the solvent after curing, which achieves the object of the present invention.

Next, the method of forming a film will be specifically explained using film forming as an example.

For example, the composition obtained by dissolving it in the above solvent is applied to a thickness of 5 to 500 μm on a mirror-treated iron plate or casting film, and is cured before drying. Here, drying is an illustrative expression of a means for removing the solvent, and is not intended to be limited to a method in which the solvent is removed by heating means.

There are no limitations on the means for curing. Curing can be performed by heat, light (for example, ultraviolet light, hereinafter abbreviated as UV), electron beam, or the like. In practice, a cheap and convenient method is curing by heat or light. After curing, it is sufficiently dried to obtain a PPO film. The above casting film is preferably a film that is insoluble in the above solvent, such as a polyester film (hereinafter abbreviated as PET) or a polyimide film, and has also been subjected to a mold release treatment. In the case of thermal crosslinking, it is desirable that the decomposition temperature of the initiator be lower than the boiling point of the solvent, but this is not particularly limited. For example, if trichlene is used as a solvent, isobutyl peroxide,
A suitable initiator is acetylcyclohexylsulfonyl peroxide.

After the PPO resin composition is cured as described above, it is dried. Since the film is cured before drying, it is easy to peel off the PPO resin composition film from the casting film during drying. This is not possible with normal casting. When the cured PPO resin film is peeled off and dried, the solvent evaporates from both sides of the cured PPO resin film, making drying easier. Note that, for drying, a method normally used as a means for removing a solvent, such as heat drying or reduced pressure drying, is employed.

Examples will be described below.

Resin compositions obtained with the formulations shown in Example Table 1 (Examples 1 to 6)
was dissolved in trichlene to make a 25% by weight solution, and PE
A film containing the solvent was obtained by casting on T to a thickness of 500 μm. Next, this film was given an output of 30 W/
After curing by irradiating UV for 5 seconds from a distance of 10 cm using three cm high-pressure mercury lamps, a cured PPO resin was obtained.

The physical properties of the cured PPO resin film obtained above are as follows:
The properties were as shown in the physical properties column of the table. Further, in the case of the formulations of Examples 7 and 8 in Table 1, thermal crosslinking was performed.

In Example 7, the solvent was trichlene, and in Example 8, the solvent was chlorobenzene. PPO in each solvent
The physical properties of the cured PPO resin film were obtained by dissolving raw materials such as, making a 25% solution by weight, casting it on PET to a thickness of 500 μm, heating it at 80°C and 120°C for 5 minutes, and drying it. The results were as in Example 7 and Example 8 of 1.

Comparative Examples The resin compositions obtained with the formulations of Comparative Examples 1 to 6 in Table 2 were dissolved in trichlene to make a 25% by weight solution, and PE
A film containing the solvent was obtained by casting onto T to a thickness of 500 μm. Next, after thoroughly drying this film, it was cured by irradiating UV for 5 seconds from a distance of 10 marks using three high-pressure mercury lamps with an output of 30 W/cm. The physical properties of the cured PPO resin film thus obtained were as shown in Comparative Examples 1 to 6 in Table 2. In addition, the resin compositions (films) obtained in Comparative Examples 7 to 9 in Table 2 were as follows:
Thermal crosslinking was performed. Comparative Examples 7 and 9 used trichlene as the solvent, and Comparative Example 8 used chlorobenzene. Dissolve raw materials such as PP0 in each of the above solvents,
A 25% by weight solution was prepared and cast onto PET to a thickness of 500 μm to obtain a film containing the solvent. Next, after sufficiently drying this film, for Comparative Example 7 and Comparative Example 9,
Comparative Example 8 was cured at 20° C. by heating at 80° C. for 5 minutes. The physical properties of the cured PPO resin films thus obtained were as shown in Comparative Example 7, Comparative Example 8, and Comparative Example 9 in Table 2.

As shown in Tables 1 and 2, the physical properties of the Examples were improved compared to the Comparative Examples. In addition, since shaping was carried out in a state containing a solvent, a cured product was obtained without any hindrance to shaping.

In Tables 1 and 2, SBS refers to styrene butadiene copolymer, TAIC refers to triallyl isocyanurate,
ACPO represents acetylcyclohexylsulfonyl peroxide, and CPO represents cumyl baroxyoftate.

The styrene-butadiene copolymer is Tsurprene T manufactured by Asahi Kasei.
411, triallyl isocyanurate is manufactured by Nippon Kasei Gll.
TA I C, acetyl cyclohexyl sulfonluperoxide is manufactured by NOF (perhexa AC3 manufactured by NOF 11), and cumyl peroxyoctate is manufactured by NOF side type Bark Mill O.
It was used.

[Remaining days below] [Effects of the invention] As seen above, the method for producing a cured PPO resin according to the present invention involves dissolving and mixing raw materials such as PPO resin in a solvent, and shaping this. Since the resin is cured before removing the solvent and the solvent is removed after curing, a cured product of PPO resin can be obtained without hindering shaping, and the strength and heat resistance of the cured product can be increased at the same time. It has the effect of being able to.

Claims (4)

[Claims] (1) Polyphenylene oxide (hereinafter referred to as PPO)
To obtain a cured product of the system resin, PPO, a crosslinkable polymer and/or a crosslinkable monomer, and a polymerization initiator are dissolved in a solvent and mixed, shaped, and cured.
A method for producing a cured PPO resin, which comprises removing a solvent and drying. (2) The method for producing a cured PPO resin according to claim 1, wherein the initiator is a radical initiator and the curing means is a heat curing method. (3) The cured PPO resin product according to claim 1, wherein the initiator is a photoinitiator that contains or does not contain a sensitizer, and the curing means is a method using ultraviolet irradiation. manufacturing method. (4) A method for producing a cured PPO resin product according to claims 1 to 3, wherein the shaped form is a film.