JPS63179963A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition suitable for precision machine, electronic and electric parts, etc., having excellent heat resistance and mechanical properties, by blending a specific block copolymer with specific amounts of epoxy resin and an inorganic filler. CONSTITUTION:(A) 100pts.wt. block copolymer consisting of a polyphenylene sulfide part and a polyphenylene sulfide sulfone part, having 10-20,000 poise melt viscosity is blended with (B) 0.1-20pts.wt., preferably 0.1-15pts.wt. epoxy resin, (C) 0-250pts.wt. inorganic filler (e.g. glass fiber, etc.).

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to a thermoplastic resin composition with excellent heat resistance and mechanical properties, and various injection molding materials, extrusion molding materials, and compression molding materials. It can be used for etc.

<Prior art and its problems> A block copolymer consisting of a polyphenylene sulfite moiety and a polyphenylene sulfide sulfone moiety developed by the inventors of the present invention is rapidly expanding as a super heat-resistant engineering plastic. It is expected to be used in a wide range of fields because it has excellent dimensional accuracy while maintaining almost the same performance as known polyphenylene sulfide. However, this resin alone has low strength, so attempts have been made to improve it by adding various inorganic fillers such as glass fiber and carbon fiber, but the appearance of the molded product deteriorates and the reinforcement effect is insufficient. Since it cannot be obtained, it has not been put into practical use.

Means for Solving the Problems> In view of the above circumstances, the inventors of the present invention have made intensive studies to obtain a thermoplastic resin composition with improved strength, and have found that the above-mentioned block copolymer and inorganic filler The present invention was achieved based on the discovery that it is effective to use an epoxy resin in combination with the epoxy resin.

That is, the present invention provides (a) 100 parts by weight of a block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety, (b) epoxy resin 11 to
and 0 to 250 parts by weight of an inorganic filler.

The block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety of the present invention is a block copolymer of a polymer moiety, and can be produced by various manufacturing methods. . For example, sodium sulfide and bis(P-chlorophenyl)sulfone, an aromatic sulfide sulfone polymer with a cucorphenyl terminal group obtained by reacting in 1-N-methylpyrrolidone, and sodium sulfide and P-dichlorobenzene are reacted in N-methylpyrrolidone. A method of producing a block copolymer by heating terminal sodium sulfide group type polyphenylene sulfide obtained by reacting in pyrrolidone in N-methylpyrrolidone, polymerizing polyphenylene sulfide by a conventionally known production method, and further reacting. A method of adding sodium sulfide and bis(P-chlorophenyl)sulfone to the system and reacting it to obtain a block copolymer,
Conversely, as described in U.S. Pat. No. 4,301,274, a sulfide sulfone polymer is polymerized by a known method, and sodium sulfide and P-dichlorobenzene are further added to the reaction system and heated to obtain a block copolymer. can be mentioned. Further, the block copolymer may contain a homopolymer of polyphenylene sulfide, a homopolymer of polyphenylene sulfide sulfone, a random copolymer of phenylene sulfide and phenylene sulfide sulfone, etc., as long as the effects of the present invention are not impaired. I don't mind.

The block copolymer has a melt viscosity of 1 at 300°C.
Those having 0 to 20,000 voids are preferred. Further, the proportion of the polyphenylene sulfide sulfone moiety constituting the block copolymer is appropriately selected in the range of 1 to 99% by weight depending on the compounding conditions of the resin composition of the present invention.

The epoxy resin used in the present invention may contain one or more epoxy groups, and may be liquid or solid. For example, bisphenol A,
Resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3.5-)lihytotetraxybenzene, bisphenol 8. Trihydroxy-diphenyldimethylmethane, 4. Glycidyl ethers of bisphenols such as 4'-dihydroxybiphenyl, 15-dihydroxynaphthalene, cashew phenol, 2,255-tetrakis(4-hydroxyphenyl)hexane, halogenated bisphenols and butanediol in place of bisphenol. Glycidyl epoxy resins such as glycidyl ether type such as diglycidyl ether, glycidyl ester type such as phthalic acid glycidyl ester, glycidyl amine type such as N-glycidylaniline;
Examples include quaternary type non-glycidyl epoxy resins such as epoxidized polyolefin and epoxidized soybean oil, and cyclic type non-glycidyl epoxy resins such as vinylcyclohexene dioxide and dicyclopentadiene dioxide.

A particularly preferred epoxy resin in the present invention is a novolac type epoxy resin. Novolac type epoxy resin is
It contains two or more epoxy groups and is usually obtained by reacting a novolac type phenol resin with epichlorohydrin. In addition, novolak type phenolic resin can be obtained by a condensation reaction between phenols and formaldehyde.

There are no particular restrictions on the phenol used as this raw material, but phenol, 〇-cresol, m-cresol, p-cresol, bisphenol, resorcinol, p-tert-butylphenol, bisphenol F, bisphenol S, and mixtures thereof are particularly preferred. used. Furthermore, an epoxidized product of poly-P-vinylphenol can also be used in the same manner as the novolac type epoxy resin. Incidentally, these novolac type epoxy resins may have halogens, hydroxyl groups, etc., and may be used alone or as a mixture of two or more.

Generally, epoxy resins contain amines, acid anhydrides, polysulfides,
It is molded by adding a hardening agent such as phenolic resin,
In the present invention, it is desirable that no curing agent be used at all, or even if it is used, the molar ratio of the active hydrogen groups to the epoxy group component is less than half. If a normal amount of a curing agent is used together, the reaction between the epoxy resin and the copolymer used in the present invention may be inhibited, or the reaction between the epoxy resin and the curing agent may cause the formation of a crosslinked network. This is because it is no longer possible to expect a stable increase in The effect of the combined use of a curing agent is expected to be to prevent bleeding and deterioration of thermal properties caused by the addition of an epoxy resin.

The amount of the epoxy resin used in the present invention is in the range of 1 to 20 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the block copolymer. If the amount of epoxy resin is less than 11 parts by weight, the reinforcing effect will be insufficient; on the other hand, if it is more than 20 parts by weight, the viscosity of the dissolved acid in the composition will decrease too much, which will have a negative impact on moldability and the appearance of the molded product. affect

Inorganic fillers that can be used in the present invention include fibrous reinforcing agents such as glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber, silicon nitride, aramid fiber; barium sulfate, calcium sulfate , kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, nephelinsinite, merk, aklepulgite, wollastonite, PMF.

Examples include titanium, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass balloons, quartz powder, etc., and are generally used alone as a fibrous reinforcing agent or in combination with one or more fibrous reinforcing agents. It is used in combination with other inorganic fillers.

In the present invention, 1. The inorganic filler is used in an amount of 0 to 250 parts by weight based on 100 parts by weight of the block copolymer.

In particular, the range of 10 to 230 parts by weight is preferable for compositions to be subjected to injection molding. In this case, if the amount used is too small, the reinforcing effect will not be sufficient, whereas if it is too large, the melt viscosity will increase, significantly impairing the moldability.

In addition, the composition of the present invention may contain a small amount of a mold release agent, a coloring agent, a heat stabilizer, and
It can contain ultraviolet stabilizers, foaming agents, rust preventives, and flame retardants. Furthermore, the composition of the present invention can be used in combination with the following resins. These resins include ethylene, propylene, butylene, pentene, phthalene,
Homopolymers or copolymers of monomers such as isoprene, chloroprene, styrene, a-methylstyrene, vinyl acetate, acrylic esters, methacrylic esters, (meth)acrylonitrile, polyurethanes, polyamides,
Polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyacecool, polysulfone, polyaryl sulfone, polyether sulfone, polyarylate, polyphenylene oxide, polyphenylene sulfide, polyphenylene ether, polyether ether ketone, polyimide, polyamideimide Examples include homopolymers, copolymers, block and graft copolymers of silicone resins, phenoxy resins, fluororesins, polyaryl ethers and the like.

The composition of the invention can be prepared in various known ways.

For example, the raw materials are uniformly mixed in advance using a mixer such as a tamp 2- or Henschel mixer, then fed to a single-screw or twin-screw extruder, melt-kneaded at 230 to 400°C, and then pelletized. be able to.

<Effects of the Invention> The resin composition of the present invention can provide molded products with excellent dimensional accuracy while maintaining high levels of heat resistance and strength, and is suitable for precision machinery, electronics, electrical parts, etc.

Kumi Example Hereinafter, the present invention will be specifically explained using examples.

Examples 1 to 7, Comparative Examples 1 to 4 N-methylpyrrolidone 1980 in 107 autoclave
g, hydrogen sulfide) IJum t2hydrate 38815.0
mol), 200 g of sodium hydroxide, and bis(P-
1436 g (5.0 mol) of chlorphenyl sulfone was charged and reacted at 200° C. for 6 hours. Furthermore, 72 g (0.25 mol) of bis(P-chlorophenyl)sulfone and N-
200 g of methylpyrrolidone was added and reacted at 200° C. for 1 hour to obtain a sulfide sulfone polymer.

Next 10! N-methylpyrrolidone 31 in the autoclave
00g, sodium hydrosulfide superdihydrate 597.5g (
7.7 mol) and 308 g of sodium hydroxide were charged, the temperature was raised while water was distilled off, and at 220°C P-dichlorobenzene 1029# (7.0 mol) and N-)lfk pyrrolidone 700II were added to 260 g. The mixture was reacted at ℃ for 2 hours to obtain polyphenylene sulfide.

The above-mentioned sulfide sulfone polymer polymerization reaction mixture,
The polyphenylene sulfide polymerization reaction mixture was charged into an autoclave and reacted at 220°C for 6 hours, and purified by a known method to obtain a block copolymer (a) containing about 50% by weight (feed ratio) of polyphenylene sulfide sulfone moieties. . The viscosity of the polymer in a dissolved acid measured by a Koka type flow tester was 600 voids at 600°C.

Next, the A8
170 (g/10
A block copolymer (b) was obtained.

Using the above polymers, mix them uniformly in the proportions shown in Table 1, and
Using a 0m extruder, the mixture was melt-kneaded at 310° to form pellets. Using the pellet, a test piece was prepared using an injection molding machine at a cylinder temperature of 610°C. Appearance and A of the molded product
Table 1 shows the bending strength results using 8TMD-790.

As shown in Table 1, it can be seen that the composition of the present invention gives molded products with good appearance and excellent strength.

Claims (1)

[Claims] (a) Block copolymer 10 consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety
(b) 0.1 to 20 parts by weight of an epoxy resin, and (c) 0 to 250 parts by weight of an inorganic filler.