JPH0525244A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic polyarylene sulfide resin composition of improved impact strength by mixing a specified polyarylene sulfide resin with a specified polyisocyanate compound. CONSTITUTION:A resin composition comprising a polyarylene sulfide resin (A) and at least one polyisocyanate compound (B) of the formula (wherein n>=1). As the polyisocyanate compound (B) to be used, polyphenylene polyisocyanate is particularly desirable. As the polyarylene sulfide resin (A) to be used, a polyarylene sulfide comprising at least 50mol% repeating units of formula II, more particularly, polyphenylene sulfide is desirable. The resin composition can be improved in impact strength without detriment to heat resistance and rigidity inherent in the polyarylene sulfide resin, and can be molded by extrusion molding, injection molding, blow molding, etc., by virtue of its excellent mechanical properties.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition, and more particularly to a thermoplastic polyarylene sulfide resin composition having improved impact properties.

[0002]

2. Description of the Related Art A polyarylene sulfide resin represented by polyphenylene sulfide is one of resins classified into heat resistant resins, and has high continuous use temperature and high rigidity, and also has high melt fluidity, It has features such as flame retardancy and excellent solvent resistance, and is widely used as various molded products and films.
However, this resin has the drawback of low mechanical strength, especially impact strength, which is a major obstacle to the further widespread application of polyarylene sulfide resins.

As a composition aiming at improving the drawbacks of the polyarylene sulfide resin, polyphenylene sulfide resin is graft-copolymerized with an unsaturated carboxylic acid or the like α
-A resin composition obtained by mixing an olefin copolymer elastomer and an epoxy resin (JP-A-59-2079).
21), a resin composition containing a polyphenylene sulfide resin and polyisobutylene (JP-A-63-952).
65), a resin composition (JP-A-3-54256) in which an ionomer is contained in a polyphenylene sulfide resin obtained by melt-kneading a polyphenylene sulfide resin and a non-block type polyfunctional isocyanate compound has been proposed. There is.

[0004]

However, although these compositions proposed hitherto have improved impact strength, they have sacrificed heat resistance and rigidity, or have not been sufficiently improved in impact strength. , Not industrially satisfactory.

An object of the present invention is to provide a thermoplastic resin composition having an improved impact strength without sacrificing the excellent heat resistance and rigidity inherent in the polyarylene sulfide resin.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that heat resistance when a polyarylene sulfide resin contains a specific polyisocyanate compound which has not been proposed so far. It was found that a resin composition excellent in impact strength was obtained and the present invention was completed.

That is, the present invention is a resin composition containing (A) a polyarylene sulfide resin and (B) at least one polyisocyanate compound represented by the general formula (1).

Specific examples of the polyisocyanate compound represented by the general formula 1 in the present invention include bis (4-isocyanatephenylmethyl) benzene isocyanate, bis (4-isocyanatephenylmethyl) diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate. Can be mentioned. Of these, the preferred polyisocyanate compound is polymethylene polyphenylene polyisocyanate. In addition,
The polymethylene polyphenylene polyisocyanate referred to herein is a mixture of a plurality of polyisocyanates represented by formulas having different values of n in the general formula 1 and diphenylmethane diisocyanate, and various mixed compositions are commercially available. A particularly preferred polyisocyanate compound is polymethylene polyphenylene polyisocyanate having a number average molecular weight of 260 to about 800.

The polyarylene sulfide resin (A) in the present invention is a polymer having a repeating unit represented by the general formula 2.

[0010]

[Chemical 2]

(Ar in the formula represents a divalent aromatic residue.) Examples of Ar include divalent aromatic residues represented by Chemical formulas 3 to 12 and their nuclear substitution products. To be

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical 12]

The polyarylene sulfide resin of the present invention also includes a polymer containing a small amount of the trifunctional group represented by Chemical formula 13 in addition to these divalent aromatic residues.

[0023]

[Chemical 13]

Specific examples of the polyarylene sulfide resin represented by the general formula 2 are polyphenylene sulfide, poly (1,4-phenylenecarbonyl-1,4-phenylene sulfide) and poly (1,4-phenylenesulfonyl-1,1,2). 4-phenylene sulfide), poly (biphenylene sulfide) and the like. Among these, preferred polyarylene sulfide is polyarylene sulfide containing 50 mol% or more of the repeating unit represented by Chemical formula 14, and more preferred polyarylene sulfide resin is polyphenylene sulfide.

[0025]

[Chemical 14]

Generally, there are two types of the above-mentioned polyarylene sulfide resin, a cross-linking type and a non-cross-linking type, but both can be used in the present invention, and the non-cross-linking type is more preferably used.

The molecular weight of the polyarylene sulfide resin is not particularly limited, but a polyarylene sulfide resin having a melt viscosity at 300 ° C. of 100 to 50,000 poises, preferably 200 to 10,000 poises is generally used.

A method for producing such a polyarylene sulfide resin is known, and for example, (i) a method of reacting a dihalogenated aromatic compound with an alkali sulfide in an organic polar solvent (US Pat. No. 2,513,188, US Pat. Four
No. 038261, Japanese Patent Publication No. 44-27671,
Japanese Patent Publication No. 45-3368, Japanese Patent Publication No. 52-12240
(See Japanese Patent Laid-Open No. 55-43139), (i
i) a condensation reaction of thiophenols in the presence of an alkali catalyst or a copper salt (see US Pat. No. 3,274,165), and (iii) a method of reacting an aromatic hydrocarbon with sulfur chlorides in the presence of a Lewis acid ( Japanese Patent Publication No. 46-2725
For example, refer to Japanese Patent Laid-Open No. 5).

The compounding ratio of the above polyarylene sulfide resin (A) and the above polyisocyanate compound (B) in the resin composition of the present invention cannot be unconditionally determined because the degree of the effect varies depending on the respective types selected. Is generally a polyarylene sulfide resin (A) 10
The polyisocyanate compound (B) is used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 0 parts by weight.

The resin composition of the present invention can be produced by a general method used for blending thermoplastic resins such as solution blending and melt kneading. Among these, melt-kneading is preferable, and various conventionally known methods can be adopted as the method. That is, each of the above ingredients was added to a Henschel mixer, super mixer, ribbon blender, V
Mixing by a known mixing means used for mixing the resins such as blender or the resin and the liquid or solid additive to form a uniform mixture, the mixture is Banbury mixer, plastomill, Brabender plastograph, A method of kneading using a kneading means such as a uniaxial or biaxial extruder can be mentioned as an example.

When kneading, the temperature is 150 to 400 ° C.,
It is preferably selected in the range of 200 to 350 ° C.

If desired, the resin composition of the present invention may include a wide variety of substances other than those mentioned above. Examples of such other substances include elastomers, flame retardants, stabilizers,
Examples include plasticizers, lubricants, pigments, reinforcing fibers and fillers.

Examples of elastomers include natural rubber, polybutadiene rubber, polyisoprene rubber, butyl rubber,
Ethylene-propylene copolymer rubber, butadiene-styrene copolymer rubber, butadiene-acrylonitrile copolymer rubber, hydrogenated and non-hydrogenated styrene-conjugated diene block copolymer rubber, polyester rubber, acrylic rubber, silicone rubber, etc. And modified products thereof.

Among these, preferred elastomers are
Ethylene-propylene copolymer rubber containing a terpolymer copolymerized with a diene compound and a modified product such as a graft copolymer obtained by graft copolymerizing an unsaturated monomer such as styrene, and a partially hydrogenated product Styrene-conjugated diene-based block copolymer rubbers such as styrene-isoprene diblock copolymers and styrene-butadiene triblock copolymers containing hydrogenated substances such as

Examples of flame retardants are triphenyl phosphate, tricresyl phosphate, phosphates obtained from a mixture of isopropylphenol and phenol,
Phosphate esters exemplified by phosphates obtained from a mixture of a bifunctional phenol such as benzohydroquinone or bisphenol A and other alcohols or phenols; decabromobiphenyl, pentabromotoluene, decabromodiphenyl ether, hexa Brominated compounds exemplified by bromobenzene, brominated polystyrene, brominated epoxy resin and the like; nitrogen-containing compounds such as melamine and melamine triisosinurate; red phosphorus,
Examples thereof include inorganic substances such as antimony trioxide and boron oxide.

Specific examples of the reinforcing fibers include inorganic fibers such as glass fibers, potassium titanate fibers, rock wool and carbon fibers; organic fibers such as aromatic polyamide fibers and polybenzimidazole fibers; brass fibers, aluminum zinc fibers and the like. Metal fibers and the like are listed.

Specific examples of the filler include glass beads, milled glass fiber, asbestos, wollastonite,
Examples thereof include inorganic fillers such as mica, talc, clay, calcium carbonate, magnesium hydroxide, silica, and diatomaceous earth; metal fillers such as aluminum flakes and zinc flakes; organic fillers such as polyimide powder.

Other examples of stabilizers include sterically hindered phenols, organic phosphites, oxalic acid diazides, and sterically hindered amines, and specific examples of pigments include titanium oxide and zinc sulfide. Specific examples of the lubricant include polyethylene wax and paraffin.

The mixing ratio of the other substances can be arbitrarily selected according to the purpose, but if the general guideline for using them is as follows, 100 parts by weight of the polyarylene sulfide resin (A) is used. On the other hand, each of the above elastomers is 100 parts by weight or less; the above flame retardant is 30 parts by weight.
Parts by weight or less, preferably 1 to 20 parts by weight; the stabilizer is 20 parts by weight or less, preferably 0.001 to 10 parts by weight; the reinforcing fiber and the filler are each 150 parts by weight or less, preferably 0.1 to 10 parts by weight. 100 parts by weight; lubricant is 2 parts by weight or less.

[0040]

The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited by the examples. The Izod impact strength (3.2 mm thickness, no notch), the tensile property and the bending property in the examples are respectively ASTM D638, ASTM D790 and AST for the test pieces prepared by injection molding.
It is a value measured at 23 ° C. according to MD648.

Example 1 100 parts by weight of non-crosslinked polyphenylene sulfide having a melt flow rate of 21 dg / min under a load of 2.16 kg / cm ^{2 at} 300 ° C. and 2,4-bis (4-isocyanatephenylmethyl) benzeneisocyanate 3 parts by weight were blended using a super mixer. The obtained compound was heated to a cylinder temperature of 300 using a 40 mm diameter uniaxial extruder.
The resin composition of the present invention was pelletized by extruding at a temperature of 90 ° C and a screw rotation speed of 90 rpm. The unnotched Izod impact strength of the resin composition, the tensile elongation and flexural modulus respectively 132kg · cm / cm ^2, was 7.0% and 28400kg / cm ^2.

Comparative Example 1 A resin composition pellet was obtained in the same manner as in Example 1 except that diphenylmethane diisocyanate was used instead of 2,4-bis (4-isocyanatephenylmethyl) benzene isocyanate. The notched Izod impact strength, tensile elongation and flexural modulus of the resin composition were 95 kg · cm / cm ² , 5.2% and 28300 k, respectively.
It was g / cm ² .

Comparative Example 2 A resin composition pellet was obtained in the same manner as in Example 1 except that 2,4-bis (4-isocyanatophenylmethyl) benzene isocyanate was not used. The notched Izod impact strength, tensile elongation and flexural modulus of the resin composition were 83 kg · cm / cm ² and 4.6%, respectively.
And 28600 kg / cm ² .

Example 2 2,4-bis (4-isocyanate phenylmethyl) benzene isocyanate was replaced with polymethylene polyphenylene polyisocyanate [Sumitou 4 manufactured by Sumitomo Chemical Co., Ltd.].
4V20], but the same operation as in Example 1 was carried out to obtain pellets of the resin composition. The notched Izod impact strength, tensile elongation and flexural modulus of the resin composition were 153 kg · cm / cm ² , 8.3% and 28, respectively.
It was 400 kg / cm ² .

[0045]

The resin composition of the present invention thus obtained is molded by various molding methods such as extrusion molding, injection molding and blow molding, taking advantage of excellent mechanical properties such as impact strength, and various useful values are obtained. It is supplied to the world as a resin product, and its industrial value is enormous.

Claims (5)

[Claims] 1. A polyarylene sulfide resin (A) and a general formula (B): ## STR1 ## (In the formula, n represents an integer of 1 or more.) A resin composition containing at least one polyisocyanate compound represented by the formula. 2. The resin composition according to claim 1, wherein the polyisocyanate compound is polymethylene polyphenylene polyisocyanate. 3. The resin composition according to claim 1, wherein the polyisocyanate compound is a polymethylene polyphenylene polyisocyanate having a number average molecular weight of 260 or more and about 800 or less. 4. The resin composition according to claim 1, wherein the polyarylene sulfide resin is polyphenylene sulfide. 5. The resin composition according to claim 1, wherein the polyarylene sulfide resin is a non-crosslinked polyphenylene sulfide.