JPH03122160A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide a polyphenylene sulfide resin composition having good compatibility and excellent mechanical strength by compounding a copolymer comprising a rubbery polymer, an aromatic vinyl monomer and vinyl cyanide and a specific copolymer with a polyphenylene sulfide resin. CONSTITUTION:A polyphenylene sulfide resin composition comprises (A) 10-97 pts. wt. of a polyphenylene sulfide resin, (B) 90-3 pts. wt. of a copolymer comprising B1: a rubbery polymer (e.g. vinyl cyanide monomer component (e.g. polybutadiene), B2: an aromatic vinyl monomer component (e.g. styrene) and B3: vinyl cyanide monomer component (e.g. acrylonitrile) and (C) a copolymer comprising an unsaturated monomer component having an epoxy or oxazolinyl group, C2: an aromatic vinyl monomer component and C3: vinyl cyanide monomer component in an amount of 0.1-40 pts. wt., preferably 0.5-30 pts. wt. based on the sum of the components A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polyphenylene sulfide (hereinafter referred to as PPS) based resin composition, and more specifically, the present invention relates to a polyphenylene sulfide (hereinafter referred to as PPS) based resin composition, and more specifically, a polyphenylene sulfide (hereinafter referred to as PPS) resin composition having a rubbery polymer, vinyl cyanide, and an aromatic vinyl component. The present invention relates to a PPS resin composition with improved compatibility with resin.

(Prior art and problems to be solved by the invention) PP
S resin has excellent heat resistance, flame retardance, chemical resistance, and high rigidity, and is an extremely useful resin as an engineering plastic, but it has the drawback of being brittle against impact. Therefore, resin compositions have been proposed that utilize the excellent properties of PPS while improving its drawbacks.

Conventionally, many attempts have been made to solve the drawbacks of each resin by blending resins with different properties. Among them, by blending PPS with a resin having a rubbery polymer, vinyl cyanide, and an aromatic vinyl component, such as ABS resin, AES (acrylonitrile-ethylenepropylene-styrene) resin, etc. (1), Attempts have been made to improve the impact strength of PPS.

For example, JP-A-63-304046 discloses a resin composition consisting of ABS and PPS to which PPS is added in order to improve the heat resistance of the ABS resin.

However, different types of polymers usually have poor compatibility, and as shown in JP-A-63-3o4o4s@publication, ABS
If PPS is simply mixed with PPS, the resulting resin composition will be brittle and will not have sufficient mechanical strength.

The present invention aims to improve the compatibility between a PPS resin and a resin containing a rubbery polymer, vinyl cyanide, and an aromatic vinyl component, and to provide a PPS resin composition that has excellent mechanical strength. purpose.

(Means for Solving the Problems) Therefore, as a result of extensive studies, the present inventors have determined that epoxy groups or The inventors have discovered that the compatibility of these resins can be improved by adding a vinyl cyanide-aromatic vinyl copolymer having an oxazolinyl group, and have arrived at the present invention.

That is, the present invention includes (A) 10 to 97 parts by weight of PPS resin, (
B) 90 to 3 parts by weight of a copolymer containing (a) a rubbery polymer, (b) an aromatic vinyl monomer component and (C) a vinyl cyanide monomer component, and (C) (a) an epoxy group Or, a copolymer containing an unsaturated monomer component having an oxazolinyl group, (a) an aromatic vinyl monomer component, and (a) a vinyl cyanide monomer component, a total of 100% of (A) and (B) 0.0% by weight.
1 to 40 parts by weight of a polyphenylene sulfide resin composition.

Next, each component will be explained in turn.

It is preferable because PPS polymerization methods include polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or polymerizing p-dichlorobenzene in the presence of sodium sulfide, sodium hydrosulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide in a polar solvent. Polymerization methods include self-condensation of p-chlorothiophenol, but sodium sulfide and p
- A method in which dichlorobenzene is reacted is suitable. At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide. 30 as a copolymer component
If it is less than mol %, it may contain alkyl, nitro, phenyl, alkoxy, carboxylic acid or a metal base of carboxylic acid), etc., as long as it does not significantly affect the crystallinity of the polymer. Preferably, the copolymerization component is 10 mol% or less. In particular, when trifunctional or higher functional phenyl, biphenyl, naphthyl sulfide bonds, etc. are selected for copolymerization, the amount is preferably 3 mol % or less, more preferably 1 mol % or less.

Such PPS can be produced by common manufacturing methods, such as (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (see U.S. Pat. No. 2,513,188, Japanese Patent Publication No. 4427671 and Japanese Patent Publication No. 45-3368); (2) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt (US Patent No. 3,274,165, British Patent No. 116)
0660), (3) Condensation reaction of aromatic compounds with sulfur chloride in the presence of a Lewis acid catalyst (Japanese Patent Publication No. 40-2
No. 7255, Belgian Patent No. 29437), and can be arbitrarily selected depending on the purpose.

PPS is currently available on the market from Philips Petroleum ■, Tosoh Sasteel ■, Toprene and Kenbetsu Kagaku ■.

There are various grades depending on crosslinking density and viscosity, and PPS with less crosslinking structure is preferred for the present invention.

Next, component (B) is a copolymer containing (a) a rubbery polymer, (b) an aromatic vinyl monofilament component, and (C) a vinyl cyanide monofilament component.

(a) Rubbery polymers used in the present invention include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, and acrylonitrile-butadiene copolymers. diene rubbers such as butadiene-isoprene copolymers, ethylene-propylene random copolymers and block copolymers, ethylene-nibutene random copolymers and block copolymers, and copolymers of ethylene and α-olefins. Copolymers of ethylene-methacrylate, ethylene-butyl acrylate, etc. and ethylenically unsaturated carboxylic acid esters, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene-ethylidenenorbornene copolymers , ethylene-propylene-hexadiene copolymer, etc.
Examples include propylene non-conjugated terpolymer, butylene-isoprene copolymer, etc., and these can be used singly or in combination.
Use on more than one species. Preferred rubbery polymers are ethylene-propylene rubber, ethylene-propylene non-conjugated terpolymers, and diene rubbers, and particularly preferred are polybutadiene and styrene-butadiene copolymers. The content is preferably 50% by weight or less.

Examples of the (b) vinyl cyanide monomer component used in component (B) in the present invention include acrylonitrile,
Methacrylate trile, etc. can be mentioned, and these 1
Use a species or two or more species.

Examples of the aromatic vinyl monomer component (C) used in component (B) in the present invention include styrene, α-methylstyrene, o-, m-, or methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene. ,
Examples include monobromostyrene, dipromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, etc.
Use a species or two or more species. Preferably styrene, α-
It is methylstyrene.

Component (B) in the present invention includes the above component (a).

In addition to (b) and (C), (d) monomers copolymerizable with these components can be used within a range that does not impair the object of the present invention. Such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. ) acrylate, 2-ethyl (meth)acrylate, 2-ethylhexyl methacrylate, etc. α, β-
Unsaturated carboxylic acid esters; α,β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride: maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenyl Examples include imide compounds of α,β-unsaturated dicarboxylic acids such as maleimide; these monomers may be used alone or in combination of two or more.

In component (B), each component (a), (b) and (
The composition ratio of C) is not particularly limited, and each component is blended according to the purpose.

The copolymer of component (B) is a graft copolymer obtained by graft copolymerizing other components in the presence of (a) a rubbery polymer, or this graft copolymer and (b) vinyl cyanide monomer. Blends with copolymerization products of aromatic vinyl monomers and (C) aromatic vinyl monomers are preferred, and more preferably A
They are BS resin and AES resin.

There are no particular limitations on the method for producing the copolymer of component (B), and commonly known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used. In addition, by blending separately copolymerized resins, component (B)
It is also possible to obtain

The blending ratio of the above components (A) and (B) is (A)
It is 90 to 3 parts by weight of (B) based on 10 to 97 parts by weight.

When (A) exceeds 91 parts by weight, impact resistance becomes poor, and when (B) exceeds 90 parts by weight, heat resistance decreases.

Next, component (C), which is a feature of the present invention, will be described. Component (C) is a copolymer containing (a) an unsaturated monomer component having an epoxy group or an oxazolinyl group, (a) an aromatic vinyl monomer component, and (a) a vinyl cyanide monomer component. be.

Examples of the unsaturated monomer component (a) having an epoxy group or oxazolinyl group used in the present invention include the following.

First, preferred epoxy group-containing unsaturated monomers include:
glycidyl methacrylate, glycidyl acrylate,
Examples include vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate, and glycidyl itaconate.

Next, preferred oxazolinyl group-containing unsaturated monomers include those represented by the general formula: where Z contains a polymerizable double bond. Preferred substituents Z are as follows.

1 CH2-CR-CH2=CR-C- In these formulas, R is a hydrogen atom or an alkyl or alkoxy group having 1 to 6 carbon atoms, such as a methyl group, a 1- and n-propyl group or a butyl group. be.

A particularly preferred compound is vinyloxazoline represented by the general formula, where R has the above meaning and is preferably a hydrogen atom or a methyl group.

In addition, (a) aromatic vinyl compounds include styrene,
Examples include α-methylstyrene, p-methylstyrene, and pt-butylstyrene, with styrene being preferred.

(1) Examples of the vinyl cyanide monomer include acrylonitrile, methacrylaterile, and the like, with acrylonitrile being preferred.

Examples of copolymers preferred as component (C) include glycidyl methacrylate/styrene/acrylonitrile, vinyloxazoline/styrene/acrylonitrile, and the like.

In the copolymer of component (C), if the proportion of the unsaturated monomer (A) having an epoxy group or oxazolinyl group is too small, the impact strength of the resin composition will decrease, and if it is too large, the viscosity will increase. Considering the decrease in fluidity caused by the above, the content is preferably 0.001 to 30% by weight.

In addition, in component (C), in addition to the above components (a), (b), and (t), (a), (b), and (t)
Other copolymerizable monomer components can be included in an amount of 0 to 70% by weight based on the total of 10 parts by weight. Such other monomers include vinyl acetate, acrylic acid (salt), methacrylic acid (salt), acrylic ester, methacrylic ester, maleic acid (anhydride), maleic ester,
Unsaturated carboxylic acid such as 2-norbornene-5,6-dicarboxylic acid (anhydride) or its derivative component; ethylene,
Propylene, 1-butene, 1-pentene, 4-methyl-
α-olefin components such as 1-pentene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene: butadiene, isoprene, 1,4-hexadiene, Examples include diene components such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.

There are no particular restrictions on the method for producing the copolymer of component (C), and commonly known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used.

The above component (C) is contained in an amount of 0.1 to 40 parts by weight, preferably 0.5 to 30 parts by weight, based on a total of 100 parts by weight of the components (A) and (B). If component (C) is too small, the compatibility of (A) and (B) will not improve, resulting in poor product appearance, while if it is too large, moldability will be reduced.

In addition, the resin composition of the present invention may contain other commonly used additives, such as pigments, dyes, reinforcing agents, fillers, heat resistant agent, oxidative deterioration inhibitor, weathering agent, lubricant, mold release agent,
A crystal nucleating agent, a plasticizer, a flame retardant, a fluidity improver, an antistatic agent, an impact resistance improver, etc. can be added.

There are no particular limitations on the method for producing the resin composition of the present invention, and conventional methods can be used satisfactorily.

However, melt mixing methods are generally preferred. Any melt mixing method can be used provided it can handle the molten viscous bowl. The method may be used batchwise or continuously.

Extruder, Banbury mixer, roller, kneader
For example,

(Example) EXAMPLES The present invention will be explained in more detail with reference to Examples below.

In addition, the following were used as each component.

Component (A): P P S ・300' C1 shear rate 200 sec-
1 (7) PPS with a melt viscosity of 3900 poise under conditions
T-4 (trademark, made by Toprene), Component (B): ABS resin...Trademark: BLENDEX 338,
Manufactured by General Electric Co., Ltd. Component (C): RAS-1005...trademark, styrene-acrylonitrile co-containing oxazolinyl group with a number average molecular weight of 50,000, consisting of 5% by weight of vinyl oxazoline, 70% by weight of styrene and 25% by weight of acrylonitrile. Polymer, Bremmer CP510SA manufactured by Nippon Shokubai Chemical ■: Trademark, styrene-acrylonitrile copolymer containing 10% by weight of glycidyl acrylate, number average molecular weight approximately 19,000, manufactured by NOF ■ Examples 1 and 2 and comparative examples 1 Mix each component in the proportions (weight ratio) shown in the table, and heat at 300°C.
Pellets were produced by extrusion using a twin-screw extruder set at 29 rpm.

After drying this pellet, it was injection molded to form a test piece for Izot impact test, and the Izot impact strength was measured. The results are shown in the table.

Note that the 178-inch isot impact strength (with and without notches) was measured in accordance with ASTH0256.

1 Examples and Comparative Examples Components (parts by weight) Component (^): PS Component (B): 8BS Component (C): RAS-1005 Bremmer CP510SA 5 5 5 5 5 5 Izot impact strength* No notch (Kc+-cm/ cm) NB NB
2B/Tutsi (NiG-Cm/Cm) 5.6
5.0 1.2NB'' indicates that it was not destroyed (effect of the invention) It has good mechanical strength.Therefore, it can be said to be a useful resin composition with a wide range of uses.

Claims (1)

[Scope of Claims] (A) 10 to 97 parts by weight of polyphenylene sulfide resin, (B) (a) rubbery polymer, (b) aromatic vinyl monomer component, and (c) vinyl cyanide monomer 90 to 3 parts by weight of a copolymer containing the components, and (C) (a) an unsaturated monomer component having an epoxy group or oxazolinyl group, (a) an aromatic vinyl monomer component, and (c) vinyl cyanide. The copolymer containing the monomer component was added in an amount of 0.0% to 100 parts by weight in total of (A) and (B).
1 to 40 parts by weight of a polyphenylene sulfide resin composition.