JPH0493356A - High-impact polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To improve impact resistance without adversely affecting moldability by compounding a polyphenylene sulfide resin with specified amts. of a specific alpha-olefin copolymer and a specific alkyl carboxylate copolymer. CONSTITUTION:70-98wt.% polyphenylene sulfide resin, 1-29wt.% alpha-olefin copolymer obtd. by graft copolymerizing 10wt.% or lower unsatd. carboxylic acid (anhydride) (e.g. a maleic anhydride-grafted polyethylene), and 1-29wt.% alkyl carboxylate copolymer comprising 2-40mol% glycidyl alpha,beta-unsatd. carboxylate (e. g. glycidyl methacrylate) and 98-60mol% alkyl alpha,beta-unsatd. carboxylate (e. g. methyl acrylate) are compounded to give a high-impact polyphenylene sulfide resin compsn.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polyphenylene sulfide resin composition with improved impact resistance, and more specifically,
- It relates to a polyphenylene sulfide resin composition made of a polyphenylene sulfide resin containing a specific copolymer elastomer.

[Prior Art] Conventionally, as a polyphenylene sulfide resin composition with improved impact resistance, Japanese Patent Application Laid-Open No. 59-207921 discloses a polyphenylene sulfide resin containing an unsaturated carboxylic acid, its anhydride, or a derivative thereof. A composition comprising a graft copolymerized α-olefin copolymer elastomer and an epoxy resin has been disclosed in JP-A-58-
No. 1547 and Japanese Unexamined Patent Publication No. 59-152953 disclose compositions in which a polyphenylene sulfide resin contains an ethylene-glycidyl methacrylate copolymer.

Furthermore, JP-A-61-207462 discloses a polyarylene sulfide resin composition obtained by mixing polyarylene sulfide containing an amino group and/or amide group with a thermoplastic elastomer. .

Further, JP-A-62-15460 discloses a polyphenylene sulfide resin composition containing an ethylene-based copolymer of ethylene-a, β-unsaturated carboxylic acid alkyl ester-maleic anhydride.
No. 2-127471 discloses specially treated polyphenylene sulfide resin and ethylene-
A composition of an ethylene copolymer consisting of α,β unsaturated carboxylic acid alkyl ester-maleic anhydride is disclosed.

Further, JP-A-63-95265 discloses a composition in which polyphenylene sulfide resin contains polyisobutylene.

However, even with the compositions described in the above-mentioned publications, the effect of improving impact resistance is still insufficient.

More specifically, polyphenylene sulfide resin has poor reactivity, and the elastomer used above is not sufficiently effective as an elastic body, so at present, sufficient impact resistance has not been improved. It is.

In addition, even if a slight effect is observed, the elastomer component gels during melt mixing, and the melt viscosity of the composition increases significantly, resulting in a significant decrease in moldability.
Since polyphenylene sulfide resin that has been specially treated in advance must be used, productivity has been poor.

[Problems to be Solved by the Invention] The present inventor has developed a polyphenylene sulfide resin that improves adhesion at the interface between a polyphenylene sulfide resin and an elastomer, exhibits the effect of the elastomer component as an elastic body, and suppresses gelation during melt-kneading. As a result of extensive research in order to provide a resin composition that retains the original moldability of sulfide resin,
The inventors have discovered that these problems can be solved by blending polyphenylene sulfide resin with an elastomer having specific components, and have completed the present invention.

Means for Solving CaS] That is, the present invention comprises (A) polyphenylene sulfide resin 70 to 98% by weight
α-olefin copolymer 1 to 2 graft-copolymerized with (B) 10% by weight or less of an unsaturated carboxylic acid or its anhydride
9% by weight, and (C) α,β-unsaturated carboxylic acid glycidyl ester 2
The present invention relates to a polyphenylene sulfide resin composition containing 1 to 29% by weight of a carboxylic acid alkyl ester copolymer consisting of ~40 mol% and 98 to 60 mol% of an α,β-unsaturated carboxylic acid alkyl ester.

Any other copolymer components may be included as long as they contain 95 mol% or more of the polyphnynylene sulfide return unit used in the present invention.

The polyphenylene sulfide resin used in the present invention is
Special Publication No. 45-3368 and Special Publication No. 52-122
A manufacturing method such as that disclosed in Publication No. 40 can be used. According to these methods, a relatively low molecular weight polymer produced by the production method typified by Japanese Patent Publication No. 45-3368, and a polymer of Japanese Patent Publication No. 52-122
An essentially linear polymer having a relatively high molecular weight can be obtained by the production method typified by Publication No. 40;
The polymer obtained by the method described in Publication No. 368 can be used by increasing the degree of polymerization by heating in an air atmosphere after polymerization, or by adding a crosslinking agent such as a peroxide and heating. In the present invention, it is possible to use polyphenylene sulfide resin obtained by any method.

In particular, 3.5-
Diaminochlorobenzene, 3,5-dichloroaniline,
It is more preferable to use a polyphenylene sulfide resin containing an amino group synthesized by adding a halogenated aniline such as P-chloroaniline.

The melt viscosity of the polyphenylene sulfide resin used in the present invention is 100 to 50,000 poise, particularly preferably 1
000 to 10,000 poise.

In the present invention, when a chemically modified polyphenylene sulfide resin is used, in particular, modified with amino groups, the dispersibility and compatibility of the formulation are improved more than when an unmodified polyphenylene sulfide resin is used. A composition with excellent interfacial adhesion can be synthesized.

The elastomer used in the present invention is an α-olefin copolymer obtained by graft copolymerizing an unsaturated carboxylic acid or its anhydride, α1 β-unsaturated carboxylic acid glycidyl ester 2 to 40 mol%, α, It is a carboxylic acid alkyl ester copolymer consisting of 98 to 60 mol% of β-unsaturated carboxylic acid alkyl ester.

The monomer component of the α-olefin copolymer used in the present invention is an α-olefin, an unsaturated carboxylic acid, or an anhydride thereof, and 10% by weight or less of an unsaturated carboxylic acid or anhydride thereof is grafted. It is a copolymerized product.

Examples of the backbone polymer of the α-olefin copolymer include polymers such as ethylene, propylene, butene-1, isobutyne, pentene-1,4-methylpentene-1, and hexene-1, or copolymers thereof. .

Examples of unsaturated carboxylic acids or anhydrides thereof to be graft copolymerized with this α-olefin backbone polymer include maleic acid, fumaric acid, itaconic acid, methylmaleic acid, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride,
Examples include methylmaleic anhydride. The amount of such graft component is 10% by weight or less, but preferably 0.1% by weight or less.
~5% by weight.

The polymerization reaction for grafting an unsaturated carboxylic acid or its anhydride onto a polymer of α-olefin as a backbone can be carried out in a solution state, suspension state, slurry state, or melt state by a known method.

For example, an unsaturated carboxylic acid (anhydride) and an organic peroxide are added to a solution of an α-olefin polymer dissolved in a solvent such as toluene or hexane, and graft polymerization is performed under heating and stirring to obtain a graft copolymer. method or
α-olefin polymer, unsaturated carboxylic acid (anhydride)
Alternatively, a method for obtaining a copolymer by graft polymerizing a blend of organic peroxides under heating and melt mixing using an extruder, mixer, or the like can be mentioned.

The monomer components of the carboxylic acid alkyl ester copolymer used in the present invention are α, β-unsaturated carboxylic acid glycidyl ester, α, β-unsaturated carboxylic acid alkyl ester, and α, β-unsaturated carboxylic acid alkyl ester. 2 to 40 mol% of acid glycidyl ester, particularly preferably 6 to 35 mol%
, a, β-unsaturated carboxylic acid alkyl ester is 98-
It is 60 mol%, particularly preferably 94 to 60 mol%.

α,β-unsaturated carboxylic acid glycidyl esters include, for example, glycidyl acrylate, glycidyl methacrylate,
Examples include glycidyl ethacrylate, and glycidyl methacrylate is particularly preferred.

α,β-Unsaturated carboxylic acid alkyl ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, such as acrylic acid,
Alkyl esters such as methacrylic acid, specific examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, and methacrylate. Methyl acid, ethyl methacrylate,
n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate,
Examples include isobutyl methacrylate, and ethyl acrylate, n-butyl acrylate, and methyl methacrylate are particularly preferred.

α,β-unsaturated carboxylic acid glycidyl ester and α,β
- For the polymerization reaction of the unsaturated carboxylic acid alkyl ester, a known method can be used, such as adding a monomer and an organic peroxide to a solvent and heating and stirring the mixture.

In the present invention, the fibrous and granular reinforcing agents are added in an amount of 300 parts by weight based on a total of 100 parts by weight of the polyphenylene sulfide resin, α-olefin copolymer, and carboxylic acid alkyl ester copolymer, if necessary. It is possible to blend within the range not exceeding, usually 10 to 300
By blending within the range of parts by weight, it is possible to improve strength, rigidity, heat resistance, dimensional stability, etc.

Fibrous reinforcing agents that can be used include inorganic fibers and carbon fibers such as glass fibers, silicon glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, and metal fibers.

Also, as a granular reinforcing agent, wollastenite is used.

Silicates such as sericite, kaolin, mica, clay, bentonite, asbestos, talc di-alumina silicate, alumina, magnesium oxide, zirconium oxide,
Examples include metal oxides such as titanium oxide, carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and barium sulfate, glass peas, boron nitride, silicon carbide, silicon oxide, Saroyan, and silica. These may be porous. Further, two or more of these reinforcing agents can be used in combination, and if necessary, they can be used after being pretreated with a coupling agent such as a silane type or a titanium type.

Although there are no particular limitations on the method for preparing the composition of the present invention, the polyphenylene sulfide resin, the α-olefin copolymer, and the carboxylic acid alkyl ester copolymer are melt-kneaded, and a reinforcing agent is added at a temperature above the melting point. A typical method is to melt and knead in an extruder and then pelletize.

In addition, the melting crosstalk temperature is preferably 280°C to 340°C,
If it is less than 280°C, the polyphenylene sulfide resin will not be sufficiently melted, and if it exceeds 340°C, the α-olefin copolymer or the carboxylic acid alkyl ester copolymer will be susceptible to thermal deterioration, which is not preferable.

[Example] The present invention will be explained in more detail with reference to Examples below.
This does not limit the invention.

The melt viscosity shown here was measured using a Koka type flow tester using a die with a diameter of 0.5 mm and a length of 2 mm at 300°C.
, 200 (seconds) - measured on hair.

Reference Example 1 Into a 15g autoclave, 5g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) was charged, and after raising the temperature to 120°C, 1866g of sodium sulfide 2,8 hydrate was charged, and the mixture was heated for about 2 hours. The temperature was gradually raised to 205° C. while stirring, and 407 g of water was distilled out. After cooling this system to 140°C, 2080g of p-dichlorobenzene was added, the temperature was raised to 225°C, and after polymerization for 3 hours, the temperature was increased to 250°C.
When the temperature reaches 250°C, a solution of 20.2 g of 3.5-diaminochlorobenzene dissolved in NMP50mi) is injected into the system, and polymerization is further carried out at 250°C for 3 hours to form polyphenylene sulfide having amino groups. Resin was obtained.

The melt viscosity of this polymer was 540 poise. Further, this polymer was treated at 250° C. for 5 hours in an air atmosphere to have a melt viscosity of 3200 poise.

Introduction of amino groups into the polymer is carried out using FT-IR (NIC
This was confirmed by the observation of absorption at 3387σ-1 using OLET (manufactured by OLET).

Reference example 2 Pour 5.0 of NMP into a 1'l autoclave, 12
After raising the temperature to 0℃, sodium sulfide 2,8 hydrate 1866
g and 330 g of lithium acetate were charged, and the temperature was gradually raised to 205° C. while stirring over about 2 hours to distill out 410 g of water. After cooling this system to 140°C, 2080g of p-dichlorobenzene was added and the temperature was raised to 225°C.
After polymerization for an hour, the temperature was raised to 250°C, and when it reached 250°C, 20.2 g of 3,5-diaminochlorobenzene was added to N
A solution dissolved in 50 mL of M P was poured into the system and further polymerized at 250° C. for 3 hours to obtain a polyphenylene sulfide resin having an amino group.

The melt viscosity of this polymer was 2950 poise.

Regarding the introduction of amino groups into this polymer, FT-I
Confirmed by R.

Reference example 3 5g of NMP was placed in a 1'l autoclave, and 120
After raising the temperature to ℃, 1866 g of sodium 2.8 hydrate sulfide
, 330 g of lithium acetate was charged, and the temperature was gradually raised to 205° C. while stirring for about 2 hours, and 403 g of water was distilled out. After cooling this system to 140°C, 2090g of p-dichlorobenzene was added and the temperature was raised to 225°C and polymerized for 3 hours, then the temperature was raised to 250°C and polymerized for another 3 hours to obtain a polyphenylene sulfide resin.

The melt viscosity of this polymer was 3100 poise.

Example 1.2 Polyphenylene sulfide resin obtained in Reference Example 1, 98% by weight of high-density polyethylene, 2% by weight of maleic anhydride
A weight ratio of 80:15:5.810:10 between an α-olefin copolymer pellet consisting of 10 mol% of glycidyl methacrylate and a carboxylic acid alkyl ester copolymer consisting of 90 mol% of ethyl acrylate. The mixture was tri-blended, supplied to a twin-screw kneading extruder (manufactured by Nippon Steel Corporation), melt-kneaded at 320°C, extruded and cut into strands, and pellets of the composition were obtained.

The pellet was injection molded using an injection molding machine (manufactured by Toshiba) at a cylinder temperature of 300°C, an injection pressure of 800 kg/cm2, and a mold temperature of 135°C to obtain a test piece for measuring physical properties.

Using the obtained test piece, the notched Izot impact strength was measured according to the ASTM D256 method in order to evaluate the impact resistance.

The results are shown in Table 1.

Example 3.4 Polyphenylene sulfide resin obtained in Reference Example 2, high density polyethylene 98% by weight, maleic anhydride 2% by weight
and a carboxylic acid alkyl ester copolymer consisting of 10 mol% of glycidyl methacrylate and 90 mol% of ethyl acrylate in a ratio of 80:15:5.80:10.10. The weight ratio was prepared in the same manner as in Example 1, and the physical properties were measured. The mold temperature during injection molding was set at 145°C.

The results are shown in Table 1.

Example 5.6 Polyphenylene sulfide resin obtained in Reference Example 3, 98% by weight of high-density polyethylene, 2% by weight of maleic anhydride
and a carboxylic acid alkyl ester copolymer consisting of 10 mol% of glycidyl methacrylate and 90 mol% of ethyl acrylate in a ratio of 80:15:5.80:10:10. The weight ratio was adjusted in the same manner as in Example 1, and the physical properties were measured. However, the mold temperature during injection molding was 145°C.

The results are shown in Table 1.

Comparative Example 1 A test piece of the polyphenylene sulfide resin obtained in Reference Example 1 was prepared in the same manner as in Example 1, and its physical properties were measured.

The results are shown in Table 1.

Comparative Example 2 An α-olefin copolymer consisting of the polyphenylene sulfide resin obtained in Reference Example 1, 98% by weight of high-density polyethylene, and 2% by weight of maleic anhydride was mixed in a ratio of 80:2.
It was prepared in the same manner as in Example 1 using a weight ratio of 0, and its physical properties were measured.

The results are shown in Table 1.

The impact strength of the resulting composition was low.

Comparative Example 3 A test piece of the polyphenylene sulfide resin obtained in Reference Example 2 was prepared in the same manner as in Example 3, and its physical properties were measured.

The results are shown in Table 1.

Comparative Example 4 An α-olefin copolymer consisting of the polyphenylene sulfide resin obtained in Reference Example 2, 98% by weight of high-density polyethylene, and 2% by weight of maleic anhydride was mixed in a ratio of 80:2.
It was prepared in the same manner as in Example 3 using a weight ratio of 0, and its physical properties were measured.

The results are shown in Table 1.

The impact strength of the resulting composition was low.

Comparative Example 5 The polyphenylene sulfide resin obtained in Reference Example 2 and a carboxylic acid alkyl ester copolymer consisting of 10 mol% glycidyl methacrylate and 90 mol% ethyl acrylate were mixed with Example 3 in a weight ratio of 90:10. It was prepared in a similar manner and its physical properties were measured.

The results are shown in Table 1.

The impact strength of the resulting composition was low.

[Effect of the invention] According to the present invention, polyphenylene sulfide resin and α-
By combining an olefin copolymer and a carboxylic acid alkyl ester copolymer, the original moldability of polyphenylene sulfide resin is maintained, and the polyphenylene sulfide resin does not require any specific treatment.
A polyphenylene sulfide resin composition with improved impact resistance can be obtained.

Claims (1)

[Claims] (A) Polyphenylene sulfide resin 70 to 98% by weight
, (B) α-olefin copolymers 1 to 2 graft-copolymerized with 10% by weight or less of unsaturated carboxylic acid or its anhydride
9% by weight, and (C) α,β-unsaturated carboxylic acid glycidyl ester 2
1. A polyphenylene sulfide resin composition comprising 1 to 29% by weight of a carboxylic acid alkyl ester copolymer consisting of ~40 mol% and 98 to 60 mol% of an α,β-unsaturated carboxylic acid alkyl ester.