JPH05163434A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition useful as an industrial material excellent in heat resistance, chemical resistance and mechanical properties. CONSTITUTION:The objective thermoplastic resin composition comprising (A) 100 pts.wt. of a resin blend comprising (1) 5-95wt.% of a polyarylene sulfide (PAS) resin and (2) 95-5wt.% of polyvinylidene fluoride and (B) 1-50 pts.wt. of a copolymer from (a) methyl methacrylate and alpha,beta-unsaturated acid glycidyl ester. At least 2wt.% of the PAS resin has SH group at its terminal.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition containing polyvinylidene fluoride and polyarylene sulfide as main components, which is useful as an industrial material, particularly an industrial material requiring heat resistance and chemical resistance. Regarding things.

[0002]

2. Description of the Related Art Polyvinylidene fluoride has excellent chemical resistance and is therefore widely used in fields requiring chemical resistance. However, its melting point is as low as about 170 ° C., and under high temperature conditions exceeding about 150 ° C. Since the strength is greatly reduced, it has not been put to practical use in the field where heat resistance is required.

On the other hand, polyarylene sulfide resin represented by polyphenylene sulfide resin has excellent heat resistance. Polyphenylene sulfide resin has a melting point of about 28.
It has a mechanical property that is as high as 0 ° C and is practically acceptable even at a high temperature of 150 ° C or higher. The polyarylene sulfide resin is a crystalline polymer and is relatively excellent in chemical resistance, but it is inferior in chemical resistance to polyvinylidene fluoride and is particularly weak in a solvent such as a halogenated hydrocarbon and nitric acid. In addition, since the polyarylene sulfide resin has a low melt viscosity, the extrusion moldability is poor, and it is hard to say that it is a preferable resin material for obtaining an extrusion molded product such as a pipe.

Even if polyvinylidene fluoride and a polyarylene sulfide resin are simply blended in order to obtain an industrial material having excellent heat resistance and chemical resistance, these resins are inferior in compatibility, and therefore, are obtained from a blend of both resins. The molded product obtained was inferior in mechanical strength.

The inventors of the present invention previously mentioned that in a resin composition based on polyvinylidene fluoride and a polyarylene sulfide resin, a copolymer of methyl methacrylate and a glycidyl ester of an α, β-unsaturated acid was used. It was found that when blended, the compatibility of both resins is improved, and not only excellent heat resistance and chemical resistance but also a molded product having good mechanical strength can be obtained, and a patent application was filed (Patent application 3 −
177657).

An object of the present invention is to provide a resin composition based on polyvinylidene fluoride and a polyarylene sulfide resin, in which the compatibility of both resins is further improved and the heat resistance and chemical resistance are superior. First, it is to provide a thermoplastic resin composition suitable for forming a molded product having better mechanical properties.

[0007]

SUMMARY OF THE INVENTION The above object is to provide 100 parts by weight of a resin mixture consisting of 5 to 95% by weight of a polyarylene sulfide resin and 95 to 5% by weight of polyvinylidene fluoride and methyl methacrylate and α, β-unsaturated resin. 1-50 parts by weight of a copolymer of saturated acid with glycidyl ester,
This is achieved by a thermoplastic resin composition characterized in that at least 2% by weight of the polyarylene sulfide resin is a polyarylene sulfide resin having a terminal --SH group.

The polyarylene sulfide resin (hereinafter referred to as PAS resin) used in the present invention is a polymer substantially composed of a repeating unit -RS- (R: arylene group). Preferably, the following formula

[Chemical 1] A polyparaphenylene sulfide resin having a repeating unit represented by, and a random copolymer and a block copolymer containing the repeating unit in an amount of 70 mol% or more, more preferably 90 mol% or more. Examples of the small amount copolymerization component in the copolymer include arylene sulfide units represented by the following formula.

[0009]

[Chemical 2]

PAS resins are generally used in Japanese Patent Publication No. 45-3.
Cross-linking and high molecular weight by heating a polymer having a relatively small molecular weight obtained by the production method typified by Japanese Patent No. 368 after polymerization in an oxygen atmosphere after polymerization or by adding a crosslinking agent such as peroxide and heating. So-called thermal cross-linked P
AS resins and linear and high molecular weight polymers obtained by the production methods represented by JP-B-52-12240, JP-B-54-8719, and JP-A-61-7332, so-called linear chains. Although there are type PAS resins and the like, any of them can be used in the present invention.

Alkali is generally used for the production of PAS resin, and the resulting PAS resin has --SNa groups at the terminals. Therefore, a typical PAS resin contains about 500 ppm or more of Na. The PAS resin used in the present invention must be at least 2% by weight PAS resin having a terminal --SH. Occupy in PAS resin-SH terminal PA
The upper limit of the amount of S resin is not particularly limited, and PAS
The total amount of resin may be a -SH-terminated PAS resin. Preferably, the proportion of -SH-terminated PAS resin is 5-100% by weight. When the proportion of the -SH-terminated PAS resin is less than 2% by weight, the high degree of improvement in the compatibility between the PAS resin and polyvinylidene fluoride, which is the object of the present invention, cannot be achieved.

To prepare a PAS resin having at least 2% by weight of --SH groups at the end for use in the present invention, a high Na content PAS resin prepared by conventional methods (substantially A convenient method is to blend a PAS resin having an SNa group) with a PAS resin having a terminal -SH group. P whose terminal is substantially a -SH group
As the AS resin, PA having a molar ratio of -SH terminal to all terminals of 0.4 to 1.0, preferably 0.6 to 1.0.
S resin is used. Such -SH-terminated PAS resin has a P-terminal having a -SNa group produced by a conventional method.
The AS resin is acid-treated or heat-treated to remove the -SNa group-
It is obtained by a method of converting to an SH group (this method is
For example, it is described in JP-A-1-268727. ). That is, -S is added to an aqueous solution of an acid such as hydrochloric acid or acetic acid.
It can be prepared by a method of immersing a PAS resin having a Na group terminal and heating if necessary, a method of hot water treatment in a pressure vessel, or a method combining these methods. It is preferable that the reaction products obtained by these treatment methods are washed with warm water to remove residual acids and salts. In addition, the end is substantially -S.
PAS resins that are H groups are commercially available.

As an alternative method for preparing the PAS resin used in the present invention, at least 2% by weight having terminal --SH groups,
PAS having -SNa group end produced by a conventional method
When the resin is acid-treated or heat-treated as described above, the -SNa group is partially converted to -S by selecting the treatment conditions.
A method of converting to an H group can also be adopted.

The melt viscosity of the PAS resin used in the present invention is not particularly limited as long as a molded product can be obtained by a usual method such as injection molding or extrusion molding, but a temperature of 300
From the viewpoint of resin physical properties and moldability, those having an apparent melt viscosity of 100 poise or more and 5,000 poise or less at a temperature of 10 ° C. and a shear rate of 10 ¹ to 10 ⁴ sec ⁻¹ are preferable. The polyvinylidene fluoride used in the present invention is not particularly limited as long as it is possible to obtain a molded product having mechanical strength that does not hinder practical use by injection molding, extrusion molding, etc., like the PAS resin, but it is generally a number average molecular weight. 10,000 ~
1,500,000 are used.

The glycidyl ester of methyl methacrylate and α, β-unsaturated acid which acts as a compatibilizer for both the PAS resin and the polyvinylidene fluoride resin is methyl methacrylate and the glycidyl ester represented by the following formula.

[Chemical 3] It is a copolymer obtained by radical copolymerization with. R in the above formula is hydrogen or a lower alkyl group, and specific examples of the glycidyl ester include glycidyl methacrylate, glycidyl acrylate, and glycidyl ethyl acrylate. Of these, glycidyl methacrylate is most preferred. This radical copolymerization can be carried out by any of emulsion polymerization, suspension polymerization, bulk polymerization and solution polymerization. Upon copolymerization of methyl methacrylate and the glycidyl ester, other monomers, for example, methyl acrylate, within a range that does not impair the effects of the present invention,
Styrene, vinyl acetate, etc. can be copolymerized.

The copolymerization ratio (molar ratio) of methyl methacrylate and glycidyl ester is preferably selected from the range of 98/2 to 20/80, particularly 90/10 to 40/60. The weight average molecular weight of the copolymer is 2,0 in consideration of mechanical strength, heat resistance and moldability of the resin molded product.
In the range of 0 to 1,000,000, especially 5,000 to 5
It is preferably in the range of 0,000.

In the resin composition of the present invention, the ratio of PAS resin to polyvinylidene fluoride is 95/5 to 5/95.
(Weight ratio), preferably 90/10 to 10/90 (weight ratio). If the proportion of the PAS resin exceeds 95% by weight, the resistance to solvents such as halogenated hydrocarbon and nitric acid is considerably lowered, and conversely, if the proportion of the PAS resin is less than 5% by weight, heat resistance and mechanical properties are lowered.

Compatibilizer methyl methacrylate and α,
The blending amount of the copolymer of β-unsaturated acid with glycidyl ester is 10 in total of polyvinylidene fluoride and PAS resin.
It is 1 to 50 parts by weight, preferably 3 to 20 parts by weight, relative to 0 parts by weight. If the blending amount of this copolymer is less than 1 part by weight, the effect of improving compatibility is not recognized and the resin composition is inferior in mechanical properties and chemical resistance. On the contrary, if the blending amount of the copolymer exceeds 50 parts by weight, the thermal properties and mechanical properties of the resin composition deteriorate.

In the resin composition of the present invention, reinforcing fibers and / or inorganic fillers may be added in order to improve strength, heat resistance, rigidity and dimensional stability. Examples of the reinforcing fiber include glass fiber, carbon fiber such as polyacrylonitrile-based and pitch-based, graphite fiber, potassium titanate fiber, silicon carbide fiber, asbestos fiber, ceramic fiber, stainless fiber and other inorganic metal fibers and aromatic polyamide (aramid). ) Examples include organic fibers such as fibers. As the inorganic filler, kaolin, clay, bentonite, zeolite, mica, mica, talc, wollastonite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, molybdenum dioxide, graphite, gypsum, glass , Beads, glass balloons and the like. If necessary, the surface of these reinforcing fibers and the inorganic filler can be pretreated with a coupling agent such as a silane type, titanate type or aluminate type before use. The compounding amounts of the reinforcing fiber and the inorganic filler are preferably 100 parts by weight or less and 80 parts by weight or less, respectively, based on 100 parts by weight of the resin mixture including the PAS resin, polyvinylidene fluoride and the compatibilizer.

The resin composition of the present invention contains a heat stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, a coloring agent, a release agent, a gas adsorbent, etc. within a range not hindering the achievement of the object of the present invention. It can be done.

The resin composition of the present invention is generally in the form of pellets, and is mainly used as a molding raw material for injection molding and injection molding. The method for producing the pellets is not particularly limited, but after PAS resin, polyvinylidene fluoride, and a compatibilizer are dry blended using a tumbler mixer, a ribbon blender, a Henschel mixer, a V blender, and the like, a kneader, a Banbury mixer, It is melt-kneaded using a single-screw or twin-screw extruder, extruded, and cut into pellets. For melt-kneading, single-screw and twin-screw extruders having a particularly high kneading force are preferable. The melt-kneading temperature in this case is a temperature equal to or higher than the melting point of the PAS resin, that is, 280 ° C to 350 ° C, preferably 290 to 330.
℃.

[0022]

In the copolymer of methyl methacrylate and the glycidyl ester of α, β-unsaturated acid used in the present invention, the glycidyl ester moiety reacts with the —SH group at the molecular end of the PAS resin, Further, the methyl methacrylate portion in the copolymer shows a large compatibility with polyvinylidene fluoride. In the present invention, as the PAS resin, -SH
Since the PAS resin having a certain proportion of those having a terminal group is used, the compatibility is greatly improved. Therefore,
The PAS resin in the resin composition of the present invention and polyvinylidene fluoride are compatible with each other to form an alloy. As a result, the molded article formed from the resin of the present invention has both excellent chemical resistance and solvent resistance originally possessed by polyvinylidene fluoride and excellent mechanical properties and heat resistance inherently possessed by PAS resin.
It should be noted that merely mixing the PAS resin and polyvinylidene fluoride does not exhibit the excellent mechanical properties inherent in the PAS resin. Therefore, the resin composition of the present invention is particularly useful as a molding material such as equipment for which heat resistance and chemical resistance are required, for example, pipes of chemical plants.

[0023]

EXAMPLES Hereinafter, the resin composition of the present invention will be specifically described with reference to Examples. As PAS resin, polyphenylene sulfide (PPS), resin powder / toprene "T"
-4 "(made by Topren, Na content 1480 ppm, 3
00 ° C melt viscosity 500 poise) and SH-terminated PPS
(Kureha Chemical Co., W-205, Na content 70 pp
m), polyvinylidene fluoride (PVDF) as “Solf 1010” (manufactured by Solvay), and methyl methacrylate / α, β-unsaturated acid glycidyl ester copolymer as methyl methacrylate / glycidyl methacrylate copolymer (MMA-co-GMA) "Blenmer CP-50M" (manufactured by NOF Corporation, glycidyl methacrylate content 31% by weight, weight average molecular weight 10,000) was used.

45 mmφ after dry blending each component
It was melt-kneaded at 290 ° C. using a twin-screw extruder to obtain pellets. The pellets were injection molded at 300 ° C. and a mold temperature of 140 ° C. to prepare test pieces, and the physical properties were evaluated according to the following criteria (Examples 1 to 9). The results are shown in Table 1.

[0025]

[Table 1] For comparison, a resin composition using PPS not containing SH-terminal PPS was similarly evaluated (Comparative Examples 1 to 1).
7). The results are shown in Table 2.

[0026]

[Table 2]

Melt Flow Rate (MFR): JIS
K-6758, 300 ° C., load 2.16 kg Flexural modulus: JIS K-7203 Tensile strength and tensile elongation at break: JIS K-7113 Heat distortion temperature (HDT): JIS K-7207, load 1
8.6kg Chemical resistance: 40 ℃ in dichloroethane (CH ₂ Cl ₂ )
For 10 days and 20% nitric acid at 100 ° C. for 10 days,
Each was dipped, and the weight change was calculated and displayed as a reduction rate (%).

[Procedure amendment]

[Submission date] October 16, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

The melt viscosity of the PAS resin used in the present invention is not particularly limited as long as a molded product can be obtained by a usual method such as injection molding or extrusion molding, but a temperature of 300
It is preferable that the apparent melt viscosity is approximately 100 poises or more and 50,000 poises or less at a temperature of 10 ° C. and a shear rate of 10 ¹ to 10 ⁴ sec ⁻¹ from the viewpoint of resin physical properties and moldability.
The polyvinylidene fluoride used in the present invention is not particularly limited as long as it is possible to obtain a molded product having mechanical strength that does not hinder practical use by injection molding, extrusion molding, etc., like the PAS resin, but it is generally a number average molecular weight. 10,000
Those of 0 to 1,500,000 are used.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

[0023]

EXAMPLES Hereinafter, the resin composition of the present invention will be specifically described with reference to Examples. As PAS resin, polyphenylene sulfide (PPS) resin powder / toprene "T-"
4 "(made by Topren, Na content 1480 ppm, 30
0 ° C melt viscosity 2,000 poise) and SH-terminated PPS
(Kureha Chemical Co., W-205, Na content 70 pp
m), “Solf1010” (manufactured by Solvay) as polyvinylidene fluoride (PVDF), and methyl methacrylate / glycidyl methacrylate copolymer as a methyl methacrylate / α, β-unsaturated acid glycidyl ester copolymer ( MMA-co-GMA) "Blemmer C
P-50M "(manufactured by NOF CORPORATION, glycidyl methacrylate content 31% by weight, weight average molecular weight 10,000) was used.

Claims (1)

[Claims] 1. A polyarylene sulfide resin 5 to 95.
100 parts by weight of a resin mixture consisting of 100% by weight and polyvinylidene fluoride 95 to 5% by weight, and a copolymer 1 of methyl methacrylate and a glycidyl ester of an α, β-unsaturated acid.
˜50 parts by weight, and at least 2% by weight of the polyarylene sulfide resin is a polyarylene sulfide resin having a terminal —SH group.