WO2020135200A1

WO2020135200A1 - Polyphenylene sulfide resin composition and molded product thereof

Info

Publication number: WO2020135200A1
Application number: PCT/CN2019/126492
Authority: WO
Inventors: 赵宸胄; 汤先文; 加藤公哉; 松田政; 胡平
Original assignee: 东丽先端材料研究开发（中国）有限公司
Priority date: 2018-12-24
Filing date: 2019-12-19
Publication date: 2020-07-02
Also published as: CN113039244A; CN113039244B

Abstract

The present invention relates to a polyphenylene sulfide resin composition, comprising 5-2000 parts by mass of an inorganic filler relative to 100 parts by mass of a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer. The composition of the present invention has excellent heat and humidity resistance, can maintain a high mechanical strength when in contact with water for a long time, and is therefore particularly suitable as a water coolant for injection molding and in antifreeze circulation systems of an automobile, etc., and in other articles which are in contact with liquids, such as water, for a long time.

Description

Polyphenylene sulfide resin composition and its molded product

Technical field

The invention relates to the field of polymer materials, in particular to a polyphenylene sulfide resin composition and its molded product.

Background technique

Polyphenylene sulfide resin (PPS) has the characteristics of excellent fluidity, high temperature resistance, corrosion resistance, flame retardancy, balanced physical and mechanical properties, excellent dimensional stability, and excellent electrical properties, so it is widely used in electrical , Electronic parts or auto parts. In recent years, with the widespread use of polyphenylene sulfide resin materials in the cooling water and antifreeze circulation systems of automobiles and the like, it is further required to have excellent water resistance and humidity resistance.

In this regard, Patent Document 1 (Japanese Laid-Open Patent Publication No. 2018-141149) discloses a resin composition containing poly-p-phenylene sulfide and an inorganic filler by increasing the content of metal sodium atoms in the polyphenylene sulfide resin To 1000ppm or more, so as to improve the tensile strength retention rate after wet heat treatment to improve its resistance to heat and humidity. However, an increase in the content of metal atoms leads to a decrease in the tensile strength of the polyphenylene sulfide resin composition when untreated.

Patent Document 2 (Japanese Laid-Open Patent Publication No. 2018-123307) discloses a resin composition containing poly-p-phenylene sulfide, inorganic filler and organic nucleating agent, which is improved by adding an appropriate amount of organic nucleating agent The melt temperature of the polyphenylene sulfide resin is lowered to the crystallization temperature (T _mc ), and the crystal area of the polyphenylene sulfide resin is reduced and uniformed, thereby improving the water pressure resistance of the molded product. However, PEEK resin added as an organic nucleating agent tends to become a foreign substance relative to the main polyphenylene sulfide resin.

On the other hand, Patent Document 3 (Japanese Laid-Open Patent Publication No. 2016-69650) discloses a poly-p-phenylene sulfide-m-phenylene sulfide copolymer by copolymerizing m-phenylene sulfide units into polyphenylene sulfide molecules A polymer with lower crystallinity is obtained, thereby improving the adhesion between the formed film and the surface of metal and resin. However, the film-forming stability is not good when it is not mixed with poly-p-phenylene sulfide homopolymer, and at the same time, the strength of the film formed by the poly-p-phenylene sulfide-m-phenylene sulfide copolymer is lower than that of poly-p-phenylene sulfide. Homopolymer is not suitable for injection molding into cooling water of automobiles, antifreeze circulation systems and other molded products with certain strength requirements that have been in contact with water and other liquids for a long time.

Summary of the invention

In order to solve the above problems, the present inventors have found that although the poly-p-phenylene sulfide-m-phenylene sulfide copolymer has low strength and poor heat and humidity resistance, when combined with inorganic fillers, it can not only increase the strength, but also be more specific. The polyphenylene sulfide resin composition thus obtained can not only expand the application of the copolymer in plastic molded products, but also further improve the heat and moisture resistance of plastic molded products.

The invention also provides a molded product prepared by the above polyphenylene sulfide resin composition. Because of its excellent resistance to heat and humidity, it is suitable for cooling water, antifreeze circulation systems of automobiles and other parts that have been in contact with liquids such as water for a long time.

That is, the technical solution of the present invention is:

1. A polyphenylene sulfide resin composition comprising:

(A) Poly-p-phenylene sulfide-m-phenylene sulfide random copolymer, and

(B) inorganic filler,

The mixing amount of the (B) inorganic filler is 5 to 2000 parts by mass relative to 100 parts by mass of the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer.

2. The polyphenylene sulfide resin composition according to the above 1, wherein in the (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer, relative to the phenylene sulfide unit in the random copolymer The total mass, the content of m-phenylene sulfide unit is 2-25wt%.

3. The polyphenylene sulfide resin composition according to the above 1, wherein the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer has a melting point of 210-280°C.

4. The polyphenylene sulfide resin composition according to 1 above, wherein the (B) inorganic filler is based on 100 parts by mass of the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer The mixing amount is 26-2000 parts by mass.

5. The polyphenylene sulfide resin composition according to the above 1, further comprising (C) a poly(p-phenylene sulfide) homopolymer.

6. The polyphenylene sulfide resin composition according to the above 5, wherein the (C) poly-p-phenylene sulfide is (C) poly-p-phenylene sulfide with respect to 100 parts by mass of the (A) poly-p-phenylene sulfide-m-phenylene sulfide copolymer The mixing amount of the ether homopolymer is 10-2500 parts by mass.

7. The polyphenylene sulfide resin composition according to the above 5, relative to (A) a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and (C) a poly(p-phenylene sulfide) homopolymer The total mass of the phenylene sulfide unit, the content of the m-phenylene sulfide unit in the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer is 1-14 wt%.

8. The polyphenylene sulfide resin composition according to the above 5, relative to the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and the (C) poly-p-phenylene sulfide The total mass of the homopolymer is 100 parts by mass, and the mixing amount of the (B) inorganic filler is 5-150 parts by mass.

9. The polyphenylene sulfide resin composition according to the above 5, relative to the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and the (C) poly-p-phenylene sulfide The total mass of the homopolymer is 100 parts by mass, and the mixing amount of the (B) inorganic filler is 26-150 parts by mass.

10. The polyphenylene sulfide resin composition according to the above 1, wherein the (B) inorganic filler is selected from glass fibers, glass flakes, glass beads, carbon fibers, calcium carbonate, silica, talc or At least one of wollastonite.

11. The polyphenylene sulfide resin composition according to the above 1, further comprising (D) a silane compound.

12. The polyphenylene sulfide resin composition according to 11 above, wherein the (D) silane compound is an alkoxysilane compound containing at least one of an epoxy group, an amino group, or an isocyanate group.

13. A molded article obtained by using the polyphenylene sulfide resin composition according to any one of 1-12 above.

14. The molded product according to 13 above, which is used in a cooling water and antifreeze circulation system.

detailed description

The specific embodiments of the present invention are described below:

1. (A) Poly-p-phenylene sulfide-m-phenylene sulfide random copolymer:

The (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer used in the present invention is a random copolymer having a repeating unit represented by the following structural formula (I) and the following structural formula (II),

In the (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer used in the present invention, the content of m-phenyl sulfide unit is preferably 2-25 wt% relative to the total mass of the phenyl sulfide unit in the copolymer . When the content of m-phenylene sulfide unit is higher than 25wt% relative to the total mass of phenylene sulfide unit in the copolymer, the melting point and crystallinity of poly-p-phenylene sulfide-m-phenylene sulfide random copolymer show a downward trend, which greatly affects the resin The heat resistance and use temperature of the composition. The content is further preferably 20% by weight or less, and more preferably 13% by weight or less. When the content of m-phenylene sulfide unit is less than 2% by weight relative to the total mass of the phenylene sulfide unit in the copolymer, the effect of improving the moisture and heat resistance of the composition is limited, and its content is further preferably 3% by weight or more, more preferably 5% by weight the above.

The (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer used in the present invention preferably has a melting point of 210-280°C. When the melting point of the poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer is higher than 280°C, the content of m-phenylene sulfide unit is too small, and the effect of improving the composition's resistance to moisture and heat is limited. The melting point is more preferably 270 Below ℃. When the melting point of the poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer is lower than 210°C, its heat resistance is greatly reduced, which is not conducive to use in a high-temperature environment. The melting point is further preferably 235°C or higher, more preferably 250°C the above.

2. (B) Inorganic filler:

The composition formed by (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and (B) inorganic filler is relative to (C) polyphenylene sulfide homopolymer and (B) inorganic filler The resulting composition has higher resistance to moisture and heat.

The inorganic filler in the present invention refers to fillers known to be used in resins. For example, glass fiber, carbon fiber, potassium titanate whisker, zinc whisker oxide, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, glass Flakes, wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, graphite, aluminosilicate, alumina, di Silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, hollow glass beads , Ceramic beads, boron nitride, silicon carbide or wollastonite, etc. The inorganic filler may be a hollow inorganic filler in structure, and further, two or more kinds of these inorganic fillers may be selected for use in combination. The average diameter of the inorganic filler is not particularly limited, and is preferably 0.001 to 20 μm. Within this range, better fluidity and better appearance can be obtained.

In particular, for comprehensive consideration of low molding shrinkage and fluidity, in order to obtain a polyphenylene sulfide resin composition excellent in performance, the inorganic filler is preferably at least one of glass fiber or carbon fiber. The glass fiber is not particularly limited, and may be glass fiber used in the prior art. The glass fiber may be a chopped strand cut with a fixed length, coarse sand, or abrasive fiber. Generally, the average diameter of the glass fiber used is preferably 5-15 μm. When using chopped strands, the length is not particularly limited, but it is preferable to use standard 3 mm length fibers suitable for extrusion and kneading operations. In addition, in the present invention, the cross-sectional shape of the fibrous filler is not particularly limited, and any one or more of round and flat fibers may be used in combination.

On the other hand, in order to obtain a better product appearance, at least one of glass flakes, glass microbeads, hollow glass microbeads, calcium carbonate, silica, talc, or wollastonite is preferred.

3. The ratio of component (B)

In the present invention, the content of the (B) inorganic filler is preferably from 5 to 2000 parts by weight with respect to 100 parts by weight of the component (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer. Within this range of addition, the polyphenylene sulfide resin composition of the present invention can have good mechanical strength while still maintaining good fluidity, processability, and toughness. In the present invention, the amount of component (B) added is preferably 26 parts by mass or more, and more preferably 40 parts by mass or more with respect to 100 parts by mass of the component (A). On the other hand, the addition amount of (B) inorganic filler is preferably 800 parts by mass or less, and more preferably 300 parts by mass or less.

4. (C) Poly (p-phenylene sulfide) homopolymer

The (A) poly(p-phenylene sulfide) homopolymer used in the present invention is a polymer having a repeating unit represented by the following structural formula (I).

In the present invention, the structure of the poly(p-phenylene sulfide) homopolymer is not particularly limited. Straight-chain poly(p-phenylene sulfide), oxidized cross-linked poly(phenylene sulfide), or a branch containing a trihalogen functional group reactant may be used. For the chain-type polyphenylene sulfide, the addition amount of the trihalogen functional group reactant is preferably less than 1 wt%.

The polyphenylene sulfide homopolymer used in the present invention is not limited to the production method. For example, the polyphenylene sulfide homopolymer having the structure of the above formula (I) can be selected from those described in Japanese Patent Publication No. 45-3368 It is prepared by the method for obtaining higher fluidity or the method for obtaining lower fluidity described in Japanese Patent Publication No. 52-12240. The difference between the former and the latter is whether there is a polymerization aid alkali metal carboxylate in the polymerization system. In the former method, the alkali metal carboxylate is not added to the polymerization system, and the fluidity is high; while in the latter method, the alkali metal carboxylate is added to the polymerization system, the fluidity is low, which is beneficial to the toughness of the resin . Therefore, the polyphenylene sulfide polymer prepared by the two methods can be used in combination, thereby balancing the fluidity and toughness of the polyphenylene sulfide resin.

In addition, the polyphenylene sulfide polymer prepared above can be end-treated to obtain a polyphenylene sulfide polymer with lower chlorine content. For example, end-capping treatment with 2-mercaptobenzimidazole under alkaline conditions can provide end-capped poly(p-phenylene sulfide) homopolymer with lower chlorine content.

5. The ratio of component (A) and component (C)

In the present invention, when the component (C) poly(p-phenylene sulfide) homopolymer is added to the component (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer, relative to the component (A) 100 parts by mass of poly-p-phenylene sulfide-m-phenylene sulfide random copolymer, and the mixing amount of the component (C) poly-p-phenylene sulfide homopolymer is preferably 10-2500 parts by mass. In the present invention, in order to achieve the improvement of moisture and heat resistance while maintaining the mechanical strength and heat resistance of the composition, the components (A) and (C) may be mixed in a more preferable ratio. In the present invention, the component (C) is preferably 40 parts by mass or more, and more preferably 60 parts by mass or more with respect to 100 parts by mass of the component (A). On the other hand, the amount of component (C) added is preferably 1000 parts by mass or less, and more preferably 900 parts by mass or less. When the content of component (C) is less than 10 parts by mass relative to 100 parts by mass of component (A), the mechanical strength of the composition decreases. When the content of the component (C) is higher than 2500 parts by mass, the effect of improving the moisture and heat resistance of the composition is limited.

In the present invention, relative to the total mass of phenylene sulfide units in (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and (C) poly-p-phenylene sulfide homopolymer, (A) poly-p-phenylene sulfide The content of the m-phenylene sulfide unit contained in the ether-m-phenylene sulfide random copolymer is preferably 1 to 14% by weight. Relative to the total mass of phenylene sulfide units in (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and (C) poly(p-phenylene sulfide) homopolymer, (A) poly(p-phenylene sulfide)-m-phenylene When the content of the m-phenylene sulfide unit contained in the sulfide random copolymer is less than 1% by weight, the effect of improving the moisture and heat resistance of the composition is limited, and the content is more preferably 2.5% by weight or more. Relative to the total mass of phenylene sulfide units in (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and (C) poly(p-phenylene sulfide) homopolymer, (A) poly(p-phenylene sulfide)-m-phenylene When the content of the m-phenylene sulfide unit contained in the sulfide random copolymer is higher than 14 wt%, the mechanical strength and heat resistance of the composition tend to decrease, and its content is further preferably 13 wt% or less, and more preferably 11 wt% %the following.

6. The ratio of component (B) to component (A) and component (C)

In the present invention, when the component (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer and the component (C) poly-p-phenylene sulfide homopolymer are mixed, relative to the component (A ) And the total mass of component (C) is 100 parts by mass, and the content of the inorganic filler of component (B) is preferably 5-150 parts by mass. Within this addition range, the polyphenylene sulfide resin composition of the present invention can have good mechanical strength while still maintaining good fluidity, processability, and toughness. In the present invention, the amount of component (B) added is preferably 26 parts by mass or more, and more preferably 40 parts by mass or more, relative to 100 parts by mass of the total mass of the component (A) and the component (C). On the other hand, the added amount of the component (B) inorganic filler is preferably 110 parts by mass or less, and more preferably 80 parts by mass or less.

7. (D) Silane compound

In the present invention, from the viewpoint of enhancing the adhesion between the resin and the inorganic filler, the (D) silane compound may be further added. The silane compound is preferably an alkoxysilane compound having one or more groups selected from epoxy groups, amino groups, isocyanate groups, hydroxyl groups, mercapto groups, and urea groups.

Specific examples of the alkoxysilane compound having at least one functional group selected from epoxy groups, amino groups, isocyanate groups, hydroxyl groups, mercapto groups, and ureido groups include γ-glycidoxypropyltrimethoxy Epoxy-containing alkoxysilane compounds such as silane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ- Mercaptopropyl trimethoxysilane and γ-mercaptopropyltriethoxysilane containing thiol-containing alkoxysilane compounds, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane Urea group-containing alkoxysilane compounds such as γ-(2-ureidoethyl)aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane Silane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyl diethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropyl Isocyanate group-containing alkoxysilane compounds such as ethyl diethoxysilane and γ-isocyanatopropyltrichlorosilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ- (2-Aminoethyl)aminopropyl trimethoxysilane and γ-aminopropyl trimethoxysilane and other amino group-containing alkoxysilane compounds, as well as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyl Hydroxy-containing alkoxysilane compounds such as triethoxysilane.

In the present invention, for the consideration of adhesion and fluidity, the poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and the component (C) poly(p-phenylene sulfide) are homopolymerized relative to the component (A) The total mass of the compound and the substance is 100 parts by mass, and the (D) silane compound is preferably 0.01 to 3 parts by mass. By adding the silane compound in the above range, the adhesion between the polyphenylene sulfide resin and the inorganic filler can be enhanced while ensuring the fluidity of the polyphenylene sulfide resin composition in the present invention. The content of the silane compound is more preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more. At the same time, the content is more preferably 2 parts by mass or less, and more preferably 1 part by mass or less.

In the present invention, in order to improve the reactivity with the polyphenylene sulfide resin, the component (D) preferably has an alkoxysilane compound containing at least one of an epoxy group, an amino group, or an isocyanate group .

8. Other additives

In addition to the components (A) to (D), the polyphenylene sulfide resin composition of the present invention may further include an elastomer, an antioxidant, and a mold release agent (montanic acid and its metal salts, its esters, and its half esters, and stearyl alcohol , Stearamide, biurea or polyethylene wax, etc., in order to reduce gas generation during molding, stearamide is preferred), pigments (cadmium sulfide, phthalocyanine, or colored carbon black masterbatch, etc.), dyes (Aniline black, etc.), crystallizer (talc, titanium dioxide, kaolin, clay, etc.), plasticizer (octyl-p-hydroxybenzoate, or N-butylbenzenesulfonamide, etc.), antistatic agent ( Alkyl sulfate type anionic antistatic agent, quaternary ammonium type cationic antistatic agent, polyoxyethylene sorbitan monostearate and other nonionic antistatic agents, or trimethylammonium lactone amphoteric antistatic agent), resistance Combustion agent (for example, red phosphorus, phosphate ester, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, polycarbonate bromide, brominated epoxy resin Or a combination of these bromine-containing flame retardants and antimony trioxide), etc., one or more of them can be selected and used in combination.

Examples of the elastomer include one or more of olefin-based elastomers, modified olefin-based elastomers, and styrene-based elastomers.

Examples of olefin-based elastomers are obtained by polymerizing individual α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, or isobutene, or a plurality of them Polymer or copolymer, α-olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, or butyl methacrylate α, β -Copolymers of unsaturated acids and their alkyl esters. From the viewpoint of excellent toughness, preferred are: polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate Copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/butyl methacrylate copolymer, etc.

The modified olefin elastomer can be obtained by introducing a monomer component (functional group-containing component) having a functional group such as an epoxy group, an acid anhydride group, or an ionomer into the above-mentioned olefin elastomer. Examples of the functional group-containing component include maleic anhydride, itaconic anhydride, citraconic anhydride, internal bicyclic [2,2,1] 5-heptene-2,3-dicarboxylic acid, or internal bicyclic [2,2, 1] monomers containing acid anhydride groups such as 5-heptene-2,3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconic acid, or lemon Epoxy group-containing monomers such as glycidyl carboxylate or ionomer-containing monomers such as metal carboxylate complexes.

The method of introducing these functional group-containing monomer components is not particularly limited, and the following methods may be used: copolymerization with the components used in the polymerization of the olefin-based elastomer; or grafting of an olefin-based (co)polymer using a radical initiator Import methods. The introduction amount of the functional group-containing component is 0.001 to 40 mol%, preferably 0.01 to 35 mol% with respect to all monomers constituting the modified olefin elastomer.

Examples of particularly useful modified olefin elastomers obtained by introducing monomer components having functional groups such as epoxy groups, acid anhydride groups, or ionomers into olefin elastomers include ethylene/propylene-g-methacrylic acid Glycidyl ester copolymer ("g" means graft, the same below), ethylene/1-butene-g-glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/methacrylic acid glycidyl Glyceride copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer, ethylene/methyl methacrylate/glycidyl methacrylate copolymer, ethylene/propylene-g-maleic anhydride copolymer, ethylene /1-butene-g-maleic anhydride copolymer, ethylene/methyl acrylate-g-maleic anhydride copolymer, ethylene/ethyl acrylate-g-maleic anhydride copolymer, ethylene/methyl methacrylate- g-maleic anhydride copolymer, ethylene/ethyl methacrylate-g-maleic anhydride copolymer, zinc complex of ethylene/methacrylic acid copolymer, magnesium complex of ethylene/methacrylic acid copolymer, Or sodium complex of ethylene/methacrylic acid copolymer, etc.

From the viewpoint of compatibility, preferred are: ethylene/glycidyl methacrylate copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer, ethylene/methyl methacrylate/glycidyl methacrylate copolymer , Ethylene/1-butene-g-maleic anhydride copolymer, or ethylene/ethyl acrylate-g-maleic anhydride copolymer. Further preferred are: ethylene/glycidyl methacrylate copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer, or ethylene/methyl methacrylate/glycidyl methacrylate copolymer.

Examples of the styrene-based elastomer include styrene/butadiene copolymer, styrene/ethylene/butadiene copolymer, styrene/ethylene/propylene copolymer, styrene/isoprene copolymer, and the like. The styrene/butadiene copolymer is preferred from the viewpoint of compatibility.

From the aspects of fluidity and toughness, the amount of elastomer added is preferably 0.5-20 parts by mass, more preferably 0.8-10 parts by mass, and more preferably 100 parts by mass of component (A) and component (C). 1-6 parts by mass. In addition, as long as the effect of the present invention is not affected, the above-mentioned elastomers may be used in combination.

The antioxidant is preferably at least one selected from phenolic antioxidants and phosphorus antioxidants. When phenolic antioxidants and phosphorus antioxidants are used in combination, heat resistance and thermal stability can be efficiently maintained, and therefore it is preferable to use both.

As the phenolic antioxidant, a hindered phenol compound is preferably used. Specific examples are: triethylene glycol bis(3-tert-butyl-(5-methyl-4-hydroxybenzyl) propionate), N,N′-hexamethylenebis(3,5-di-tert Butyl-4-hydroxy-hydrocinnamide), tetrakis(methylene-3-(3′,5′-di-tert-butyl-4′-hydroxybenzyl)propionate) methane, pentaerythritol tetra(3- (3′,5′-di-tert-butyl)-4′-hydroxybenzyl)propionate), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s -Triazine-2,4,6-(1H,3H,5H)-trione, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4 , 4′-butylene bis(3-methyl-6-tert-butylphenyl), n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4, 8,10-tetraoxaspiro(5,5)undecane, or 1,3,5-trimethyl-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxybenzyl Group) benzene and so on. Among them, ester type polymer hindered phenols are preferred, and specifically, tetrakis(methylene-3-(3′,5′-di-tert-butyl-4′-hydroxybenzyl)propionate)methane, pentaerythritol tetra( 3-(3′,5′-di-tert-butyl)-4′-hydroxybenzyl)propionate), or 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy- 5-methylphenyl) propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane and the like.

Examples of phosphorus-based antioxidants include bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol-di Phosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, tri(2,4-di-tert-butylphenyl) phosphite, tetra(2,4-di-tert-butyl) Phenyl)-4,4′-bisphenylene phosphite, distearoyl pentaerythritol-diphosphite, triphenyl phosphite, or 3,5-dibutyl-4-hydroxybenzyl phosphate Ester diethyl ester and so on.

The amount of the antioxidant added is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, and most preferably 0.1 to 1 part by mass relative to 100 parts by mass of the components (A) and (C).

The polyphenylene sulfide resin composition of the present invention can be molded by a general resin molding method, and the polyphenylene sulfide resin composition of the present invention has excellent mechanical strength and heat and humidity resistance, and is particularly suitable for cooling of injection molding into automobiles and the like Water, antifreeze circulation system and other products that have been in contact with water for a long time.

The following further describes the present invention through specific examples. The following examples are implemented on the premise of the technical solution of the present invention, and provide detailed embodiments and specific operation procedures, but the scope of protection of the present invention is not limited to the following Examples.

Examples

1. Raw material of polyphenylene sulfide resin composition

Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-1: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 1wt%, weight average molecular weight: 50,000)

Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-2: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 2wt%, weight average molecular weight: 49,000)

Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-3: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 5wt%, weight average molecular weight: 54,000)

Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-4: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 8wt%, weight average molecular weight: 51,000)

Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-5: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 10wt%, weight average molecular weight: 52,000)

Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-6: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 20wt%, weight average molecular weight: 58,000)

Poly-p-phenylene sulfide-m-phenyl sulfide random copolymer (p-PPS/m-PPS random copolymer) A-7: Straight-chain p-phenyl sulfide-m-phenyl sulfide random copolymer (m-benzene Sulfide unit 25wt%, weight average molecular weight: 53,000)

Poly(p-phenylene sulfide)-m-phenylene sulfide block copolymer (p-PPS/m-PPS block copolymer) A'-1: Straight-chain p-phenylene sulfide-m-phenylene sulfide block copolymer (between Phenyl sulfide unit 10wt%, weight average molecular weight: 54,000)

Poly-p-phenylene sulfide homopolymer (p-PPS) C-1: linear p-PPS resin (weight average molecular weight: 49,000)

Glass fiber B-1: Nippon Electric Glass Co., Ltd. T-760H (single fiber diameter 10.5 μm)

Calcium carbonate B-2: Calfine KSS-1000

Silane compound D-1: Dow Chemical Company, XIAMETER ^TM OFS-6040

Release agent E-1: PRIME POLYMER, PE7000FB

Pigment F-1: Carbon black masterbatch, Toray S771B2

2. The test descriptions involved in the examples and comparative examples are as follows:

1) Melting point determination

The polyphenylene sulfide resin composition particles obtained by extrusion granulation and drying obtained in Examples and Comparative Examples were cut with a cutter to obtain a sample of about 5 mg. Subsequently, the cut samples were raised from 0°C to 340°C at a heating rate of 20°C/min under a nitrogen atmosphere with a DSC-discover 250 differential scanning calorimeter (DSC) of a TA company under a nitrogen atmosphere. After a constant temperature of 340°C for 5 minutes, The temperature was reduced from 340°C to 0°C at a rate of 20°C/min, and kept at 0°C for 3 minutes. Subsequently, the temperature is increased from 0°C to 340°C at a heating rate of 20°C/min, and the endothermic peak-to-peak temperature that appears during the heating process is the melting point.

2) Tensile strength test:

The injection molded standard splines obtained in the examples and comparative examples are measured according to the ISO 527-1,-2 standard, the drawing rate is 5 mm/min, the distance between the marking lines is 50 mm, the distance between the fixtures is 115 mm, and the average of 5 pieces in each group is averaged The value is taken as the tensile strength.

3) Tensile strength test after PCT treatment:

The injection-molded standard splines obtained in the examples and comparative examples were placed in a constant temperature and humidity chamber of the EHS-221M model manufactured by espec, and treated at 121°C×100% relative humidity for 100 hours. The tensile strength test evaluates the tensile strength after PCT treatment, and the average value of 5 of each group is taken as the tensile strength after PCT treatment.

4) Calculation of tensile strength retention after PCT treatment:

Assuming that the tensile strength evaluated in the above test method is S1 and the tensile strength after PCT treatment is S2, the retention rate of tensile strength after PCT treatment is calculated according to the following formula (1):

5) Shear strength test when the resin matrix and glass fiber are peeled:

The central part of the standard spline obtained in the examples and comparative examples was cut into thin slice samples along a plane perpendicular to the longitudinal direction of the spline, and the single glass fibers present in the obtained thin slice sample were passed through Hysitron Corporation The hemispherical indenter of the micro hardness tester Triboindenter TI950 is pushed out of the resin matrix in a direction perpendicular to the cross section of the glass fiber in the sliced sample, thereby measuring the shear strength when the resin and glass fiber are peeled off. The higher the shear strength when the resin matrix and the glass fiber are peeled off, the better the adhesion between the resin and the glass fiber.

6) Determination of the resin adhesion ratio of the glass fiber surface after PCT treatment:

The central part of the PCT-treated standard spline obtained in Examples and Comparative Examples was cut out, dissolved in α-chloronaphthalene, filtered at high temperature, and the glass fiber remaining on the funnel after high temperature filtration was washed After recycling and drying, PHI Quantera SXM was used to perform elemental analysis on the glass fiber surface. The relative content S (atomic%) of the sulfur element derived from the polyphenylene sulfide resin in the detected elements was obtained. The larger the value of S, the greater the proportion of polyphenylene sulfide resin contained in the detected element.

Examples 1-5, Comparative Examples 1-3:

The raw materials are as shown in Table 1. Pelletizing is carried out by TEX30α type twin-screw extruder (L/D=45.5) manufactured by Japan Steel Co., Ltd. The extruder has 13 heating zones and two feeding devices with measuring instruments And with vacuum exhaust equipment. Except for the glass fiber, after the other raw materials are mixed, they are added from the main feed port of the extruder, and the glass fibers are added from the feed port on the side of the extruder. The temperature of the extruder is set at 200 ℃-330 ℃, after melting, extruding , Cooling and pelletizing to obtain a granular polyphenylene sulfide resin composition; after drying the pellets in an oven at 130 ℃ for 3 hours, using a NEX50 model injection molding machine manufactured by Nissei Resin Co., Ltd. according to a molding temperature of 330 ℃ and a mold temperature of 130 ℃ The conditions are injection molded into ISO standard splines (spline mold size is 10mm wide x 4mm thick), and the performance test is performed according to the above test method. The composition melting point, tensile strength, and heat and humidity resistance data (evaluated by the tensile strength after 100 hours of PCT treatment and the tensile strength retention ratio) are shown in Table 1.

Example 6-7, Comparative Example 4-8:

An NEX50 injection molding machine manufactured by Nissei Resin Co., Ltd. was used to injection mold an ISO standard spline (spline mold size is 10 mm wide × 4 mm thick) under the conditions of a molding temperature of 330° C. and a mold temperature of 70° C. in an oven at 145° C. After 1 hour heat treatment (when the sample shown in Table 1 is molded under the same conditions, the curing speed is too slow, resulting in deformation of the ISO standard spline during demolding, so heat treatment is performed after low temperature molding), according to the above test method Performance Testing. Except for this, it is the same as the preparation method of Example 1, and the composition melting point, tensile strength, and hygrothermal resistance data (evaluated by the tensile strength after 100 hours of PCT treatment and the tensile strength retention ratio) are shown in Table 2. Table 4 shows the data of the peeling shear strength between the glass fiber and the resin matrix of Example 6 and Comparative Example 4 and the resin adhesion ratio on the glass fiber surface.

Examples 8-15:

Except for the addition of polyphenylene sulfide homopolymer, the same as the preparation method and evaluation method of Example 1, the composition melting point, tensile strength, and heat and humidity resistance data (in 100 hours after the PCT treatment of tensile strength and tensile The strength retention rate was evaluated) as shown in Table 3.

Table 1

Table 2

table 3

Table 4

1) The shear strength at the time of peeling between the glass fiber and the resin matrix was calculated based on the strength of the standard sample of Comparative Example 4 before PCT treatment as 100%

It can be seen from the comparison between Examples 1-5 and Comparative Examples 1-2, and between Examples 6-7 and Comparative Example 4, that the present invention is achieved by mixing (A) a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer Compared with the resin composition formed by (B) inorganic filler, compared to the resin composition formed by poly-p-phenylene sulfide-m-phenylene sulfide block copolymer or poly-p-phenylene sulfide homopolymer and inorganic filler, After 100 hours of PCT treatment, the tensile strength and strength retention rate are high, and the resin composition has better resistance to moisture and heat.

As can be seen from the comparison between Example 5 and Comparative Example 3, and between Example 6 and Comparative Example 5, when no inorganic filler is added, the tensile strength and strength retention rate of the polyphenylene sulfide resin composition after 100 hours of PCT treatment are low .

As can be seen from the comparison between Example 6 and Comparative Examples 6-8, when the amount of the inorganic filler added is too small, the tensile strength and strength retention rate of the polyphenylene sulfide resin composition after 100 hours of PCT treatment are low. Conversely, when the amount of the inorganic filler added is too large, the composition cannot be kneaded by the extruder.

From the comparison between Examples 8-15 and Comparative Example 2, it can be seen that the resin composition and (C) polymer formed by mixing (A) a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer, (B) an inorganic filler The resin composition formed of the phenylene sulfide homopolymer has a high tensile strength and strength retention rate after 100 hours of PCT treatment.

It can be seen from the comparison between Example 6 and Comparative Example 4 that the present invention is a resin composition formed by mixing (A) a poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer and (B) an inorganic filler, compared to A resin composition formed of a poly(p-phenylene sulfide) homopolymer and an inorganic filler has a higher shear strength for peeling between the glass fiber and the resin matrix after 100 hours of PCT treatment, and the resin adhered to the surface of the glass fiber The proportion is greater.

Claims

A polyphenylene sulfide resin composition, comprising:

(A) Poly-p-phenylene sulfide-m-phenylene sulfide random copolymer, and

(B) inorganic filler,

The mixing amount of the (B) inorganic filler is 5 to 2000 parts by mass relative to 100 parts by mass of the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer.
The polyphenylene sulfide resin composition according to claim 1, wherein in the (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer, relative to the total phenyl sulfide unit in the random copolymer Mass, the content of m-phenylene sulfide unit is 2-25wt%.
The polyphenylene sulfide resin composition according to claim 1, wherein the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer has a melting point of 210-280°C.
The polyphenylene sulfide resin composition according to claim 1, wherein the (B) inorganic filler is relative to 100 parts by mass of the (A) poly(p-phenylene sulfide)-m-phenylene sulfide random copolymer. The mixing amount is 26-2000 parts by mass.
The polyphenylene sulfide resin composition according to claim 1, further comprising (C) a poly(phenylene sulfide) homopolymer.
The polyphenylene sulfide resin composition according to claim 5, wherein the (C) poly p-phenylene sulfide is (C) poly p-phenylene sulfide with respect to 100 parts by mass of the (A) poly p-phenylene sulfide-m-phenylene sulfide copolymer The mixing amount of the homopolymer is 10-2500 parts by mass.
The polyphenylene sulfide resin composition according to claim 5, wherein the poly(phenylene sulfide)-m-phenylene sulfide random copolymer and (C) poly(phenylene sulfide) homopolymer in benzene The total mass of the sulfide unit, the content of the m-phenylene sulfide unit in the (A) poly-p-phenylene sulfide-m-phenylene sulfide random copolymer is 1-14 wt%.
The polyphenylene sulfide resin composition according to claim 5, wherein the poly(phenylene sulfide)-m-phenylene sulfide random copolymer (A) and the (C) poly(phenylene sulfide) are both The total mass of the polymer is 100 parts by mass, and the mixing amount of the (B) inorganic filler is 5-150 parts by mass.
The polyphenylene sulfide resin composition according to claim 5, wherein the poly(phenylene sulfide)-m-phenylene sulfide random copolymer (A) and the (C) poly(phenylene sulfide) are both The total mass of the polymer is 100 parts by mass, and the mixing amount of the (B) inorganic filler is 26-150 parts by mass.
The polyphenylene sulfide resin composition according to claim 1, wherein the (B) inorganic filler is selected from glass fibers, glass flakes, glass beads, carbon fibers, calcium carbonate, silica, talc or silicon At least one of limestone.
The polyphenylene sulfide resin composition according to claim 1, further comprising (D) a silane compound.
The polyphenylene sulfide resin composition according to claim 11, wherein the (D) silane compound is an alkoxysilane compound containing at least one of an epoxy group, an amino group, or an isocyanate group.
A molded article obtained by using the polyphenylene sulfide resin composition according to any one of claims 1-12.
The molded article according to claim 13, which is used in a cooling water and antifreeze circulation system.