JP3054340B2 - Polyarylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a practically excellent fluidity,
The present invention relates to a polyarylene sulfide resin composition having mechanical properties.

[0002]

2. Description of the Related Art In recent years,
Electrical and electronic equipment parts materials, automotive equipment parts materials, and chemical equipment parts materials require thermoplastic resins that have high heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy. Is coming. Polyarylene sulfide (PAS) resin typified by polyphenylene sulfide (PPS) is also one of the resins that meet this demand.
In general, the physical properties are improved by blending a fiber reinforcing material such as glass fiber and other inorganic fillers, and the demand is increasing. In particular, calcium carbonate is inexpensive as a filler, and is also known as a relatively preferable filler in physical properties. For example, a PAS resin blended with glass fiber has a good physical property ratio to cost and a fibrous form. It is used in various fields because it relaxes the anisotropy peculiar to the reinforcing agent and has excellent dimensional stability. In general, when calcium carbonate is added to and mixed with a resin, depending on the type of calcium carbonate, the type of resin, and the purpose of use of the resin composition (required characteristics),
Various proposals have been made to modify the surface of calcium carbonate. Among them, improving the mechanical strength and impact properties by improving the adhesion between the calcium carbonate and the resin requires mechanical properties and other properties (dimensional stability). Gender) is one of the major issues. As a technique for solving this problem, an example of improving the affinity with the resin and improving the strength by conventionally performing a surface treatment on the surface of calcium carbonate with various coupling agents such as a silane type or an epoxy type is shown. Have been. However, in the case of a PAS resin, the effect alone is not sufficient, and there are also problems such as deterioration of fluidity. Also, use fine spherical or cubic colloidal calcium carbonate to improve dimensional stability, or use spindle- or whisker-like synthetic light calcium carbonate to improve mechanical properties and reduce burr characteristics. Some suggestions to do so. Many of these synthetic calcium carbonates have strong cohesiveness, and fatty acids and resin acids are sometimes used as surface treatment agents to prevent such cohesion. The melt kneading property of the extruder deteriorates, and the strand resin discharged from the die portion of the extruder becomes liable to be cut off in the middle, which causes a problem in production and lowers the mechanical properties. As described above, a calcium carbonate surface treatment agent suitable for a PAS resin that simultaneously satisfies the improvement in mechanical properties and the stability during melt-kneading has not been proposed yet.

[0003]

The present inventors have studied to solve the above-mentioned problems, and as a result, by adding and mixing calcium carbonate surface-treated with a specific resin as a filler to a PAS resin, the purpose thereof has been achieved. The inventors have found that the present invention can be achieved, and have completed the present invention. That is, the present invention relates to (A) 100 parts by weight of a polyarylene sulfide resin, (B) 5-200 parts by weight of calcium carbonate previously surface-treated with a resin having a carboxyl group and a hydroxyl group, (C) inorganic substances other than (B). It is a polyarylene sulfide resin composition containing 0 to 200 parts by weight of a filler.

[0004] The components of the present invention will be described below. The PAS resin as the component (A) in the composition of the present invention is mainly composed of repeating units (-Ar-S-) (where Ar is an arylene group). Arylene group (-A
Examples of r-) include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group (provided that the substituent is an alkyl group, preferably a C _{1 to} C ₅ alkyl group, or a phenyl group), , p'-diphenylene sulfone group, p, p'-
Biphenylene group, p, p'-diphenylene ether group, p, p '
-Diphenylenecarbonyl group, naphthalene group and the like.
In this case, in the arylene sulfide group composed of the above-mentioned arylene group, a polymer using the same repeating unit, that is, a homopolymer can be used.From the viewpoint of processability of the composition, a heterogeneous repeating unit is used. Included copolymers may be preferred. As a homopolymer, a p-phenylene group was used as an arylene group.
P having a p-phenylene sulfide group as a repeating unit
PS is a typical one, and PPS having a substantially linear molecular structure is particularly preferably used. As the copolymer, a copolymer mainly comprising an arylene sulfide group comprising the above-mentioned arylene group and comprising two or more different combinations can be used.
A combination mainly with a phenylene sulfide group and another repeating unit is particularly preferably used. P-
Substantially linear ones containing a phenylene sulfide group in an amount of 60 mol% or more, more preferably 70 mol% or more, are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. In this case, those in which the repeating unit of the component is contained in a block shape rather than in a random shape have good workability, and are excellent in heat resistance and mechanical properties, and can be preferably used. A preferable copolymerization component includes, for example, an m-phenylene group, but is not limited thereto. Further, a branched or cross-linked PAS resin polymerized by using a small amount of a monomer having three or more functional groups as a part of the monomer can also be used. Particularly, a blended resin obtained by blending the above linear polymer with a moderately branched or crosslinked PAS resin is mentioned as an example of a preferable combination from the viewpoint of moldability (for example, prevention of burrs and molding cycle). Further, the PAS resin used in the present invention may be a modified PAS into which various substituents are introduced. or,
A branched or crosslinked PAS obtained by curing a low molecular weight linear PAS by a curing treatment such as oxidative crosslinking or thermal crosslinking can also be used.

[0005] The calcium carbonate used as the component (B) in the present invention is not particularly limited as long as it has been surface-treated in advance with a resin having a carboxyl group and a hydroxyl group. Both heavy calcium carbonate produced by mechanical pulverization and classification in a wet system and precipitated calcium carbonate produced by introducing carbon dioxide gas into a water slurry of calcium hydroxide and reacting it can be used. or,
The shape and size are also arbitrary, and may be granular, spindle-shaped, or whisker-shaped.
The following are preferred, and those having a thickness of 0.1 to 15 μm are particularly preferred in terms of smoothness and physical properties. Here, the resin used for the surface treatment of calcium carbonate is not particularly limited as long as it has the above two types of functional groups.
A copolymer obtained by copolymerizing a β-unsaturated carboxylic acid and an α, β-unsaturated carboxylic acid hydroxyester or a polyvinyl alcohol containing a carboxyl group is particularly preferred. The ratio of the functional groups of the carboxyl group and the hydroxyl group can be arbitrarily changed according to the type of calcium carbonate and the type of PAS resin. Further, even if a part or all of the carboxyl group in the resin for surface treatment is an alkali metal salt or an alkaline earth metal salt of a carboxylic acid, there is no problem from the object of the present invention. The amount of the resin used for the surface treatment is not particularly limited as long as the amount of the resin sufficiently covers the surface of the calcium carbonate, but is generally 0.1 to 10% by weight based on the calcium carbonate, and is preferably used. Is 0.2 to 3% by weight. The surface treatment may be performed by a general method, for example, by directly adding to a water slurry solution of calcium carbonate, or adding and blending to a dehydrated cake-like substance, stirring, and attaching to the surface and drying it. The method is not particularly limited. The amount of the component (B) in the present invention is 5 to 200 parts by weight, preferably 10 to 150 parts by weight, per 100 parts by weight of the PAS resin (A). If the amount is too small, the effect of blending calcium carbonate (ratio of physical properties to cost, dimensional stability, etc.) cannot be obtained, and if it is too large, problems arise in extrudability and molding workability, and in addition to mechanical properties. Is not preferred. The amount of calcium carbonate is also related to the amount of the other filler (C) described later.

Next, in the composition of the present invention, an inorganic filler (C) other than the calcium carbonate (B) can be used in combination. The filler of the component (C) used in the present invention is not an essential component, but should be blended in order to obtain a molded article having excellent mechanical strength, rigidity, heat resistance, and dimensional stability performance. Is preferred. For this purpose, a fibrous, powdery or plate-like filler is used depending on the purpose. As the fibrous filler, glass fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber,
Silicon nitride fiber, boron fiber, potassium titanate fiber, calcium sulfate fiber, asbestos fiber, aluminum borate fiber,
In addition, inorganic fibrous materials such as fibrous materials of metals such as stainless steel, aluminum, titanium, copper, and brass can be used. Further, high melting point organic fibrous substances such as fluororesins and aramid resins can also be used. Particularly representative fibrous fillers are glass fibers and carbon fibers. On the other hand, as the particulate filler, carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, oxides Oxides of metals such as iron, zinc oxide, titanium oxide and alumina; sulfates of metals such as barium sulfate and sodium sulfate; carbonates of metals other than calcium carbonate such as magnesium carbonate and zinc carbonate; other silicon carbide; nitrided Silicon etc. are mentioned. Examples of the plate-like filler include mica and glass flake. These fillers are desirably treated in advance with a sizing agent or a surface treatment agent in order to improve the mechanical strength of the composition. Examples of the treating agent include an epoxy compound,
Examples include isocyanate-based compounds, silane-based compounds, and titanate-based compounds, and may be the same resin as the calcium carbonate surface treatment agent of the present invention. The above-mentioned various fillers (C) may be used in combination of two or more. For example, the combined use of a fibrous filler and a plate-like filler is a preferable combination in terms of both strength and dimensional accuracy. (C) The amount of the fibrous filler, the particulate filler, and the plate-like filler used as the component is also related to the blending amount with the specific surface-treated calcium carbonate (B).
200 parts by weight or less, preferably 5 to 150 parts by weight, based on 100 parts by weight of S resin (A), and the total amount with calcium carbonate (B) is 300 parts by weight or less based on 100 parts by weight of PAS resin. preferable. If it is excessively large, the molding processability is impaired and the mechanical properties are undesirably reduced.

Next, the composition of the present invention is preferably, but not necessarily, further added with an alkoxysilane compound (D). The alkoxysilane compound (D) is preferably at least one selected from the group consisting of aminoalkoxysilane, vinylalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane, and allylalkoxysilane. As the aminoalkoxysilane, any silane compound having at least one amino group in one molecule and having two or three alkoxy groups is effective. For example, γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ
-Aminopropylmethyldiethoxysilane, N- (β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like. As the vinylalkoxysilane, any silane compound having one or more vinyl groups in one molecule and having two or three alkoxy groups is effective. For example, vinyltriethoxysilane, vinyltrimethoxysilane And vinyltris (β-methoxyethoxy) silane. As the epoxyalkoxysilane, any silane compound having one or more epoxy groups in one molecule and having two or three alkoxy groups is effective. For example, γ-glycidoxypropyltrimethoxysilane is effective. , Γ-glycidoxyprohirtriethoxysilane and the like. Any mercaptoalkoxysilane is effective as long as it is a silane compound having one or more mercapto groups in one molecule and having two or three alkoxy groups, such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane. -Mercaptopropyltriethoxysilane and the like. As the allylalkoxysilane, any one of silane compounds having one or more allyl groups in one molecule and having two or three alkoxy groups is effective. For example, γ-diallylaminopropyltrimethoxysilane,
γ-allylaminopropyltrimethoxysilane, γ-allylthiopropyltrimethoxysilane, and the like. For the purposes of the present invention, among the above silane compounds, aminoalkoxysilanes are most preferred. The amount of the alkoxysilane compound (D) is 5 parts by weight or less, preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the PAS resin. If it is too large, the viscosity of the composition increases, which is not preferable.

The composition of the present invention further comprises, for toning,
If necessary, a desired color tone can be adjusted by blending a pigment or a dye. In addition, known substances generally added to the PAS resin depending on the purpose, that is, various stabilizers, antistatic agents,
A flame retardant, a lubricant, a crystallization accelerator, a crystal nucleating agent, a release agent, a plasticizer, and the like can be appropriately added as necessary.
In addition, a small amount of other thermoplastic resins, for example, a polyolefin resin, a polyamide resin, a polystyrene resin (including AS, ABS, etc.), a polyester resin, a polyether resin, or the like may be added as a supplement.

[0009] The resin composition of the present invention can be prepared by equipment and a method generally used for preparing a synthetic resin composition. Generally, necessary components are mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded to form molding pellets. It is also a preferable method to melt-extrude the resin component and add and mix an inorganic component such as calcium carbonate during the extrusion. The material pellets obtained in this manner can be molded by using a generally known thermoplastic resin molding method such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, etc., but the most preferable is injection molding. Molding.

[0010]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Examples 1 to 16 and Comparative Examples 1 to 15 PPS resin (manufactured by Kureha Chemical Industry Co., Ltd., “Fortron K”
PS)), various calcium carbonates as the component (B), glass fibers as the component (C), and various alkoxysilanes as the component (D) in the amounts shown in Tables 1 to 3, and mixed in a blender for 2 minutes. This was melt-kneaded with an extruder having a cylinder temperature of 310 ° C. to produce resin material pellets. The state of the strand resin at this time was observed and compared as extrusion stability. Using the pellets, the melt viscosity was measured with a Toyo Seiki Seisakusho (manufactured) Capillograph 1B type apparatus. The capillary is 1mmΦ × 10mmL and the temperature is 3
The value at 10 ° C. and a shear rate of 1200 / sec was defined as the melt viscosity. In addition, cylinder temperature 320 ° C, mold temperature with injection molding machine
Tensile specimen according to ASTM D638 at 150 ° C, ASTM D790
Each of the bending test pieces was molded in accordance with the standards described above, and mechanical properties such as strength were measured. The results are shown in Tables 1 to 3.

[0011]

[Table 1]

Note) 1) Calcium carbonate manufactured by Shiroishi Kogyo Co., Ltd. A: Heavy calcium carbonate "P-10" (average particle size 4 μm) B: Heavy calcium carbonate "P-50" (average particle size 11 μm) C : Light calcium carbonate "Silver W" (spindle shape) D: Colloidal calcium carbonate "Brilliant-15"
(Cubic) 2) Surface treatment agent (1% by weight based on calcium carbonate) a: acrylic acid-methacrylic acid hydroxyethyl ester copolymer b: carboxyl group-containing polyvinyl alcohol c: γ-aminopropyltriethoxysilane d: Polyfunctional epoxy oligomer e: fatty acid 3) Extrusion stability (strand break, etc.) ○: good (no strand break) △: slightly poor (a little strand break) ×: poor (a lot of strand breaks) (also in the table below) Same)

[0013]

[Table 2]

[0014]

[Table 3]

Note 4) Alkoxysilane i) γ-aminopropyltriethoxysilane ii) γ-glycidoxypropyltriethoxysilane iii) γ-mercaptopropyltrimethoxysilane

[0016]

The polyarylene sulfide resin composition of the present invention has excellent workability at the time of melt-kneading, good flowability, excellent moldability, and good mechanical strength. I am satisfied with the characteristics of
It is extremely useful in practical use.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C09C 1/02 C09C 1/02 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 81/00-81/02 C08K 3 / 18-3/26 C08K 9/04-9/06 C08K 5/541-5/5419

Claims (5)

(57) [Claims] (A) Polyarylene sulfide resin 100
(B) 5 to 200 parts by weight of calcium carbonate preliminarily surface-treated with a resin having a carboxyl group and a hydroxyl group (C) 0 to 200 parts by weight of an inorganic filler other than (B) Arylene sulfide resin composition. 2. The resin for surface treatment of component (B) comprises a copolymer obtained by copolymerizing an α, β-unsaturated carboxylic acid and an α, β-unsaturated carboxylic acid hydroxyester and / or a carboxyl group. The polyarylene sulfide resin composition according to claim 1, which is a polyvinyl alcohol contained therein. 3. The polyarylene sulfide resin composition according to claim 1, wherein the component (C) is 5 to 150 parts by weight of glass fiber or carbon fiber. 4. The method of claim 1, wherein the alkoxysilane compound (D) is
The polyarylene sulfide resin composition according to any one of claims 1 to 3, wherein 0.1 to 5 parts by weight of (A) polyarylene sulfide resin is blended. 5. The polyarylene sulfide resin composition according to claim 4, wherein (D) the alkoxysilane compound is at least one of aminoalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane, vinylalkoxysilane and allylalkoxysilane.