JPH0643557B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a novel thermoplastic resin composition. More specifically, the present invention is extremely excellent in impact resistance, and also has excellent tensile elongation, moldability, surface gloss, etc., and is a structural component or precision component in, for example, electric / electronics, machinery, automobile fields and marine fields. Alternatively, the present invention relates to a composite thermoplastic resin composition containing a filler, which is suitable as a material for general industrial parts and industrial materials.

[Prior Art] Thermoplastic resins are easier to process than metal materials, have excellent corrosion resistance, are lightweight, and are relatively inexpensive. Therefore, in recent years, mechanical parts, precision parts, general industrial parts, furniture,
It is widely used in many fields as a material for daily sundries and structural materials.

However, thermoplastic resins are generally inferior in mechanical properties such as tensile strength, impact resistance, and hardness to metal materials, and are not always satisfactory in heat resistance and dimensional stability. Has the drawback of.

Therefore, in order to improve the drawbacks of such a thermoplastic resin, conventionally, powdery, granular, plate-like, or fibrous ones are appropriately selected from inorganic fillers and organic fillers according to the purpose. It is performed by selecting and filling a thermoplastic resin. Then, in order to obtain a composite resin composition having a desired physical property by enhancing the affinity with the matrix resin and uniformly dispersing them in these fillers, various surface treatments are usually carried out by a wet method or a dry method. Has been processed.

However, conventional methods for surface treatment of fillers are not always sufficient and have various problems. For example, when the surface treatment of the filler is performed by a wet method, a surfactant such as metal soap and an organic fatty acid such as stearic acid are usually used as the surface treatment agent, and these treatment agents are soluble as the solvent, and Using a material that does not adversely affect the filler, use a ball mill, stirring mill, or the like to adsorb the treatment agent on the surface of the filler, and then separate and dry the filler to remove the solvent, and treatment-fill. A method of obtaining an agent is used. However, in such a method, it is possible to treat the primary particles, but the particles are likely to agglomerate during drying, and the solvent may remain, and the treatment time is long and the manufacturing cost is high. There are drawbacks such as not being.

On the other hand, when the surface treatment of the filler is carried out by a dry method, usually a silane coupling agent, a titanate coupling agent,
Stir the filler with a high-speed mixer such as a Henschel mixer, using a surface treatment agent such as a surfactant or organic fatty acid.
By spraying or adding the surface treatment agent to this,
A method of obtaining a treated filler is used. However, in this method, processing in a short time is possible,
Although it has the advantage of low manufacturing cost, it is difficult to make the filler into primary particles, and it is easy to perform surface treatment on the agglomerates, and it is difficult to perform sufficient surface treatment on the particles inside the agglomerates. There are drawbacks. Therefore, the conventional dry-processed filler has a problem that it is difficult to obtain a composite resin composition having sufficiently desired physical properties.

[Problems to be Solved by the Invention] The present invention provides a filler-containing thermoplastic resin composition having excellent practical properties such as excellent impact resistance, high tensile elongation, excellent moldability and surface gloss. It was made for the purpose of providing.

[Means for Solving the Problems] As a result of intensive research conducted by the present inventors to develop such a thermoplastic resin composition having excellent practical physical properties, the specific 2
It has been found that the drawbacks of the above-mentioned dry treatment method can be improved and the object thereof can be achieved by combining various surface treatment agents, and the present invention has been completed based on this finding.

That is, the present invention relates to a mixture of (A) 10 to 95% by weight of a thermoplastic resin and (B) 90 to 5% by weight of at least one selected from an inorganic filler and an organic filler. 0.1 to 3% by weight of polyorganosiloxane (C) and (D) organic fatty acid, metal salt of organic fatty acid, N-alkyl substituted ammonium salt of organic fatty acid and N-alkylol substitution based on the weight of component (B) The present invention provides a thermoplastic resin composition containing 0.1 to 3% by weight of at least one selected from ammonium salts.

Hereinafter, the present invention will be described in detail.

In the composition of the present invention, the thermoplastic resin used as the component (A) is not particularly limited, and any one can be selected and used from those conventionally used as molding materials. Examples of the thermoplastic resin include polyolefin resin, polyvinyl chloride resin, polyamide resin, polyimide resin, polyester resin, polyacetal resin, polycarbonate resin,
Examples thereof include polyaromatic ether or thioether resins, polyaromatic ester resins, polysulfone resins, styrene resins, and acrylate resins.

Examples of the polyolefin resin include α, such as ethylene, propylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, and 4-methylpentene-1.
Examples thereof include olefin homopolymers, copolymers thereof, and copolymers of these with other copolymerizable unsaturated monomers. As typical examples, high-density, medium-density, low-density polyethylene and linear polyethylene, ultra-high molecular weight polyethylene, ethylene-vinyl acetate copolymer, ethylene-polyethylene such as ethyl acrylate copolymer,
Examples thereof include atactic, syndiotactic, isotactic polypropylene, polypropylene such as propylene-ethylene block copolymer or random copolymer, and poly-4-methylpentene-1.

Examples of the polyvinyl chloride-based resin include a vinyl chloride homopolymer and a copolymer of vinyl chloride and an unsaturated monomer copolymerizable with vinyl chloride. Examples of the copolymer include vinyl chloride-acrylic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-vinyl acetate copolymer. Examples thereof include polymers and vinyl chloride-vinylidene chloride copolymers. Further, those obtained by post-chlorinating these polyvinyl chloride resins to increase the chlorine content can be used.

Examples of polyamide resins include 6-nylon and 12
-Ring-opening polymerization of cycloaliphatic lactam such as nylon, 6,6-nylon, 6,10-nylon, 6,12
-A polycondensation product of an aromatic diamine and an aliphatic dicarboxylic acid, such as a polycondensation product of an aliphatic diamine and an aliphatic dicarboxylic acid such as nylon, or a polycondensation product of m-xylenediamine and adipic acid, Polycondensation products of p-phenylenediamine and terephthalic acid, polycondensation products of m-phenylenediamine and isophthalic acid, polycondensed aromatic diamines and aromatic dicarboxylic acids, 11-nylon and other amine acids And the like.

Polyimide resins include polyimides and polyamideimides, and specific examples of polyimides include pyromellitic dianhydride and diaminodiphenyl ether, 3,
Examples thereof include those obtained from combinations of 4,3 ′, 4′-benzophenone tetracarboxylic acid anhydride and diaminodiphenyl ether, bismaleimide and diaminodiphenylmethane, and specific examples of polyamideimides include trimellitic anhydride. And a combination of diaminodiphenyl ether and the like.

Examples of the polyester resin include those obtained by polycondensing an aromatic dicarboxylic acid and an alkylene glycol,
Specific examples include polyethylene terephthalate and polybutylene terephthalate.

Examples of the polyacetal resin include homopolymer polyoxymethylene and formaldehyde-ethylene oxide copolymer obtained from trioxane and ethylene oxide.

Examples of the polycarbonate-based resin include 4,4′-dihydroxydiarylalkane-based polycarbonate, particularly a phosgene method in which bisphenol A and phosgene are reacted,
A bisphenol A-based polycarbonate obtained by a transesterification method in which a carbonic acid diester such as bisphenol A or diphenyl carbonate is reacted is preferably used. Also, some of the bisphenol A is 2,2-
Modified bisphenol A-based polycarbonate and flame-retardant bisphenol A-based polycarbonate substituted with bis (4-hydroxy-3,5-dimethylphenyl) propane or 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane Etc. can also be used.

The polyaromatic ether or thioether-based resin has an ether bond or a thioether bond in the molecular chain, and examples of such a resin include polyphenylene oxide, polyphenylene oxide grafted with styrene, polyether ether ketone, and polyphenylene. Examples include sulfide.

Examples of the polyaromatic ester resin include polyoxybenzoyl obtained by polycondensation of p-hydroxybenzoic acid, polyarylate obtained by polycondensation of bisphenol A and an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid. Can be mentioned.

The polysulfone-based resin has a sulfone group in its molecular chain. Examples of such a resin include polysulfone obtained by condensation polymerization of bisphenol A and 4,4′-dichlorodiphenylsulfone, and phenylene group as an ether group. Examples thereof include a polyether sulfone having a structure linked to the p-position via a sulfone group, and a polyaryl sulfone having a structure in which diphenylene groups and diphenylene ether groups are alternately linked via a sulfone group.

Examples of the styrene-based resin include homopolymers such as styrene and α-methylstyrene, copolymers thereof, and copolymers with unsaturated monomers copolymerizable therewith. As typical examples, general-purpose polystyrene, impact-resistant polystyrene, heat-resistant polystyrene (α-methylstyrene polymer), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), acrylonitrile- Chlorinated polyethylene-styrene copolymer (ACS), acrylonitrile-ethylene propylene rubber-styrene copolymer (AE
S), acrylic rubber-acrylonitrile-styrene copolymer (AAS) and the like.

Examples of the acrylate resin include methacrylic acid ester polymers and acrylic acid ester polymers, and examples of these monomers include methacrylic acid and acrylic acid methyl, ethyl, n-propyl, isopropyl,
Butyl ester and the like are used, and as a typical industrial molding material, a methyl methacrylate resin can be mentioned as a typical example.

Among these thermoplastic resins, polyethylene, polypropylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyoxymethylene, polycarbonate, polyphenylene oxide, polyphenylene sulfide, ABS and the like are preferable.

In the composition of the present invention, one kind of these thermoplastic resins may be used, or two or more kinds thereof may be used in combination.

The filler used as the component (B) in the composition of the present invention is not particularly limited, and any one can be selected and used from those conventionally used in resin compositions. That is, both an inorganic filler and an organic filler can be used, and the shape thereof can also be powder, granular, plate-like, fibrous, whisker-like or the like.

As the inorganic filler, an inorganic filler, a metal filler,
Ceramics-based fillers and the like can be used. Examples of the inorganic filler include silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice, oxides such as pumice balloon, aluminum hydroxide, magnesium hydroxide, hydroxides such as basic magnesium carbonate, calcium carbonate, Magnesium carbonate, dolomite, carbonate such as dawsonite, calcium sulfate, barium sulfate, ammonium sulfate, sulfate or sulfite such as calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, calcium silicate, Silicates such as montmorillonite, bentonite,
Carbons such as carbon black, graphite, carbon fibers and hollow carbon spheres, molybdenum sulfide, boron fibers, zinc borate, barium metaborate, calcium borate, sodium borate and the like can be mentioned.

Further, as the metal-based filler, a metal element, a metal compound,
Powders and granules such as alloys, metal fibers and metal whiskers are used. Specifically, zinc, copper, iron,
Metal elements such as lead, aluminum, nickel, chromium, titanium, manganese, tin, platinum, tungsten, gold, magnesium, cobalt, strontium and oxides of these metals, alloys such as stainless steel, solder, brass, aluminum fibers , Stainless steel fibers, copper fibers, brass fibers, nickel fibers, potassium titanate fibers, and other metal fibers such as single metal fibers and alloy fibers, and metal whiskers corresponding to these.

Furthermore, examples of the ceramic-based filler include powders of silicon carbide, silicon nitride, zirconia, aluminum nitride, titanium carbide and the like, granules, fibers, and whiskers.

On the other hand, as the organic filler, for example, shell fiber such as fir shell, wood powder, cotton, jute, paper strip, cellophane piece, aromatic polyamide fiber, cellulose fiber, nylon fiber, polyester fiber, polypropylene fiber, thermosetting Examples of the resin include powdery resin.

These fillers may be used alone or in combination of two or more.

In the composition of the present invention, it is necessary to use the thermoplastic resin as the component (A) and the filler as the component (B) in a weight ratio of 10:90 to 95: 5. If the amount of the filler used is less than the above range, the effect of its addition is not sufficiently exerted and a composition having desired physical properties cannot be obtained, and if the amount is more than the above range, the moldability and the appearance of the molded product become poor. .

In the composition of the present invention, a combination of the polyorganosiloxane as the component (C) and the N-alkyl-substituted or alkylol-substituted ammonium salt of the organic fatty acid as the component (D) is used as the surface treatment agent for the filler. Examples of the polyorganosiloxane of the component (C) include compounds represented by the general formula (At least one of R ¹ to R ⁸ in the formula is a hydrogen atom,
A polar group or an organic residue having a polar group, the rest being an alkyl group, an alkoxy group, an aryl group or an aryloxy group, and n is the number of repeating units), and at least one active hydrogen atom in the molecule Alternatively, those having a polar group are preferably used.

Examples of the polar group include a hydroxyl group, an amino group,
Examples thereof include an epoxy group, a carboxyl group, a sulfonic acid group, a mercapto group, an acryl group, and a vinyl group. Specific examples of preferable polyorganosiloxane used as the component (C) include polymethylhydrosiloxane and polydimethylsiloxane in which any one or more of one end, both ends and side chains are substituted with the polar group. Examples thereof include derivatives.

These polyorganosiloxanes may be used alone or in combination of two or more, and the amount thereof is 0.1 to 3% by weight based on the filler of the component (B).
It is selected in the range of. If this amount is less than 0.1% by weight, the effect of the surface treatment of the filler will not be sufficiently exerted, and a composition having desired physical properties cannot be obtained. If it exceeds 3% by weight, the impact resistance and surface gloss of the composition will not be achieved. Etc. tend to decrease.

On the other hand, as the component (D), at least one selected from organic fatty acids, metal salts of organic fatty acids, N-alkyl-substituted ammonium salts of organic fatty acids, and N-alkylol-substituted ammonium salts is used. Among them, especially N-alkyl-substituted ammonium salts of organic fatty acids and N-
Alkyrol-substituted ammonium salts are preferred. The organic fatty acid in the organic fatty acid and the alkyl-substituted ammonium salt or the N-alkylol-substituted ammonium salt of the organic fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and may have a carboxyl group in the molecule. It may be a polycarboxylic acid containing two or more. Specific examples of such organic fatty acids include lauric acid, myristic acid, palmitic acid, suaric acid, isostearic acid, behenic acid, oleic acid, ricinoleic acid, linoleic acid, relenonic acid, coconut oil fatty acid, beef tallow fatty acid, castor oil. Fatty acids, tall oil fatty acids and the like can be mentioned. Specific examples of the metal salt of organic fatty acid include calcium stearate, magnesium stearate, zinc stearate, calcium laurate, magnesium laurate, zinc laurate and the like.

Further, as ammonium salts of these organic fatty acids,
General formula (Z in the formula is a residue of a chain portion of an organic fatty acid, R ⁹ , R ¹⁰
And R ¹¹ is at least one is an alkyl group or an alkylol group, and the rest is a hydrogen atom, an alkyl group or an alkylol group). Used. Specific examples of such ammonium salt include mono-, di- or tri-
N-alkyl-substituted ammonium salts such as methylammonium salt, ethylammonium salt, propylammonium salt and butylammonium salt, N-substituted alkylolammonium salts such as mono-, di- or tri-ethanolammonium salt, propanolammonium salt and butanolammonium salt. Is mentioned. When the organic fatty acid is a polycarboxylic acid, all of the carboxyl groups may form the ammonium salt, or a part thereof may form the ammonium salt.

These ammonium salts of organic fatty acids may be used alone or in combination of two or more, and the amount thereof is 0.1 to the filler of the component (B).
It is selected in the range of 3% by weight. The amount used is 0.1% by weight
If the amount is less than the above, the effect of treating the filler is not sufficiently exhibited, and a composition having desired physical properties cannot be obtained. If the amount exceeds 3% by weight, impact resistance and surface gloss tend to be lowered.

The method of surface-treating the filler of the component (B) using the components (C) and (D) is not particularly limited as long as it is a dry treatment method, and the surface treatment is performed by a commonly used method. However, from the viewpoint that the temperature and the processing speed can be arbitrarily changed, a method of adding the components (C) and (D) to the filler and mixing and stirring the mixture in a Henschel mixer is preferable. In the present invention, by using the component (C) and the component (D) together as a surface treatment agent, it is possible to treat the primary particles even in such a dry treatment method, and to uniformly disperse the particles individually. Can be surface treated.

At this time, if desired within the range not impairing the object of the present invention,
Other commonly used surface treatment agents can also be used in combination. Examples of other surface treatment agents include silane coupling agents, titanate coupling agents, silica powder, other silicone oils, higher fatty acids, higher alcohols and waxes. Among these, silane coupling agents and titanate coupling agents are preferable. These surface treatment agents may be used alone or in combination of two or more.

In the composition of the present invention, a chemical modifier may be blended, if desired, for the purpose of improving the compatibility between the matrix resin and the filler. Examples of the chemical modifier include modified polyolefin, low molecular weight polypropylene, and oxidized low molecular weight polypropylene.

Further, in the composition of the present invention, if desired, various additives usually used in the resin composition, for example, a lubricant, a colorant,
Stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, plasticizers and the like can be added.

The thermoplastic resin composition of the present invention comprises a predetermined amount of the thermoplastic resin of the component (A), a filler of the component (B) which has been surface-treated with the components (C) and (D) in advance, and if desired. It can be prepared by melt-kneading various additive components to be used according to a conventional method to form a composite. Melt kneading can be performed by, for example, a method using a Henschel mixer, a single-screw or twin-screw extruder, a Banbury mixer, a roll or the like, and other conventional methods, but particularly using a Henschel mixer, an extruder, a Banbury mixer. Is preferred.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The invention is in no way limited by these examples.

In addition, each physical property was evaluated as follows.

(1) Impact resistance Izod impact strength (notched) is ASTM D25
It was determined according to 6.

(2) Tensile elongation rate Determined according to ASTM D638.

(3) Glossiness It was determined according to ASTM D523. The test piece was injection molded to prepare a 100 × 100 × 3 mm # 1000 gloss surface plate and used.

(4) Moldability With the injection molding machine, set the cylinder temperature for each resin, and evaluate the moldability when molding a 100 x 100 x 1 mm plate at an injection pressure of 40 kg / cm ² according to the following symbols. did.

◯: Good molding, Δ: Partly short shot ×: Short shot The test pieces used for the evaluation of the physical properties are the Nissei Plastic Industry Co., Ltd.
Manufactured by an FS-150S injection molding machine, and molded at the following cylinder temperature.

Resin type Cylinder temperature (° C) PP 200 HDPE 200 HIPS 200 6-PA 240 PC 270 PBT 230 In addition, the following components were used.

(A) Thermoplastic resin PP: Idemitsu polypropylene (M13, d0.901
g / cm ³ ) HDPE: Idemitsu Polyethylene (M16, d 0.97 g /
cm ³⁾ HIPS: Idemitsu Polystyrene (M14) 6-PA: Kaneka 6-nylon, MC102 PC: Idemitsu Polycarbonate (Mw25,000) PBT: Mitsubishi Kasei polybutylene terephthalate, Nobaduru 5010 (B) Filler heavy calcium carbonate A: Weight Calcium carbonate, specific surface area 31,000
0 cm ² / g heavy carbon cal B: heavy calcium carbonate, specific surface area 12,50
0 cm ² / g light carbon calcium: light calcium carbonate, specific surface area 50000
0 cm ² / g Burr sulfate: Precipitable barium sulfate, particle size 1.5 μm ZnO: Particle size 1.5 μm Talc: Particle size 3.8 μm Zn: Particle size 13 μm GF: Glass fiber, diameter 13 μm, length 3 mm The surface area is measured by a powder specific surface area measuring device (air permeation method) manufactured by Shimadzu Corporation, and the particle size is calculated by Shimadzu Corporation.
Manufactured by SA-CP2 particle size distribution analyzer.

(C) Polyorganosiloxane A: Polymethylhydrosiloxane (commercially available product) B: Epoxy modified polydimethylsiloxane at both ends (commercially available product) C: Epoxy modified polydimethylsiloxane at one end (commercially available product) D: Side chain epoxy modified polydimethyl Siloxane (commercial item) E: Both-terminal amine-modified polydimethylsiloxane (commercial item) (D) Organic fatty acid ammonium salt F: Tall oil fatty acid alkylol ammonium salt (commercial item) Examples 1-40, Comparative Examples 1-20 The filler was surface-treated in advance by a Henschel mixer using the types and amounts of the filler and treating agent shown in Table 1.

The type and amount of the thermoplastic resin shown in Table 1 and the surface-treated filler were kneaded at a barrel temperature below by using a PCM45-II twin-screw extruder manufactured by Ikegai Iron and Steel Co., Ltd. and pelletized. To prepare a thermoplastic resin composition. The physical properties of this product are shown in the table.

Resin type Barrel temperature (° C) PP 200 HDPE 200 HIPS 200 6-PA 240 PC 270 PBT 230 [Effects of the Invention] According to the present invention, the surface treatment of the filler is carried out by using the polyorganosiloxane and the N-alkyl-substituted or alkylol-substituted ammonium salt of the organic fatty acid in combination as the surface-treatment agent, thereby treating the filler. The thermoplastic resin composition obtained by blending the compound (1) has excellent impact resistance, has a high tensile elongation, and has excellent moldability and surface gloss, and thus has excellent practical physical properties.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Hideo Okawa Hideo Okawa, No. 104 Shimohosoya Tojo, Yoshimi-cho, Hiki-gun, Saitama Calpe Industry Co., Ltd.

Claims (1)

[Claims] 1. A mixture of (A) 10 to 95% by weight of a thermoplastic resin and (B) 90 to 5% by weight of at least one selected from an inorganic filler and an organic filler, B)
Based on the weight of the components, (C) 0.1 to 3% by weight of polyorganosiloxane and (D) organic fatty acid, organic fatty acid metal salt, organic fatty acid N-alkyl-substituted ammonium salt and N-alkylol-substituted ammonium salt A thermoplastic resin composition containing 0.1 to 3% by weight of at least one selected from the above.