JPH06306253A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a molded article of an engineering plastic, etc., having improved impact resistance, fluidity and appearance without impairing the physical properties such as heat-resistance and mechanical properties of the resin. CONSTITUTION:The thermoplastic resin composition is composed of (1) 50-99wt.% of a thermoplastic resin and (2) 1-50wt.% of a specific graft copolymer. The graft copolymer is composed of 5-95wt.% of a thermoplastic elastomer segment and 95-5wt.% of a vinyl polymer segment. The copolymer has a poly- phase structure consisting of a continuous phase composed of one of the segments and a disperse phase composed of the other segments and dispersed in the continuous phase in the form of fine particles having diameter of 0.01-5mum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having improved impact resistance, surface properties and molding processability of a thermoplastic resin, particularly engineering plastics. The composition can be used in a wide range of fields such as electric and electronic parts, mechanical parts and automobile parts.

[0002]

Engineering plastics such as polyester resins, polyamide resins, polyacetal resins, polyphenylene ether resins, polycarbonate resins, polyphenylene sulfide resins, etc.
It is widely used as a molding material in various fields due to its excellent heat resistance and mechanical properties. However, these engineering plastics have a problem in impact resistance or fluidity, and improvement thereof is required. For example, as a method for improving the impact resistance of polyester resins, JP-A-51-144452 and JP-A-52-3 are known.
No. 2045, Japanese Patent Laid-Open No. 53-117049 and the like disclose a method of blending a copolymer of α-olefin and α, β-unsaturated glycidyl ester. Further, JP-A-1-132661 discloses a method for improving fluidity by blending an olefin polymer with a polycarbonate resin.

[0003]

However, although engineering plastics such as polyester resins are blended with a copolymer of α-olefin and α, β-unsaturated acid glycidyl ester to improve impact resistance,
The heat resistance and fluidity are extremely reduced. In addition,
Since there is no compatibility between the carbonyl-based resin and the olefin-based polymer at all, there is a problem that the phase-separation is greatly caused by simply blending and the fluidity is improved but the mechanical properties are deteriorated. Is desired.

The present invention has been made in view of the above conventional problems. The purpose is to improve properties such as impact resistance and fluidity without deteriorating the physical properties such as heat resistance and mechanical properties that thermoplastic resins such as engineering plastics originally had. It is to provide a plastic resin composition.

[0005]

In order to achieve the above object, the thermoplastic resin composition of the present invention comprises (1) 50 to 99% by weight of a thermoplastic resin, (2) a thermoplastic elastomer segment and vinyl. 1 to 50% by weight of a graft copolymer having a multiphase structure in which one segment is a continuous phase formed by the other segment and a dispersed phase of fine particles is formed in the continuous phase formed by the other segment. is there.

Next, each component of the present invention will be described in detail. First, as the thermoplastic resin used in the present invention, engineering plastics such as polyester resins, polyamide resins, polyacetal resins, polyphenylene ether resins, polycarbonate resins, polyphenylene sulfide resins, etc. Su, AS, ABS,
Examples include styrene resins such as high impact polystyrene (HIPS), acrylic resins such as MMA, vinyl resins such as vinyl chloride resins, and olefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene. it can. Among them, engineering plastics are preferable, and polyester resin, polyamide resin, polyacetal resin, and polyphenylene sulfide resin resin are particularly preferable from the viewpoint of improving impact resistance. From the viewpoint of improving the fluidity, polyphenylene ether resin, polycarbonate resin, and ABS are particularly preferable.

Next, the thermoplastic elastomer which is a constituent of the graft copolymer used in the present invention means, specifically, thermoplastic polyolefin type elastomer, polystyrene type elastomer, polyurethane type elastomer and polyester. Examples thereof include a system elastomer, a polyamide system elastomer, and a polyvinyl chloride system elastomer. Among these thermoplastic elastomers, polyolefin-based elastomers, polystyrene-based elastomers, and polyurethane-based elastomers are preferable because of their high impact resistance and fluidity improving effects.

The polyolefin elastomer as the thermoplastic elastomer used in the present invention comprises an olefin copolymer rubber and a crystalline olefin polymer,
Further, those in which these are bonded and crosslinked are preferable. The olefin-based copolymer rubber constituting the polyolefin-based elastomer is essentially a non-polymer composed of a copolymer of at least one polyene (usually a diene) and two or more non-polar α-olefin monomers. Is a crystalline rubber-like copolymer,
Ethylene-propylene-diene copolymer rubber (EPD
M) is preferred.

The crystalline olefin polymer constituting the polyolefin elastomer is obtained by polymerizing a non-polar α-olefin monomer such as ethylene, propylene, butene-1, pentene-1 by a conventional method. Is a crystalline polymer. Typically, polyethylene and its copolymers, polypropylene and its copolymers, polybutene, etc. are mentioned, but polypropylene and its copolymers are preferable.

The ratio of the olefin copolymer rubber and the crystalline olefin copolymer is usually 40 to 80% by weight of the olefin copolymer rubber, and the crystalline olefin polymer, based on the total amount of both components. Is preferably 60 to 20% by weight. Both components are kneaded at a melting point or higher to form a thermoplastic polyolefin elastomer.

In order to impart properties useful as an elastomer, it is preferable to vulcanize the olefin copolymer rubber. In this case, the kneading treatment is carried out by using a peroxide or a phenol.
It is carried out in the presence of a vulcanizing agent such as resin and sulfur.

The thermoplastic polyolefin-based elastomer may contain other components as long as the rubber properties and the like are not impaired. Specifically, for example, oil, filler, carbon black, stabilizer and the like.

The polystyrene elastomer as the thermoplastic elastomer used in the present invention is at least 1
A block copolymer comprising a polymer of one vinyl aromatic monomer and a polymer of at least one conjugated diene,
It may be linear or radial. Also,
The polymer containing the conjugated diene may be a random copolymer with a small amount of a vinyl aromatic monomer, or the so-called taper type block copolymer in which the amount of the vinyl aromatic monomer is temporarily increased. It doesn't matter.

The structure of the block copolymer is not particularly limited, and any of (AB) n type, (AB) n-A type and (A, B) n-C type can be used. In the formula, A
Is a polymer of vinyl aromatic monomer, B is a polymer of conjugated diene, C is a coupling agent residue, and n is an integer of 1 or more. In addition, in the above block copolymer, it is also possible to use a block copolymer in which a conjugated diene portion is hydrogenated.

Examples of the vinyl aromatic monomer constituting the polystyrene elastomer used in the present invention include styrene, α-styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl naphthalene and the like. Although used, styrene is particularly preferable. Further, as the conjugated diene, 1,3-butadiene, isoprene, piperylene, etc. are used, and among them, 1,3
-Butadiene and isoprene are particularly preferred.

The weight average molecular weight of the block copolymer is 1
It is preferably 50,000 to 800,000, more preferably 50,000 to 500,000. The content of the vinyl aromatic monomer in the block copolymer is preferably 5 to 60% by weight, more preferably 20 to 50% by weight.

The polyurethane elastomer used as the thermoplastic elastomer in the present invention means a long-chain polyolefin.
, Short chain polyol, short chain glycol, diisocyanate
It is a polymer obtained by a polyaddition reaction using glutamine and the like as a raw material through a urethane bond in the molecule.

The long-chain polyol, which is the raw material of the thermoplastic polyurethane elastomer, includes poly (1,4-butylene adipate) and poly (1,6-hexane adipate).
G), polycaprolactone, polyethylene glycol,
Examples include polypropylene glycol and polyoxytetramethylene glycol. The short-chain glycols include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like, and further diisocyanates include tolylene diisocyanate, 4,4. -Diphenylmethane disocinate, hexamethylene diisocyanate, isophorone diisocyanate and the like. The long-chain polyol and diisocyanate form a soft segment, and the short-chain glycol and diisocyanate form a hard segment.

The preferred molecular weight of the thermoplastic polyurethane elastomer is preferably 5,000 to 500,000.
It is 0, and more preferably 10,000 to 300,000. Specific examples of the vinyl-based monomer used in the present invention include styrene, nucleus-substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, α-substituted styrene such as α.
-Vinyl aromatic monomers such as methylstyrene and α-ethylstyrene, acrylic acid or methacrylic acid, alkyl esters of acrylic acid or methacrylic acid having 1 to 7 carbon atoms, for example, methyl- and ethyl (meth) acrylic acid. (Meth) acrylic acid ester monomers such as-, propyl-, isopropyl-, butyl-, glycidyl-, 2-hydroxyethyl, 2-hydroxypropyl-, vinyl cyanide monomers such as acrylonitrile or methacrylonitrile, Vinyl ester monomers such as vinyl acetate and vinyl propionate, (meth) acrylamide monomers such as acrylamide and methacrylamide, maleimides such as maleic anhydride, phenylmaleimide and cyclohexylmaleimide, maleic acid mono- and di- Vinyl monomers such as esters. Among these, vinyl aromatic monomers, (meth) acrylic acid ester monomers, vinyl cyanide monomers and vinyl ester monomers are particularly preferably used.

Particularly, vinyl aromatic monomer or (meth)
A vinyl-based polymer obtained by polymerizing 50% by weight or more of an acrylic acid ester monomer is preferable because it has good dispersibility when the graft copolymer is blended with another polymer.
Further, a vinyl-based polymer obtained by copolymerizing a monomer having a functional group such as an epoxy group, a hydroxyl group, an acid (anhydride group), and an amino group together with the above-mentioned monomer is further different from that of the graft copolymer. This is preferable because the dispersibility in the polymer is improved and the effect of modifying various functions is improved. Further, from the viewpoint of heat resistance, a vinyl copolymer composed of 50 to 100% by weight of a vinyl aromatic monomer and 0 to 50% by weight of a vinyl cyanide monomer is preferable.

The graft copolymer used in the present invention is
A vinyl polymer segment or a thermoplastic elastomer segment, which is a different component from the thermoplastic elastomer segment or the vinyl polymer segment, is uniformly dispersed in a continuous phase formed by the thermoplastic polymer segment or the vinyl polymer segment. The dispersed segment may be either a thermoplastic elastomer or a vinyl polymer,
From the viewpoint of moldability, a vinyl polymer is preferable.

The dispersed segments are fine particles, and the particle diameter thereof is preferably 0.01 to 5 μm, more preferably 0.05 to 1 μm. When the particle diameter of the dispersed segment is less than 0.01 μm or exceeds 5 μm, the compatibility of the graft copolymer with the thermoplastic resin becomes insufficient, and for example, the appearance is deteriorated or the mechanical properties are deteriorated, which is preferable. Absent.

The number average degree of polymerization of the vinyl polymer constituting the graft copolymer used in the present invention is 5 to 10,000,
Preferably 10-5000, most preferably 100-2
It is 000. When the number average degree of polymerization is less than 5, the thermoplastic resin such as polyester resin may have poor heat resistance and a poor appearance when blended, which is not preferable. Further, if the number average degree of polymerization exceeds 10,000, the melt viscosity is high, and when blended, the moldability of a thermoplastic resin such as a polycarbonate resin is deteriorated or the surface gloss is deteriorated, which is not preferable. .

The graft copolymer used in the present invention preferably comprises 5 to 95% by weight of a thermoplastic elastomer segment, more preferably 20 to 90% by weight, most preferably 50 to 90% by weight. . Therefore, the vinyl polymer segment is preferably 95 to 5% by weight,
More preferably 80 to 10% by weight, most preferably 5
It is 0 to 10% by weight.

When the thermoplastic elastomer segment is less than 5% by weight, the flexibility is insufficient and the impact resistance improving effect when blended is small, which is not preferable. Further, if the thermoplastic elastomer segment exceeds 95% by weight, the effect of improving heat resistance and moldability is insufficient, which is not preferable.

The grafting method for producing the graft copolymer used in the present invention may be any of well-known methods such as chain transfer method and ionizing radiation irradiation method, but the most preferable method is Is the method shown below. This is because the grafting efficiency is high and secondary agglomeration due to heat does not occur, so that the various physical properties are excellent and the manufacturing method is simple.

The method for producing the graft copolymer will be described in detail below. That is, 100 parts by weight of thermoplastic elastomer particles are suspended in water. Separately, from 5 to 400 parts by weight of at least one vinyl monomer, one or a mixture of two or more radically polymerizable organic peroxides represented by the following general formula 1 or 2, Radical polymerization of 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl monomer and a radical polymerization initiator having a decomposition temperature of 40 to 90 ° C. for obtaining a half-life of 10 hours. 0.01-10 with respect to 100 parts by weight in total with the organic peroxide.
Parts by weight and a solution of the dissolved parts are added. The particles of the thermoplastic elastomer are impregnated with the vinyl monomer, the radical-polymerizable organic peroxide and the radical-polymerization initiator by heating under the condition that decomposition of the radical-polymerization initiator does not substantially occur. The temperature of this aqueous suspension is raised and the vinyl monomer and the radically polymerizable organic peroxide are copolymerized in the particles of the thermoplastic elastomer to obtain a grafted precursor.

In the grafting precursor of the present invention, the vinyl polymer blended therein preferably contains 0.003 to 0.73% by weight of active oxygen. If the amount of active oxygen is less than 0.003% by weight, the grafting ability of the graft precursor is extremely reduced, which is not preferable. On the other hand, if it exceeds 0.73% by weight, gel is often generated during grafting, which is not preferable. The amount of active oxygen in this case is calculated by extracting the vinyl polymer from the grafted precursor of the present invention by solvent extraction and determining the amount of active oxygen of this vinyl polymer by the odometry method. be able to.

Next, 100 to 30 of the grafted precursor is added.
The graft copolymer of the present invention can be obtained by kneading under melting at 0 ° C. At this time, a graft copolymer can also be obtained by separately mixing a thermoplastic elastomer or a vinyl polymer with the grafting precursor and kneading them under melting. Most preferred is a graft copolymer obtained by kneading a grafting precursor under melting.

The radical-polymerizable organic peroxide represented by the above general formula 1 is a compound represented by the following formula.

[0031]

[Chemical 1]

In the formula, R ₁ is a hydrogen atom or has 1 to 2 carbon atoms.
Alkyl group, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each an alkyl group having 1 to 4 carbon atoms, R ₅ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or a carbon group. The cycloalkyl group of the numbers 3 to 12 is shown. m is 1 or 2.

The radical-polymerizable organic peroxide represented by the general formula 2 is a compound represented by the following formula.

[0034]

[Chemical 2]

In the formula, R ₆ is a hydrogen atom or has 1 to 4 carbon atoms.
Alkyl group, R ₇ is a hydrogen atom or a methyl group, R ₈ and R ₉ are each an alkyl group having 1 to 4 carbon atoms, R ₁₀ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or a carbon group. The cycloalkyl group of the numbers 3 to 12 is shown. n is 0, 1 or 2.

Specific examples of the radical-polymerizable organic peroxide represented by the general formula 1 include t-butylperoxyacryloyloxyethyl carbonate; t-amylperoxyacryloyloxyethyl carbonate. -To; t-hexyl peroxyacryloyloxyethyl carbonate;
1,1,3,3-Tetramethylbutylperoxyacryloyloxyethyl carbonate; cumylperoxyacryloyloxyethyl carbonate; p-isopropyl cumylperoxyacryloyloxyethyl carbonate ;
t-Butylperoxymethacryloyloxyethyl carbonate; t-Amylperoxymethacryloyloxyethyl carbonate; t-hexylperoxymethacryloyloxyethyl carbonate; 1,1,3,3- Tetramethylbutylperoxymethacryloyloxyethyl carbonate; cumylperoxymethacryloyloxyethyl carbonate; p-isopropyl cumylperoxymethacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxy Ethyl carbonate-bonate; t-
Amyl peroxyacryloyloxy ethoxyethyl carr
Carbonate; t-hexylperoxyacryloyloxyethoxyethyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate; cumylperoxyacryloyloxyethoxyethyl Carbonate; p-Isopropylcumylperoxyacryloyloxyethoxyethyl carbonate;
t-butylperoxymethacryloyloxyethoxyethyl carbonate; t-amylperoxymethacryloyloxyethoxyethyl carbonate; t-hexylperoxymethacryloyloxyethoxyethyl carbonate;
1,1,3,3-Tetramethylbutylperoxymethacryloyloxyethoxyethyl carbonate; cumylperoxymethacryloyloxyethoxyethyl carbonate
P-isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate; t-butylperoxyacryloyloxyisopropyl carbonate; t-amylperoxyacryloyloxyisopropyl carbonate; t-hexyl Peroxyacryloyloxy isopropyl carbonate; 1,1,3,3-tetramethylbutyl peroxyacryloyloxy isopropyl carbonate; cumyl peroxyacryloyloxy isopropyl carbonate; p-isopropyl chloride Milperoxyacryloyloxy isopropyl carbonate; t-butyl peroxymethacryloyloxy isopropyl carbonate
T; amylperoxymethacryloyloxyisopropyl carbonate; t-hexylperoxymethacryloyloxyisopropyl carbonate; 1,1,3,3-
Examples thereof include tetramethylbutylperoxymethacryloyloxyisopropyl carbonate; cumylperoxymethacryloyloxyisopropyl carbonate; p-isopropylcumylperoxymethacryloyloxyisopropyl carbonate.

Further, as the compound represented by the general formula 2, t-butylperoxyallyl carbonate; t-
Amyl peroxyallyl carbonate; t-hexyl peroxyallyl carbonate; 1,1,3,3-tetramethylbutyl peroxyallyl carbonate; p-menthane peroxyallyl carbonate; Cumyl peroxyallyl carbonate; t-butyl peroxy methallyl carbonate; t-amyl peroxy methallyl carbonate
T; t-hexyl peroxymethalyl carbonate;
1,1,3,3-Tetramethylbutylperoxymethallyl carbonate; p-menthane peroxymethallyl carbonate
Bonate; cumyl peroxymethalyl carbonate; t
-Butylperoxyallyloxyethyl carbonate; t
-Amyl peroxyallyloxyethyl carbonate; t
-Hexyl peroxyallyloxyethyl carbonate;
t-Butylperoxymetallyloxyethyl carbonate
T; t-amyl perxyl metalyloxyethyl carbonate
T-hexyl peroxymetalloxyethyl carbonyl; t-butyl peroxyallyloxy isopropyl carbonyl; t-amyl peroxyallyloxy isopropyl carbonyl; t-hexyl peroxyallyloxy isopropyl carbonyl Carbonate; t-Butylperoxymetallyloxyisopropyl carbonate; t-Amylperoxymetalloyloxyisopropyl carbonate; t-Hexylperoxymetalloyloxyisopropyl carbonate
And the like.

Among them, t-butylperoxyacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t-butylperoxyallylcarbonyl carbonate; t-butylperoxy It is a methallyl carbonate.

The thermoplastic resin composition of the present invention can be obtained by blending 50 to 99% by weight of the above-mentioned (1) thermoplastic resin with 1 to 50% by weight of (2) the graft copolymer. When the thermoplastic resin content is less than 50% by weight, that is, when the graft copolymer content exceeds 50% by weight, the fluidity of the thermoplastic resin composition is mainly lowered. On the other hand, when the thermoplastic resin exceeds 99% by weight, that is, when the graft copolymer is less than 1% by weight, impact resistance of the thermoplastic resin composition is not particularly improved.

In the present invention, the resin component 100 containing the above-mentioned (1) thermoplastic resin and (2) graft copolymer.
An inorganic filler of less than 150 parts by weight can be blended with respect to parts by weight.

As the above-mentioned inorganic filler, powdery, flat, scale-like, needle-like, spherical or hollow and fibrous ones can be used. Specifically, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite,
Powder and granular filler such as silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black; mica,
Glass plate, sericite, pyrophyllite, metal foil such as aluminum flake, flat plate-like or scale-like filler such as graphite; Silas balun, metal balun, glass bal
Hollow fillers such as carbon and pumice; glass fiber, carbon fiber,
Examples thereof include graphite fibers, whiskers, metal fibers, silicon carbide-bite fibers, asbestos, and mineral fibers such as wstonite.

If the blending amount of this inorganic filler exceeds 150 parts by weight, the fluidity of the molded article will be reduced, which is not preferable.
The surface of the inorganic filler is stearic acid, oleic acid, palmitic acid or metal salts thereof, paraffin wax, polyethylene wax or modified products thereof,
Surface treatment is preferably performed using organic silane, organic borane, organic titanate, or the like.

The resin composition of the present invention has a temperature of 120 to 35.
It is produced by melting and mixing at 0 ° C, preferably 150 to 330 ° C. If the temperature is lower than 120 ° C., the melting is incomplete, the melt viscosity is high, the mixing becomes insufficient, and phase separation or layered peeling appears in the molded product, which is not preferable. On the other hand, if it exceeds 350 ° C., the resin to be mixed is decomposed or gelated, which is not preferable.

As a method of melting and mixing, Banbury
It can be carried out by a commonly used kneader such as a mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, or a roll. In the present invention, within a range not departing from the gist of the present invention, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, halogen-based and phosphorus-based organic flame retardants, organic fillers such as wood powder, and antioxidants. It is possible to add additives such as an ultraviolet ray inhibitor, a lubricant, a dispersant, a coupling agent, a foaming agent, a cross-linking agent, a colorant, and other thermoplastic resins.

[0045]

The present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples. Reference Example 1 (Production of Graft Copolymer (2A)) 2500 g of pure water was placed in a stainless steel autoclave having a volume of 5 liters, and 2.5 g of polyvinyl alcohol was further dissolved as a suspending agent. In this, as a thermoplastic elastomer, a thermoplastic polyolefin elastomer
700 g of "Santoprene 101-80" (trade name, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) was put and stirred and dispersed. Separately, benzoyl peroxide “Nypa-B” (trade name, manufactured by NOF CORPORATION) as a radical polymerization initiator 1.5
g, t-butylperoxymethacryloyloxyethyl carbonate 6 g as a radical-polymerizable organic peroxide was dissolved in 300 g of styrene as a vinyl monomer, and this solution was charged into the autoclave. It was stirred.

Then, the autoclave is heated to 60 to 65 ° C. and stirred for 2 hours to change the vinyl monomer containing the radical polymerization initiator and the radical polymerizable organic peroxide to a thermoplastic polyolefin elastomer. -Impregnated in the particles. Subsequently, the temperature was raised to 80 to 85 ° C., and the temperature was maintained for 7 hours to complete the polymerization, followed by washing with water and drying to obtain a grafted precursor (2a). The styrene polymer in this grafted precursor (2a) was extracted with ethyl acetate to give G
It was 850 when the number average degree of polymerization was measured by PC. Further, the active oxygen content of the styrene polymer was measured by the iodometry method and found to be 0.13% by weight.

Next, this grafting precursor (2a) is extruded at 200 ° C. by a Labo Plastomill uniaxial extruder (manufactured by Toyo Seiki Seisakusho Ltd.) to carry out a grafting reaction to obtain a graft copolymer (2A). Obtained.

When the graft copolymer (2A) was observed with a scanning electron microscope "JEOL JSM T300" (manufactured by JEOL Ltd.), the particle size was 0.3 to 0.
It was a multiphase structure in which a spherical resin of 5 μm was uniformly dispersed.

At this time, the graft efficiency of the styrene polymer was 56.1% by weight. Reference Example 2 (Production of Graft Copolymer (2B)) In Reference Example 1, 300 g of styrene monomer as a vinyl monomer was mixed with 210 g of styrene monomer and 90 g of acrylonitrile monomer, Further, 1.5 g of benzoyl peroxide was added to 3 g of di-3,5,5-trimethylhexanoyl peroxide "paroyl 355" (trade name, manufactured by NOF CORPORATION), and t-butylperoxymethacryloyloxyethyl carbohydrate. 6g of Bonnet was changed to 30g, and α-methylstyrene dimer "Nofuma-MSD" (trade name, manufactured by NOF CORPORATION) as a molecular weight modifier
Reference example 1 was repeated except that 0.3 g was used, and the grafted precursor (2b) and the graft copolymer (2B) were obtained.
Got

At this time, the number average degree of polymerization of the styrene-acrylonitrile copolymer in the grafted precursor (2b) was 1200 and the amount of active oxygen was 0.64% by weight. The graft efficiency of the styrene-acrylonitrile copolymer in the graft copolymer (2B) was 78.7%. Furthermore, the average particle diameter of the resin dispersed in this graft copolymer (2B) was 0.3 to 0.5 μm.

Reference Example 3 (Production of Graft Copolymer (2C)) In Reference Example 1, the thermoplastic polyolefin-based elastomer was replaced by a thermoplastic polystyrene-based elastomer "TR10".
00 "(trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.)
Butyl peroxymethacryloyloxyethyl carbonate
A graft copolymer (2C) was obtained by repeating Reference Example 1 except that 6 g was changed to 0.3 g.

At this time, the number average degree of polymerization of the styrene polymer in the grafted precursor (2c) was 850, and the amount of active oxygen was 0.06% by weight. Further, the graft copolymer (2
The graft efficiency of the styrene polymer in C) was 45.4%. Furthermore, the average particle size of the resin dispersed in the graft copolymer (2C) was 0.2 to 0.4 μm.

Reference Example 4 (Production of Graft Copolymer (2D)) In Reference Example 3, 300 g of styrene monomer as a vinyl monomer was mixed with 240 g of styrene monomer and 60 g of glycidyl methacrylate monomer. A graft copolymer (2D) was obtained by repeating Reference Example 3 except that the amount was changed.

At this time, the number average degree of polymerization of the styrene-glycidyl methacrylate copolymer in the grafting precursor (2d) was 1600, and the amount of active oxygen was 0.11% by weight. The graft efficiency of the styrene-glycidyl methacrylate copolymer in the graft copolymer (2D) was 61.
It was 2%. Furthermore, the average particle size of the resin dispersed in the graft copolymer (2D) was 0.2 to 0.4 μm.

Reference Example 5 (Production of Graft Copolymer (2E)) In Reference Example 3, the styrene monomer as a vinyl monomer was changed to a methyl methacrylate monomer, and 1-dodecanethio as a molecular weight modifier. Example 3 was repeated, except that 1.5 g of the copolymer was used to obtain a graft copolymer (2E).

At this time, the number average polymerization degree of the methyl methacrylate polymer in the grafting precursor (e) was 600, and the amount of active oxygen was 0.12% by weight. The graft efficiency of the methyl methacrylate polymer in the graft copolymer (2E) was 55.9%. Furthermore, the average particle size of the resin dispersed in this graft copolymer (2E) is 0.
It was 08 to 0.2 μm.

Reference Example 6 (Production of Graft Copolymer (2F)) In Reference Example 1, a thermoplastic polyolefin-based elastomer as the thermoplastic elastomer was replaced with a thermoplastic polyurethane-based elastomer "Kuramiron U3190" (trade name, Kuraray). Example 1 was repeated, except that the graft copolymer (2F) was obtained.

At this time, the number average degree of polymerization of the styrene polymer in the grafted precursor (2f) was 900, and the amount of active oxygen was 0.12% by weight. Further, the graft copolymer (2
The graft efficiency of the styrene polymer in F) was 52.8. Furthermore, the average particle size of the resin dispersed in this graft copolymer (2F) was 0.4 to 0.6 μm.

Reference Example 7 (Production of Blend (2G)) Thermoplastic Polyolefin Elastomer "Santoprene 101-80" (trade name, Mitsubishi Monsanto Kasei Co., Ltd.)
700 g) and styrene polymer "Dialex HF"
-55 "(trade name, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) 30
After dry blending with 0 g, a blended product (2G) was obtained by extrusion at 200 ° C. with a Labo Plastomill uniaxial extruder (manufactured by Toyo Seiki Seisakusho KK).

At this time, the graft efficiency of the styrene polymer in the blend (2G) was 0.1% or less. The average particle size of the resin dispersed in this blend (2G) was 11 to 14 μm.

Reference Example 8 (Production of Blend (2H)) In Reference Example 7, the styrene polymer “DIALEX H” was used.
F-55 "(trade name, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) is a styrene-acrylonitrile copolymer" Sunlex S ".
AN-C "(trade name, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) was repeated to obtain a blended body (2H).

At this time, the graft efficiency of the styrene-acrylonitrile copolymer in the blend (2H) was 0.1.
% Or less. The average particle size of the resin dispersed in this blend (2H) was 12 to 15 μm.

Reference Example 9 (Production of Blend (2I)) In Reference Example 7, a thermoplastic polyolefin elastomer “Santoprene 101-80” (trade name, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) was used as a thermoplastic polystyrene elastomer. TR1000 "(trade name, Japan Synthetic Rubber Co., Ltd.
A blended body (2I) was obtained by repeating Reference Example 7, except that the blended product was changed to (Production).

At this time, the graft efficiency of the styrene polymer in the blend (2I) was 0.1% or less. The average particle size of the resin dispersed in this blend (2I) was 10 to 12 μm.

Reference Example 10 (Production of Blend (2J)) In Reference Example 9, the styrene polymer “DIALEX H” was used.
F-55 "(trade name, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) was changed to methyl methacrylate polymer" Delpet 50N "(trade name, Asahi Kasei Kogyo Co., Ltd.), and blended by repeating Reference Example 9 ( 2J) was obtained.

At this time, the graft efficiency of the methyl methacrylate polymer in the blend (2J) was 0.1% or less. The average particle size of the resin dispersed in this blend (2J) was 10 to 12 μm.

Reference Example 11 (Production of Blend (2K)) In Reference Example 7, a thermoplastic polystyrene elastomer was used.
Reference Example 9 was repeated except that "SANTOPREN 101-80" (trade name, manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) was changed to thermoplastic polyurethane elastomer "Kuramilon U3190" (trade name, manufactured by Kuraray Co., Ltd.). A blend (2K) was obtained.

At this time, the graft efficiency of the styrene-acrylonitrile copolymer in the blend (2K) was 0.1%.
It was below. The average particle size of the resin dispersed in this blend (2K) was 13 to 15 μm.

Examples 1 to 10 Polybutylene terephthalate (1A) "Duranex 2002" (trade name, manufactured by Polyplastics Co., Ltd.)
(Displayed as PBT in the table) and the graft copolymers (2A) to (2F) obtained in Reference Examples 1 to 6 were dry blended. Then, the mixture was fed to a coaxial twin-screw extruder having a screw diameter of 30 mm set to a cylinder temperature of 250 ° C., and granulated after extrusion. The granulated resin was dried at 110 ° C. for 3 hours, then a test piece was prepared by injection molding, and the following test was performed.

Size of test piece Izod impact test piece 13 mm × 65 mm × 6 mm (with notch) Deflection temperature test piece 13 mm × 130 mm × 6 mm Bending test piece 10 mm × 130 mm × 4 mm The test method is as follows. Is like. (1) Izod impact value (with notch): JIS K7110 (2) Deflection temperature under load: JIS K7207 (3) Bending test: JIS K6758 (4) Fluidity (spiral flow) Molding temperature 220 ° C, 260 ° C, 300 ° C In each of the above, an injection molding machine (manufactured by Tabata Machine Industry Co., Ltd., TS-35)
-FV25 type) with a die having a spiral groove with a width of 4 mm and a thickness of 2 mm, injection speed 95%, injection pressure 1000
Injection molding is performed under the conditions of kg / cm ² and mold temperature of 60 ° C.
The formed spiral length was measured and used as an index of fluidity. (5) Appearance of molded product Regarding the appearance of the molded product, the presence or absence of delamination was visually determined and ranked as follows.

State of layered peeling ⊚: No layered peeling at all, ○: Slightly layered peeling, ×:
Delamination throughout

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[Table 1]

Examples 11 to 20 Instead of the PBT of Examples 1 to 10, polyamide (1
B) "UBE Nylon 1013B" (trade name, manufactured by Toray Industries, Inc.) (displayed as PA in the table), polyacetal (1C) "Duracon M90" (trade name, manufactured by Polyplastics Co., Ltd.), or Table 2 shows an example using polyphenylene sulfide (1D) "Photron KPS" (trade name, manufactured by Polyplastics Co., Ltd.) (displayed as PPS in the table).

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[Table 2]

Examples 21 to 30 Instead of the PBT of Examples 1 to 10, polycarbonate (1E) "Panlite L-1250" (trade name, Teijin Kasei Co., Ltd.) (PC as shown in the table. Display), polyphenylene ether (1F) "Noryl 534J-801" (trade name, manufactured by Nippon D-Plastics Co., Ltd.) (displayed as PPE in the table), or ABS resin (1G) "stylac". ABS 283 "(trade name, Asahi Kasei Corporation)
Table 3 shows an example using (made in the table as ABS).

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[Table 3]

As shown in Tables 1 to 3, Examples 1 to 30
The thermoplastic resin composition is composed of various thermoplastic resins mixed with a certain amount of a graft copolymer having a predetermined multiphase structure. Therefore, each thermoplastic resin composition is excellent in heat resistance shown in deflection temperature under load and mechanical properties shown in bending strength, and also excellent in impact resistance shown in Izod impact value and fluidity shown in spiral flow. ing. Moreover, the appearance of each molded product is good.

Comparative Examples 1 to 10 Instead of the graft copolymers of Examples 1 to 10, blends (2G) to (2K) obtained in Reference Examples 7 to 11 or a thermoplastic polyolefin-based elastomer "Santoprene 101". -80 "(trade name, Mitsubishi Monsanto Kasei Co., Ltd.
(Made in the table as TPO), thermoplastic polystyrene-based elastomer "TR1000" (trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.) (displayed as SBC in the table), thermoplastic polyurethane-based elastomer "Cramiron U319".
Table 4 shows an example using "0" (trade name, manufactured by Kuraray Co., Ltd.) (displayed as TPU in the table).

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[Table 4]

Comparative Examples 11 to 20 Table 5 shows examples in which the blends (2G) to (2K) obtained in Reference Examples 7 to 11 were used instead of the graft copolymers of Examples 11 to 20.

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[Table 5]

Comparative Examples 21 to 20 Table 6 shows examples in which the blends (2G) to (2K) obtained in Reference Examples 7 to 11 were used instead of the graft copolymers of Examples 21 to 30.

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[Table 6]

As shown in Tables 4 to 6, Comparative Examples 1 to 30
In the thermoplastic resin composition, the blend is blended as a polymer with the thermoplastic resin. Therefore, many of the thermoplastic resin compositions have poor impact resistance represented by Izod impact value and poor appearance.

Comparative Examples 31 and 32 PBT was used as the thermoplastic resin and (2D) of Reference Example 4 was used as the graft copolymer, and they were mixed in the proportions shown in Table 7 to obtain thermoplastic resin compositions. The same test as in Example 1 was conducted on this thermoplastic resin composition. The results are shown in Table 7.

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[Table 7]

As shown in Table 7, when the PBT is more than the range of the present invention, that is, when the graft copolymer is too small (Comparative Example 31), the impact strength is not improved. Conversely, PB
When T is less than the range of the present invention, that is, when the amount of the graft copolymer is too large (Comparative Example 32), the bending strength and the deflection temperature under load are lowered and the fluidity is lowered.

From the above results, the graft copolymer comprising the thermoplastic elastomer segment and the vinyl polymer segment exerts a great effect in improving the impact resistance and fluidity of the thermoplastic resin such as engineering plastics. It Therefore, the thermoplastic resin composition of the present invention can improve impact resistance, fluidity and appearance while maintaining heat resistance and mechanical properties as compared with those of Comparative Examples.

[0089]

As described above in detail, the thermoplastic resin composition of the present invention can be used without impairing the physical properties such as heat resistance and mechanical properties that are inherent in thermoplastic resins such as engineering plastics. In addition, it is possible to improve properties such as impact resistance and fluidity, and at the same time, it is possible to improve the appearance of the molded product. Therefore, the thermoplastic resin composition of the present invention is widely used for automobile parts, electric / electronic parts, mechanical parts, other industrial parts and the like.

Claims (1)

[Claims] (1) Thermoplastic resin 50 to 99% by weight
And (2) a graft copolymer having a multiphase structure comprising a thermoplastic elastomer segment and a vinyl polymer segment, one segment forming a dispersed phase of fine particles in a continuous phase formed by the other segment. A thermoplastic resin composition comprising 1 to 50% by weight of a polymer.