JPH08134315A - Thermoplastic polymer composition - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic resin composition which is excellent in impact resistance, toughness and thermal stability. CONSTITUTION: This thermoplastic polymer composition excellent in impact resistance comprises 100 pts.wt. of a polymer blend composed of (a) 2-60wt.% of a polyamide elastomer and/or polyester elastomer and (b) 98-40wt.% of a styrene resin which is prepared by polymerizing an aromatic vinyl compound or a mixture thereof with other vinyl monomers copolymerizable with the aromatic vinyl monomers in the presence or in the absence of a rubber polymer and 0.01-10 pts.wt. of an oxidized polyethylene wax.

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 excellent rigidity, antistatic property, impact resistance and thermal stability.

[0002]

2. Description of the Related Art Styrenic resins such as ABS resins have excellent molding processability, physical properties and mechanical properties, and are therefore widely used in the electric and electronic fields, home appliances fields, automobile fields and the like. ing. However, although such a resin is an electric insulator and is convenient as an insulating material, it has the drawback that it cannot leak charged electricity and dust adheres to its surface. In addition, there is a disadvantage in electronic devices that charged electricity causes interference. As a method of improving these drawbacks, a method of kneading an antistatic agent is generally known, but in this method, since the surface specific resistance value increases with time, there is a problem that the antistatic effect does not last. is there. As a method of improving the durability of the antistatic effect, there has been proposed a method of blending a polyether amide elastomer containing polyethylene glycol and polyamide as main components with an ABS resin. The composition obtained by this method certainly has a longer lasting antistatic effect than the ABS resin containing an antistatic agent. However, since such a composition is inferior in impact resistance and rigidity, there is a problem that a molded product obtained by injection molding or extrusion molding of the composition is cracked.

[0003]

The present invention is intended to solve the above problems and to provide a polymer composition excellent in rigidity, antistatic property, impact resistance and thermal stability.

[0004]

The present invention provides an aromatic vinyl compound in the presence or absence of (a) a polyamide elastomer and / or a polyester elastomer of 2 to 60% by weight and (b) a rubbery polymer. Alternatively, a styrene resin 98 obtained by polymerizing an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound
To 100 parts by weight of 40% by weight,
(C) A thermoplastic polymer composition having excellent impact resistance, which comprises 0.001 to 10 parts by weight of a polyolefin-based wax and / or an oxidized polyolefin-based wax,
Is provided.

The present invention will be described in detail below. The component (a) of the present invention is a polyamide elastomer (a-1) and / or a polyester elastomer (a-2), and also includes a polyetheresteramide elastomer. Examples of the polyamide elastomer (a-1) include a hard segment (X) composed of an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a nylon mn salt in which m + n is 12 or more, and a polyol such as poly (alkylene oxide) glycol. A soft segment (Y) such as, and the proportion of the hard segment (X) in the elastomer is 10 to 95% by weight,
20-90% by weight, more preferably 30-
80 wt% can be mentioned. When the proportion of the hard segment (X) in the polyamide elastomer (a-1) is less than 10% by weight, the compatibility with the styrene resin which is the component (b) of the present invention is poor and 95% by weight.
If it exceeds, the polymer composition obtained is inferior in antistatic property.

The above-mentioned aminocarboxylic acid or lactam having 6 or more carbon atoms, or nylon m having m + n of 12 or more
As the hard segment (X) composed of n-salt, ω
-Aminocaproic acid, ω-aminoenoic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and other aminocarboxylic acids; lactams such as caprolactam laurolactam Nylon 6,6, nylon 6,10, nylon 6,12, nylon 11,6, nylon 11,10, nylon 12,6, nylon 11,1
2. Nylon salts such as 2, nylon 12,10 and nylon 12,12 can be mentioned. Further, as the soft segment (Y) such as polyol, polyethylene glycol,
Poly (1,2- and 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, block or random copolymer of ethylene oxide and propylene oxide, ethylene oxide and tetrahydrofuran Examples thereof include block or random copolymers. The number average molecular weight of these soft segments (Y) is 200 to 6,000, preferably 250 to 4,000.
Is. Among these soft segments (Y),
From the viewpoint of antistatic property, polyethylene glycol is particularly preferable. In the present invention, both terminals of poly (alkylene oxide) glycol (Y) may be aminated or carboxylated before use. The bond between the component (X) and the component (Y) may be an ester bond or an amide bond corresponding to the terminal group of the polyetheramide elastomer (a). Further, when forming such a bond, a third component such as dicarboxylic acid or diamine may be added.

In the present invention, as the polyamide elastomer (a-1), an aminocarboxylic acid or lactam having 6 or more carbon atoms or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms; polyethylene glycol having a number average molecular weight of 200 to 6000 Or a polyether ester amide composed of a dicarboxylic acid having 4 to 20 carbon atoms, preferably a polyether ester unit having a polyether ester unit content of 10 to 95% by weight, has a more excellent antistatic effect. A thermoplastic resin composition can be obtained.

Among these components, caprolactam, 1,2-aminododecanoic acid and hexamethylenediamine-adipate are preferable as components. Further, when the number average molecular weight of the component is in the range of 200 to 6000, preferably 250 to 4000, a resin composition excellent in mechanical properties and antistatic effect can be obtained. Examples of the dicarboxylic acid as the component include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-
4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acid such as sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid,
Aliphatic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-dicarboxylic acid,
Examples thereof include aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and mixtures of these dicarboxylic acids. Particularly, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacine Acid, adipic acid and dodecanedicarboxylic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties. When the content of the polyether ester unit in the component polyether ester amide is 10 to 95% by weight, a composition having more excellent mechanical properties and antistatic properties can be obtained.

Reduced viscosity η _{sp / c of} polyamide elastomer (a-1) (0.5 g / 100 ml, 25 g in formic acid solution)
(Measured in ° C) is preferably 0.5 to 3. The polyamide elastomer (a-1) may cause a decrease in molecular weight due to heat deterioration during the production and molding of the composition of the present invention, but the reduced viscosity η _{sp / c} in the final product is 0. It is preferably 3 or more.

The polyester elastomer (a-2) is
Polycondensation of a dicarboxylic acid compound and a dihydroxy compound,
Polycondensation of an oxycarboxylic acid compound A polyester obtained by ring-opening polycondensation of a lactone compound, or polycondensation of a mixture of these components, and the effect of the present invention can be obtained by using either a homopolyester or a copolyester. To be Examples of the dicarboxylic acid compound include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid and sebacic acid.
These alkyl, alkoxy or halogen substitution products are also included. In addition, these dicarboxylic acid compounds,
It is also possible to use them in the form of ester-formable derivatives, for example lower alcohol esters such as dimethyl esters. In the present invention, these dicarboxylic acid compounds may be used alone or in combination of two or more. Examples of the dihydroxy compound include ethylene glycol, propylene glycol, butanediol,
Neopentyl glycol, butenediol, hydroquinone, resorcin, dihydroxydiphenyl ether,
Examples thereof include cyclohexanediol, hydroquinone, resorcin, dihydroxydiphenyl ether, cyclohexanediol, and 2,2-bis (4-hydroxyphenyl) propane, and polyoxyalkylene glycol and alkyl, alkoxy or halogen-substituted products thereof are also included. These dihydroxy compounds can be used alone or in combination of two or more.
Examples of the oxycarboxylic acid compound include oxybenzoic acid, oxynaphthoic acid, diphenyleneoxycarboxylic acid and the like, and their alkyl, alkoxy and halogen substitution products are also included. These oxycarboxylic acid compounds can be used alone or in combination of two or more kinds. In addition, polyester elastomer (a-
A lactone compound such as ε-caprolactone may be used for the production of 2).

The styrene resin as the component (b) of the present invention is an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable therewith in the presence or absence of a rubbery polymer. It is obtained by polymerizing a monomer. As the rubbery polymer, polybutadiene, styrene-butadiene copolymer (styrene content is preferably 5 to 60% by weight), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin copolymer. , Ethylene-α-olefin-polyene copolymer, acrylic rubber, butadiene-acrylic copolymer, polyisoprene, styrene-butadiene block copolymer, hydrogenated butadiene-based polymer, ethylene-based ionomer, silicone rubber and the like. . Among them, the styrene-butadiene block copolymer and the styrene-isoprene block copolymer are classified into AB type and A type.
Those having a BA type, a taper type and a radial teleblock type structure are included. Examples of the hydrogenated butadiene-based polymer include hydrogenated products of the block copolymers, hydrogenated products of blocks of styrene polymers and styrene-butadiene random copolymers, and -A block containing less than 20% by weight of vinyl bonds and 1,
A hydrogenated product of a block polymer composed of polybutadiene having a 2-vinyl bond of more than 20% by weight can be used. The amount of the rubbery polymer used is 0 to 90% by weight in the component (b).
From the viewpoint of impact resistance, it is preferably 3 to 70% by weight, more preferably 5 to 60% by weight, and particularly preferably 10 to 60% by weight. The ratio of the rubber polymer to the thermoplastic resin composition of the present invention is preferably 5 to 25% by weight from the viewpoint of the balance between impact resistance and fluidity.
More preferably, it is about 6 to 20% by weight.

Further, as the aromatic vinyl compound,
Styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene,
Monobromostyrene, dibromostyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene, o-
Methyl styrene, dimethyl styrene, etc. are mentioned, and these can be used individually or in combination of 2 or more types. Styrene is preferably used among these aromatic vinyl compounds, and it is preferable to use styrene in an amount of 40% by weight or more even when two or more aromatic vinyl compounds are used in combination.

Other vinyl monomers copolymerizable with the above aromatic vinyl compounds include vinyl cyan compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, alkyl acrylates such as cyclohexyl acrylate, methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, maleimide, N- Methylmaleimide, N-ethylmaleimide, N-phenylmaleimide,
Maleimide compounds such as N-cyclohexylmaleimide, epoxy group-containing unsaturated compounds such as glycidyl metal acrylate and allyl glycidyl ether, acrylic acid,
Unsaturated acids such as methacrylic acid, itaconic acid, maleic acid, etc., unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, acrylic amine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, etc. An amino group-containing unsaturated compound,
3-hydroxy-1-propene, 4-hydroxy-1-
Butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-
Examples thereof include a hydroxyl group-containing unsaturated compound such as methyl-1-propene, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, and acrylamide and vinyloxazoline. These compounds may be used alone or in combination of two or more kinds. it can.

Preferred as the above-mentioned monomer component (aromatic vinyl compound or aromatic vinyl compound and other vinyl monomer copolymerizable therewith) are aromatic vinyl compound and cyanide from the viewpoint of impact resistance. It is a monomer mixture composed of a vinyl compound, and a preferable ratio is aromatic vinyl compound / vinyl cyanide compound = 80 to 60/20 to 40.
% By weight. The (co) polymer of the aromatic vinyl compound and the other vinyl monomer may be polymerized in the presence of the rubbery polymer or may be polymerized in the absence thereof to obtain ( The (co) polymers can be used alone or in combination. The styrene resin (b) used in the present invention is obtained by emulsion polymerization of the above monomer component in the presence or absence of a rubbery polymer, which is a known polymerization method.
It can be obtained by polymerization by a polymerization method such as solution polymerization or suspension polymerization. As the polymerization initiator, molecular weight modifier, emulsifier, dispersant, solvent and the like used for the polymerization at this time, those usually used in these polymerization methods can be used as they are.

As the styrene resin (b), a resin obtained by graft-polymerizing a monomer component in the presence of a rubbery polymer as described above is preferable from the viewpoint of impact resistance. The graft ratio is preferably 20 to 200% by weight, more preferably 30 to 120% by weight. The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component of the styrene resin (b) is preferably 0.3 to 1.5.

The mixing ratio of the polyamide elastomer (a-1) and the polyester elastomer (a-2), which are the component (a) of the present invention, and the styrene resin (b) is
In the composition of the present invention, 2 to 60/98 to 40% by weight, preferably 5 to 30/95 to 70% by weight, more preferably 7 to 25/93 to 75% by weight, particularly preferably 7 to 20% by weight.
/ 93 to 80% by weight. When the amount of the component (a) is less than 2% by weight and the amount of the component (b) exceeds 98%, the antistatic performance of the resulting composition is poor, and the amount of the component (a) exceeds 60% by weight and the amount of the component (b) is 40% by weight. When it is less than 1, the rigidity and thermal stability are poor.

In order to further improve the performance of the thermoplastic resin composition of the present invention, a compatibilizing agent that improves the compatibility of the components (a) and (b) of the present invention can be used. . Preferred compatibilizers include the above (b)
A styrene resin obtained by copolymerizing a vinyl monomer having a functional group such as a hydroxyl group, an epoxy group, a carboxyl group, an acid anhydride group, an amino group, or an oxazoline group as a part of the component, or an α-olefin and these. Examples thereof include a copolymer with a vinyl-based monomer having a functional group. Among the above functional groups, an epoxy group, a carboxyl group and a hydroxyl group are preferable, and a hydroxyl group is particularly preferable from the viewpoint of impact resistance and thermal stability of the composition. When a compatibilizer containing such a functional group is used, as the monomer component of the component (b), an aromatic vinyl compound and an alkyl methacrylic acid ester and / or a vinyl cyanide compound,
It is preferable to use a combination of the above functional group-containing vinyl monomers. The functional group-containing vinyl monomer is preferably used in an amount of 0.5 to 30% by weight based on the styrene resin (b) of the present invention. The amount of the functional group-containing vinyl monomer used is preferably 0.1 to 30% by weight, more preferably 0.3 to 20% by weight in the composition comprising (a) and (b) of the present invention. % By weight. Preferred functional group-containing vinyl monomers include (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate.

The component (c) of the present invention is a polyolefin wax and / or an oxidized polyolefin wax.
An olefin oxide wax is preferable, and an oxidized polyethylene wax is particularly preferable. Examples of the polyolefin wax include low molecular weight polyethylene and polypropylene. As the olefin oxide wax, one obtained by oxidizing a low molecular weight polyolefin can be used. The particularly preferred component (c) is obtained by, for example, oxidizing polyethylene, and specifically is polyethylene containing a hydroxyl group, a carboxylic acid group and the like. The dropping point of the component (c) is preferably 95 to 125 ° C,
More preferably 100 to 120 ° C., particularly preferably 1
It is 05-120 degreeC. The dropping point is a value measured by the DFF standard method. The acid value of the component (c) is preferably 10 to 40, more preferably 15 to 30, and particularly preferably 15 to 28. The acid value is a value measured by the DFF standard method. The molecular weight of the component (c) is preferably 1,000 to 10,000, more preferably 1,500 to 5,000, particularly preferably 2,000 to.
It is 4,500. When the component (c) within the above range is used, the thermoplastic polymer composition having improved impact resistance, which is the object of the present invention, can be obtained. The blending amount of the component (c) is
It is 0.001 to 10 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, relative to 100 parts by weight of the resin composition comprising (a) and (b). It is particularly preferably 0.01 to 0.1 parts by weight.
When the blending amount of the component (c) is less than 0.001 part by weight,
The effect of improving impact resistance cannot be sufficiently obtained, and if it exceeds 10 parts by weight, the component (c) bleeds out and a good molded appearance cannot be obtained. The component (c) may be added by adding the component (c) when pelletizing the composition comprising the component (a) and the component (b), or by adding the component (a) and the component (b). A method of adding (spraying) the component (c) at the time of injecting or extruding pellets of the composition comprising

The effect of improving the impact resistance by adding the component (c) is particularly remarkable when applied to a resin composition containing a flame retardant. The preferable amount of the flame retardant compounded is
Resin composition 1 comprising the components (a) and (b)
The amount is 1 to 30 parts by weight, more preferably 10 to 25 parts by weight, relative to 00 parts by weight. When the component (c) is added to the resin composition containing the flame retardant in the above blending amount, a resin composition having excellent impact resistance can be obtained without impairing the flame retardancy. Examples of the flame retardant include halogen compounds, phosphorus compounds, antimony compounds and the like. Specific halogen compounds include tetrabromobisphenol A, tetrabromobisphenol A oligomers, brominated epoxy oligomers, and brominated polycarbonate oligomers. Specific phosphorus compounds include triphenyl phosphate, trixylenyl phosphate, and phosphate oligomers. Specific antimony compounds include antimony trioxide and antimony pentoxide. The above flame retardants may be used in combination. A preferred combination is a combination of a halogen compound and an antimony compound.

Further, in the thermoplastic polymer composition of the present invention, the following (d) and / or (e) and / or
Alternatively, the heat stabilizer and the antioxidant of (f) may be added. (D) Phenolic compound having double bond in molecule (e) Hindered phenolic antioxidant (f) Sulfur antioxidant (d) and / or (e) and / or (f) component added By doing so, a thermoplastic polymer composition having excellent impact resistance and thermal stability can be obtained. Above (d),
The components (e) and (f) can be used in combination.

The specific component (d) is as follows:

Embedded image It is a phenolic compound having a double bond in the molecule represented by.

(In the formula, R ₁ and R ₃ are each 1 to 1 carbon atoms.
8 represents an alkyl group, and R ₂ represents an alkylene group having 1 to 8 carbon atoms. ) the above

## STR1 ## In the phenol compound represented by, R ₁
And R ₃ is an alkyl group having 1 to 8 carbon atoms, and R ₂ is an alkylene group having 1 to 8 carbon atoms. In order to achieve the object of the present invention, these groups have 1 to 5 carbon atoms. And more preferably R ₁ and R ₃ are alkyl groups having 1 to 5 carbon atoms, and R ₂ is an alkylene group having 1 or 2 carbon atoms. Particularly preferred compounds are

R ₁ and R ₃ in the formula are

Embedded image And R ₂ is

Embedded image belongs to.

The preferable addition amount of the component (d) is 0. 0 per 100 parts by weight of the total of the components (a) and (b) of the present invention.
01 to 5 parts by weight, more preferably 0.05 to 3
Parts by weight, particularly preferably 0.05 to 1 part by weight. If the addition amount is less than 0.01 parts by weight, the thermal stability of the obtained resin will be poor, and if it exceeds 5 parts by weight, the thermal stability will be poor.

As the component (e), all of the known phenolic antioxidants and sulfur antioxidants other than the component (d) can be used. A preferred phenolic antioxidant (e) has a molecular weight of 500 or more, and specifically, pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 3,9-bis [2- [3- (3-t-
Butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,
4,8,10-Tetraoxaspiro [5.5] undecane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol- Screw [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2-thio-
Diethylenebis [3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy) -Hydrocinmide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,
3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Tris- (3,5-di-t-butyl-4-hydroxybenzyl)- Isocyanurate, tetrakis [methylene-3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and the like. Also,
Preferred sulfur antioxidants (f) include dilauryl-3,3'-thiodipropionate and dimyristyl-
3,3'-thiodipropionate, distearyl-3,
3'-thiodipropionate, pentaerythrityl tetrakis (3-lauryl thiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole and the like can be mentioned.

The above-mentioned components (e) and (f) may be used alone or in combination of two or more kinds. Phenol type antioxidant (e) and sulfur type antioxidant (f)
The preferable ratio when using a combination of e is f / f = 8
It is 0 to 20/20 to 80% by weight. The preferred amount of the component (e) used is 0.01 to 4 parts by weight, more preferably 0.03 to 2 parts by weight, based on 100 parts by weight of the total of the components (a) and (b) of the present invention. , Particularly preferably 0.
It is from 03 to 1 part by weight. If it is less than 0.01 parts by weight, the thermal stability is poor, and if it exceeds 4.0 parts by weight, the thermal stability is poor.
The preferable amount of the component (f) used is 0.01 to 4 parts by weight, more preferably 0.03 to 2 parts by weight, based on 100 parts by weight of the total of the components (a) and (b) of the present invention. And particularly preferably 0.03 to 1 part by weight. If it is less than 0.01 parts by weight, the thermal stability will be poor, and if it exceeds 4 parts by weight, the thermal stability will be poor.

The thermoplastic resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls, etc., but is preferably produced using extruders. In kneading the respective components of the present invention, the respective components may be kneaded together or may be kneaded by a multi-stage addition method. When using the thermoplastic resin composition of the present invention, glass fiber, carbon fiber, metal fiber, glass beads, wollastonite, rock filler, calcium carbonate, talc, mica, glass flakes, kaolin, barium sulfate, graphite, two Fillers such as molybdenum sulfide, magnesium oxide, zinc oxide whiskers can be used alone or in combination. Among these fillers, glass fibers are preferable, and carbon fibers having a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more are preferable. These fillers are preferably used in an amount of 5 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition of the present invention. Further, the resin composition of the present invention can be used by adding various additives such as other antioxidants such as phosphorus-based antioxidants, plasticizers, colorants, and lubricants. Furthermore, other polymers such as polyethylene, polypropylene, polyamide, polyester, polycarbonate, polysulfone, depending on the performance required,
Polyether sulfone, polyphenylene sulfide, liquid crystal polymer, vinylidene fluoride polymer, EVA and the like can be appropriately blended. The thermoplastic resin composition obtained by the present invention can be molded into various molded articles by molding methods such as injection molding, sheet extrusion, vacuum molding, irregular shape, foam molding, press molding, stampable molding, and the like. By utilizing this property, it can be used as various parts in the field of automobiles, various parts of home appliances, housings, miscellaneous goods, various parts and housings in the field of OA equipment.

[0026]

EXAMPLES The present invention will be described below in more detail with reference to production examples and examples, but they are merely illustrative and do not limit the content of the present invention. In the examples,
Parts and% indicate parts by weight and% by weight, respectively.

Various physical properties in the following examples were evaluated according to the following methods. (1) Antistatic property: A disc having a diameter of 100 mm and a thickness of 2 mm was molded and conditioned for 7 days at 23 ° C x 50% relative humidity, and then 4329A manufactured by Yokogawa Hewlett-Packard Company.
The surface resistivity was measured using a super insulation resistance tester. (2) Impact resistance; thickness 1/4 according to ASTM D256
The Izod impact strength was measured at 23 ° C with a notch. (3) Stiffness: Flexural modulus was measured according to ASTM D790. (4) Thermal stability: The produced pellets were sufficiently dried by a dehumidifying dryer and continuously molded in an injection molding machine set at 270 ° C. for 5 minutes to obtain 10 flat plate-shaped molded articles. . The number of black foreign matters on the surface of the obtained molded product was counted, and the following ranks were assigned from the number. ◎: Foreign matter 8 points or less ○: Foreign matter 10 points or less △: Foreign matter 10 points to 20 points ×: Foreign matter exceeds 20 points (5) Molding appearance: The appearance of the injection-molded molded product was visually evaluated. Good ○ ＞ △ ＞ × Bad

Preparation of Component (a) Polymer (a) -1 Polyamide-6 having a melting point of 200 ° C. was obtained by ring-opening polymerization of ε-caprolactam. Both ends of the obtained polyamide-6 were converted to carboxylic acid with adipic acid, and then the molecular weight was 1
The polyethylene glycol of 500 was added and esterification reaction was performed to obtain a polymer (a) -1. Polymer (a) -2 terephthalic acid and 1,4-butanediol were subjected to condensation polymerization to obtain polybutylene terephthalate having a melting point of 200 ° C.
Both ends of the obtained polybutylene terephthalate were converted to carboxylic acid with adipic acid, and then polyethylene glycol having a molecular weight of 1500 was added to carry out an esterification reaction to obtain a polymer (a) -2.

Preparation of Polymer (b) The rubbery polymer used in the production of the polymer (b) was as shown in Table 1.

[Table 1]

In the presence or absence of the rubbery polymer (rubbery polymer-1, rubbery polymer-2, rubbery polymer-3), various monomers (styrene, acrylonitrile, methacrylic acid) are used. , 2-hydroxyethyl methacrylate) were polymerized to produce polymers (b) -1 to (b) -6 shown in Table 2. The polymers (b) -1, (b) -4 and (b) -5 were emulsion polymerized, and the polymers (b) -2,
(B) -3 and (b) -6 were obtained by solution polymerization.

[0031]

[Table 2]

(C) Component Oxidized polyethylene waxes PED121 (c-1) and PED191 (c-2) manufactured by Hoechst Co. were used as the component (c). Component (d) The component (d) has the following structure.

[Chemical 4]

Component (e) The following was used as the component (e). Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4
-Hydroxyphenyl) propionate] [manufactured by Ciba Geigy; Irganox 1010 (hindered phenolic antioxidant)] (f) component pentaerythrityl tetrakis (3-laurylthiopropionate) [manufactured by Sumitomo Chemical Co., Ltd .; Sumilizer TP
-D (Sulfur-based antioxidant)] Other components A brominated epoxy oligomer was used as a flame retardant.
In addition, antimony trioxide was used as a flame retardant aid.

Examples 1 to 7; Comparative Examples 1 to 5: The above various polymers were dried to a water content of 0.1% or less, the above various components were mixed at the compounding ratios shown in Tables 3 and 4, and vented. It was melt-kneaded and pelletized using a twin-screw extruder attached. The obtained pellets were dried with a dehumidifying dryer until the water content was 0.1% or less, and the pellets were molded with an injection molding machine to prepare test pieces. The obtained test pieces were evaluated for antistatic property, impact resistance, rigidity and thermal stability, and the results are shown in Tables 3 and 4.

[0035]

[Table 3]

[0036]

[Table 4]

From the results shown in Table 3 and Table 4, Example 1
It can be seen that the compositions of to 7 have excellent antistatic properties, impact resistance, rigidity and thermal stability. As is clear from the comparison between Example 1 and Comparative Example 1, it is understood that the impact resistance is improved by adding the component (c). It is also found that the addition of the heat stabilizer and the antioxidant makes it possible to obtain a thermoplastic resin composition having excellent impact resistance and heat stability. On the other hand, in the compositions of Comparative Examples 1 and 3, the amount of the component (c) used was less than the range of the present invention, and the impact resistance was insufficient. In addition, the composition of Comparative Example 2 has an amount of component (c) exceeding the range of the present invention, and is inferior in molding appearance and rigidity. Furthermore, the composition of Comparative Example 4 has a lower amount of component (a) than the range of the present invention and a higher amount of component (b) than the range of the present invention, and is inferior in antistatic performance. ing. In the composition of Comparative Example 5, the amount of the component (a) used exceeds the range of the present invention, and the amount of the component (b) used is less than the range of the present invention. Is inferior.

[0038]

According to the present invention, since excellent impact resistance can be obtained, it is possible to prevent the molded article from cracking or breaking. That is, the thermoplastic resin composition of the present invention has improved impact resistance without lowering rigidity, antistatic property and thermal stability. As described above, since the thermoplastic resin composition of the present invention is excellent in rigidity, antistatic property, impact resistance and thermal stability, it is required to adhere to dust or prevent electrostatic damage. It can be preferably used as various parts and housings in the field of home appliances and OA equipment.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08L 77:00 67:02 23:00) (72) Inventor Hisao Nagai 2 Tsukiji, Chuo-ku, Tokyo No. 11-24, Nippon Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. An aromatic vinyl compound or an aromatic vinyl compound and an aromatic vinyl compound in the presence or absence of (a) a polyamide elastomer and / or polyester elastomer and 2 to 60% by weight of (b) a rubbery polymer. (C) Polyolefin-based wax and / or oxidized polyolefin-based wax based on 100 parts by weight of a total of 100 to 40% by weight of a styrene resin obtained by polymerizing a vinyl compound and another vinyl monomer copolymerizable with the vinyl compound. A thermoplastic polymer composition having excellent impact resistance, which comprises 0.001 to 10 parts by weight.