TW201343763A - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

A thermoplastic resin composition and a molded article thereof have excellent mechanical properties and surface gloss properties, wherein the thermoplastic resin composition comprises 0.001 to 1 parts by mass of an epoxy group-containing acrylic-styrene-based copolymer (III) with respect to 100 parts by mass of a resin composition composed of a styrene-based resin (I) and a polyethylene terephthalate resin (II).

Description

Thermoplastic resin composition and molded article thereof

The present invention relates to a thermoplastic resin composition containing a styrene resin and a polyethylene terephthalate resin, and a molded article thereof.

The styrene-based resin represented by the ABS resin has excellent mechanical properties, moldability, and electrical insulation properties, and is used in a wide range of fields including household electrical equipment, OA equipment, and automobiles.

On the other hand, polyethylene terephthalate (PET) resin which is a polyester resin is widely used in various bottles, food trays, sheets, and the like because of its excellent mechanical strength, transparency, and gas barrier properties.

The PET resin has a high impact resistance when it is extended, and has high heat resistance when it is crystallized. Therefore, although the use ratio in the above-mentioned use is high, the current impact is low in impact resistance in the injection molding method. The disadvantages are remarkably produced, and the use ratio as the injection molded article is extremely low.

In addition, in recent years, due to the rise in environmental problems, the green procurement method or the US electronic device standard (EPEAT) has been used to utilize the specifications of recycled resins. In view of the background art, there is an increasing demand for resin compositions that are used in recycled resins or recycled resins. Among them, the amount of discarded PET resin products has also increased to a year-to-year increase, and the recycling and reuse of such wastes has attracted much attention.

Therefore, if the disadvantage of the PET resin as the injection molded product can be eliminated, not only the use of the virgin material but also the use of the virgin material can be expanded, and an increase in the amount of use can be expected.

One of the methods for improving the impact resistance which is the subject of the present invention is to blend with the polymer of the ABS resin. Patent Document 1 discloses a composition and a manufacturing condition for improving impact resistance by blending an ABS resin in a recycled PET resin. However, it has been found that the compatibility of the PET resin with the ABS resin is not as good as the original, and it is not always possible to obtain good impact resistance in the composition obtained by the method described in the patent document.

Therefore, research on improving the compatibility of the blended composition of the PET resin and the ABS resin has been conducted since ancient times. Patent Document 2 discloses an example in which an acrylonitrile ‧ styrene copolymer having an epoxy group is used as a modifier, and Patent Document 3 proposes to use ethylene having an epoxy group in addition to acrylonitrile and styrene. A method in which a monomer is graft-copolymerized with a diene rubber to improve compatibility. However, in these methods, although the improvement of the mechanical strength can be attained, a crosslinked product is generated in the extruder or in the molding machine, which may impair the surface gloss.

On the other hand, an acrylic acid/styrene copolymer containing an epoxy group is added to a composition containing a recycled PET resin and a linear low-density polyethylene resin (Patent Document 4), and a polylactic acid resin is included. An example of the composition of the ABS resin (Patent Document 5) is not used to improve the compatibility and obtain a good surface glossiness in a composition comprising a PET resin and an ABS resin.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2004-67728

Patent Document 2 Japanese Patent Laid-Open Publication No. 2003-286382

Patent Document 3 Japanese Patent Laid-Open No. 2-16145

Patent Document 4 Japanese Patent Laid-Open Publication No. 2005-200534

Patent Document 5 Japanese Patent Laid-Open Publication No. 2008-106091

An object of the present invention is to provide a thermoplastic resin composition which can eliminate the disadvantages of the prior art described above and which contains a styrene resin excellent in mechanical properties and surface gloss and a polyethylene terephthalate. Ester resin.

In order to solve the above problems, the present inventors have repeatedly studied and found that a resin composition containing styrene resin (I) and polyethylene terephthalate resin (II) is blended with respect to 100 parts by weight. 0.01 to 1 part by weight of the epoxy group-containing acrylic acid ‧ styrene copolymer (III) can solve the above problems.

In other words, the thermoplastic resin composition described in the following (1) to (7) and a molded article thereof.

(1) A thermoplastic resin composition containing 0.01 to 1 part by weight of an epoxy resin based on 100 parts by weight of the resin composition containing the styrene resin (I) and the polyethylene terephthalate resin (II) Based on acrylic acid ‧ styrene copolymer (III).

(2) The thermoplastic resin composition according to (1), wherein the epoxy group-containing acrylic acid ‧ styrene copolymer (III) has a weight average molecular weight of 2,000 to 20,000.

(3) The thermoplastic resin composition according to (1) or (2), wherein the epoxy group-containing acrylic acid ‧ styrene copolymer (III) has an epoxy value of 0.5 to 4.0 (meq/g).

(4) The thermoplastic resin composition according to any one of (1) to (3), wherein the weight ratio of the styrene resin (I) and the polyethylene terephthalate resin (II) is 50:50 to 99:1.

(5) The thermoplastic resin composition according to any one of (1) to (4), wherein the styrene resin (I) contains a graft copolymer (A) and a vinyl (co) polymer (B) a composition having a weight ratio of 10:90 to 50:50, wherein the graft copolymer (A) is selected from the group consisting of aromatic vinyl monomers (b) and vinyl cyanide in the rubbery polymer (a). The monomer (c) and one or more monomers of the copolymerizable other vinyl monomer (d) are graft copolymerized, and the vinyl (co)polymer (B) is selected from the group consisting of aromatic vinyl monomers. (b) A monomer obtained by polymerizing one or more monomers of a vinyl cyanide monomer (c) and another copolymerizable vinyl monomer (d).

(6) The thermoplastic resin composition according to any one of (1) to (5), wherein the polyethylene terephthalate resin (II) is a recycled material of a polyethylene terephthalate resin molded article. All or part of it.

(7) A molded article obtained by molding the thermoplastic resin composition according to any one of (1) to (6).

According to the present invention, a thermoplastic resin composition containing a styrene resin excellent in mechanical properties and surface glossiness, and a polyethylene terephthalate resin can be obtained, and a molded article thereof.

The form for carrying out the invention will be specifically described below.

In the present invention, the styrene resin (I) means one or more types selected from the group consisting of an aromatic vinyl monomer (b), a vinyl cyanide monomer (c), and another copolymerizable vinyl monomer (d). The ethylene-based (co)polymer (B) or the rubber-based polymer (a) is added to the vinyl (co)polymer (B).

In the case where the styrene-based resin (I) is added to the rubber-based polymer (a) in the vinyl-based (co)polymer (B), the vinyl-based (co)polymer (B) and the rubbery polymer (a) The viewpoint of the compatibility of the rubbery polymer (a) is preferably a composition containing a graft copolymer (A) and a vinyl (co)polymer (B), wherein the graft copolymerization The material (A) is obtained by graft-copolymerizing one or more monomers selected from the group consisting of an aromatic vinyl monomer (b), a vinyl cyanide monomer (c), and another copolymerizable vinyl monomer (d). The vinyl-based (co)polymer (B) contains one selected from the group consisting of an aromatic vinyl monomer (b), a vinyl cyanide monomer (c), and another copolymerizable vinyl monomer (d). On the single. Further, the monomer mixture blended in the graft copolymer (A) is not necessarily bonded to the rubbery polymer (a) to be grafted, and may also contain monomers in the monomer mixture bonded to each other and as A polymer which is not grafted. However, the graft ratio is preferably from 10 to 100%, more preferably from 20 to 50%.

The blending amount of the rubbery polymer (a) used for the graft copolymer (A) is not particularly specified, but is preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, still more preferably 35 to 65 parts by weight. Further, the compounding amount of the monomer mixture in the graft copolymer (A) is preferably from 20 to 90 parts by weight, more preferably from 30 to 80 parts by weight, still more preferably from 35 to 65 parts by weight. By using the rubbery polymer (a) and the monomer mixture in these ratios, good impact resistance and moldability can be obtained. Further, the ratio of the monomer mixture to be blended in the graft copolymer (A) is not particularly limited, and it is preferably 20 to 99% by weight of the aromatic vinyl monomer (b), and the vinyl cyanide series The body (c) is used in an amount of from 1 to 40% by weight and from 0 to 79% by weight based on the other copolymerizable vinyl monomer (d), and good impact resistance and moldability can be obtained.

The ratio of the monomer mixture to be blended in the vinyl (co)polymer (B) is not particularly limited, but is preferably 20 to 99% by weight of the aromatic vinyl monomer (b), and the vinyl cyanide series When the body (c) is used in an amount of from 1 to 40% by weight and from 0 to 79% by weight of the other copolymerizable vinyl monomer (d), good impact resistance and moldability can be obtained.

The mixing ratio of the graft copolymer (A) to the vinyl (co)polymer (B), and the weight of (A): (B) is preferably from 10:90 to 50:50, more preferably 20:80. To 40:60. The ratio of the graft copolymer (A) is less than the above When the ratio of the range or the ethylene-based (co)polymer (B) exceeds the above range, the tendency to reduce the punching strength tends to decrease. Moreover, when the ratio of the graft copolymer (A) exceeds the above range, the fluidity tends to decrease.

The reducing viscosity (?sp/c) of the acetone-soluble component of the graft copolymer (A) is not particularly limited, but is preferably 0.1 to 0.6 dl/g. In other cases, the impact resistance is lowered, or the melt viscosity is increased, and the formability is easily deteriorated. Further, it is preferably from 0.3 to 0.5 dl/g.

The reducing viscosity (ηsp/c) of the vinyl-based (co)polymer (B) is not particularly limited, but is preferably 0.1 to 0.6 dl/g. In other cases, the impact resistance is lowered, or the melt viscosity is increased, and the formability is easily deteriorated. It is further preferably from 0.3 to 0.5 dl/g.

The rubbery polymer (a) is not particularly limited, and a diene rubber, an acrylic rubber, a vinyl rubber or the like can be used. Specific examples thereof include polybutadiene, poly(butadiene-styrene), poly(butadiene-acrylonitrile), polyisoprene, poly(butadiene-butyl acrylate), and poly(butyl). Ethene-methyl methacrylate), poly(butyl acrylate-methyl methacrylate), poly(butadiene-ethyl acrylate), ethylene-propylene rubber, ethylene-propylene-diene rubber, poly(ethylene- Isoprene), poly(ethylene-acrylic acid methyl), and the like. These rubbery polymers (a) may be used alone or in combination of two or more. Among the rubbery polymers (a), polybutadiene, poly(butadiene-styrene), poly(butadiene-acrylonitrile), ethylene-propylene are preferably used in terms of impact resistance. rubber.

The weight average particle diameter of the rubbery polymer (a) is not particularly limited, and the balance between the mechanical strength such as impact resistance and the appearance of the molded article is preferably 0.1 to 0.5 μm. Less than 0.1μm, the resulting thermoplastic composition When the impact strength of the material is lowered, when the thickness exceeds 0.5 μm, the appearance of the molded article is lowered. More preferably, it is 0.15 to 0.4 μm.

The aromatic vinyl monomer (b) used in the graft copolymer (A) and the ethylene (co)polymer (B) is not particularly limited, and specific examples thereof include styrene, α-methylstyrene, and o Methylstyrene, p-methylstyrene, p-terphenyl styrene, and halogenated styrene may be used alone or in combination of two or more. Among them, styrene and α-methylstyrene are preferred, and styrene is particularly preferred.

The vinyl cyanide monomer (c) used in the graft copolymer (A) and the ethylene (co)polymer (B) is not particularly limited, and specific examples thereof include acrylonitrile and methacrylonitrile, and can be used. One or more. Among them, acrylonitrile is preferred in terms of impact resistance.

The other copolymerizable vinyl monomer (d) to be used for the graft copolymer (A) and the ethylene (co)polymer (B) is not particularly limited, and specific examples thereof include methyl (meth)acrylate, Ethyl methyl acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclomethacrylate An unsaturated carboxylic acid ester such as ester, chloromethyl (meth) acrylate or 2-chloroethyl (meth) acrylate; N-methyl maleimide, N-cyclohexyl maleic acid a maleimide compound such as an imine or N-phenylmaleimide; an unsaturated dicarboxylic acid such as maleic acid; or an unsaturated dicarboxylic acid anhydride such as maleic anhydride. And a copolymerizable vinyl compound represented by an unsaturated guanamine compound such as acrylamide, or the like, which may be used alone or in combination of two or more. Further, a plurality of kinds of the vinyl-based (co)polymer (B) can be used.

The production method of the graft copolymer (A) or the ethylene (co)polymer (B) is not particularly limited, and may be any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the like. The method of charging the monomer is not particularly limited, and any method may be employed in which the initial assembly is carried out, a part or all of the monomer is continuously charged, or a part or all of the monomer is divided and loaded.

Specific examples of the styrene resin (I) used in the present invention include, for example, polystyrene, high impact polystyrene (HIPS), AS resin, AAS resin, AES resin, ABS resin, and MAS resin. , MABS resin, MBS resin or blending of these resins with other resins.

In the present invention, the polyethylene terephthalate resin (II) refers to a high molecular weight thermoplastic polyester resin having an ester bond for use in the acid component of citric acid and ethylene glycol in the main chain of the diol component. In addition, as the acid component, isophthalic acid, adipic acid, oxalic acid or the like can be used, and as the diol component, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5 can be used. - pentanediol, 1,6-hexanediol, decanediol, cyclohexanedimethanol, cyclohexanediol, etc., or a long-chain diol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly - 1,3-propanediol, polytetramethylene glycol or the like is used in an amount of 20 mol% or less.

Further, in the present invention, the polyethylene terephthalate resin (II) may be a raw material which does not suffer from a thermal history such as a forming process, or may be a polyethylene terephthalate resin. The recycled material of the molded article preferably contains all or a part of the recycled material from the viewpoint of resource protection. Specific examples of the recycled materials include A waste material obtained by recovering a molded article formed in a plastic bottle or the like at least once, or a scrap produced in a trimming step at the time of forming a sheet-shaped object, in a specific example of re-recycling the shape of the material, Specific examples of the re-granulation of a flake or a powder or a foreign matter for removing foreign matter are exemplified. Further, it is preferable that the recycled material is a material which does not contain a reinforcing material such as glass fiber.

In the resin composition comprising the styrene resin (I) and the polyethylene terephthalate resin (II), the weight of the styrene resin (I) and the polyethylene terephthalate resin (II) The ratio of the styrene resin (I) to the polyethylene terephthalate resin (II) is preferably a weight ratio of 100 parts by weight of the total amount of the resin composition when the effect of the present invention is achieved. A ratio of 50:50 to 99:1 is more preferably a ratio of 55:45 to 90:10 by weight. When the ratio of the styrene resin (I) is less than the above range or the ratio of the polyethylene terephthalate resin (II) exceeds the above range, the mechanical strength may be lowered.

In the present invention, the epoxy group-containing acrylic acid ‧ styrene copolymer (III) is not particularly limited, and examples thereof include a (meth) acrylate monomer having an epoxy group, a method of copolymerizing a monomer having no epoxy group such as methyl)acrylic acid and styrene, or copolymerizing a monomer having no epoxy group such as (meth)acrylic acid with styrene, in the copolymer A method in which an alcohol having an epoxy group is added by a condensation reaction in a carboxyl group of a (meth)acrylic acid unit.

In the case of the epoxy group-containing (meth) acrylate monomer which can be used in the copolymerization of the acrylic ‧ styrene copolymer (III) having an epoxy group, a glycidyl methacrylate may be mentioned. The glycidyl acrylate or the like is preferably a glycidyl methacrylate.

Specific examples of the monomer having no epoxy group such as (meth)acrylic acid include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl). N-propyl acrylate, n-butyl (meth)acrylate, butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, chloromethyl (meth)acrylate and Among them, 2-methylethyl (meth)acrylate or the like is preferable, and among them, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate can be preferably used. These may be used alone or in combination of two or more.

The weight average molecular weight of the epoxy group-containing acrylic acid ‧ styrene copolymer (III) is preferably from 2,000 to 20,000, more preferably from 5,000 to 15,000, from the viewpoint of suppressing fluidity and bleeding out. Further, the weight average molecular weight is a value converted to polystyrene measured by gel permeation chromatography (GPC).

The epoxy value of the epoxy group-containing acrylic acid ‧ styrene copolymer (III) is preferably from 0.5 to 4.0 (meq/g), more preferably from 1.0 to 3.5 (meq), from the viewpoint of mechanical strength and surface gloss. /g). In addition, the epoxy price here is based on hydrochloric acid-two The value determined by the alkane method.

The polymerization method of the epoxy group-containing acrylic acid ‧ styrene copolymer (III) is not particularly limited, and a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization can be used, and the temperature is 150 ° C or higher. And under the pressurized condition (preferably 1 MPa or more), the method of continuous bulk polymerization is carried out in a short time (preferably 5 minutes to 30 minutes), and the point of high polymerization rate is not used as impurities or sulfur. The reason for the polymerization initiator or the chain transfer agent and the solvent is more preferable.

The epoxy group-containing acrylic acid ‧ styrene copolymer (III) used in the present invention with respect to 100 parts by weight of the resin composition containing the styrene resin (I) and the polyethylene terephthalate resin (II) The blending amount is from 0.01 to 1 part by weight, preferably from 0.03 to 0.7 part by weight, more preferably from 0.05 to 0.5 part by weight. The addition amount of the epoxy group-containing acrylic acid ‧ styrene copolymer (III) is less than the above range, and the mechanical strength is not sufficient. On the contrary, when it exceeds the above range, the surface glossiness of the obtained thermoplastic resin composition tends to be deteriorated. So it is not good.

One of the characteristics of the thermoplastic resin composition of the present invention is that the surface gloss is excellent by blending (I) to (III). The surface glossiness as described herein is evaluated by the numerical value measured according to the regulations of JIS Z 8741 (1997), and the surface property described in Patent Document 4 (JP-A-2005-200534). (Evaluation of the object) is the evaluation of different content. Since the thermoplastic resin composition of the present invention has a surface gloss of 90 or more, preferably 95 or more, it can be suitably used as an appearance product.

Further, in the thermoplastic resin composition of the present invention, it is also possible to blend a polyolefin such as polyvinyl chloride, polyethylene or polypropylene, nylon 6 or nylon 66, etc., without damaging the object of the present invention. A polyester such as decylamine, polybutylene phthalate or poly(p-hexane dimethyl phthalate), a fluorine-based resin such as polycarbonate or polytetrafluoroethylene, or various elastomers.

Further, in the thermoplastic resin composition of the present invention, one or more of the following general additives may be further blended as needed, without impairing the object of the present invention: glass fiber, glass powder, glass beads, glass flakes, aluminum oxide, Aluminoxy fiber, carbon fiber, graphite fiber, stainless steel fiber, whisker, potassium titanate fiber, ash stone Inorganic fillers of (wollastonite), asbestos, hard clay, burnt clay, talc, kaolin, mica, calcium carbonate, magnesium carbonate, alumina and minerals, or hindered phenolic, sulfur-containing compounds or phosphorus Antioxidants such as organic compounds; heat stabilizers such as phenols and acrylics; ultraviolet absorbers such as benzotriazole, diphenylketone or salicylate; hindered amine light stabilizers, advanced A fatty acid or an acid ester or an acid amide, further blended with a slip additive and a plasticizer such as a higher alcohol, montanic and a salt thereof, an ester thereof, a half ester thereof, a stearyl alcohol, a stearylamine (Stearamide) and release agent such as vinyl wax; anti-coloring agent for various flame retardants, flame retardant additives, phosphites, hypophosphorous acid salts, etc.; phosphoric acid, monosodium phosphate, maleic anhydride A neutralizing agent such as succinic anhydride; an antistatic agent such as a nucleating agent, an amine system, a citric acid type or a polyether type; a coloring agent such as carbon black, a pigment or a dye.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and (I) to (III) or the other components described above, for example, a V-type blender, an ultra-mixer, a superfloater, and Henscher are used. A mixer such as a Henschel mixer may be a composition to be mixed, and usually it is a mixture in which the preliminary mixture is uniformly melt-mixed. Such a mixture is obtained by subjecting the preliminary mixture to a granulation by a kneading method, for example, by melt kneading at a temperature of preferably from 230 to 300 ° C, more preferably from 250 to 285 ° C. In the specific method of melt-kneading and granulating, various kinds of melt mixers such as a kneader, a uniaxial and biaxial extruder, and the like are used, and the resin composition is melted and then extruded. A method of granulating granulators.

The thermoplastic resin composition of the present invention obtained as described above can be formed by a known method for molding a thermoplastic resin such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, and gas-assisted molding, and a molding method. There is no particular limitation in itself.

Example

The present invention will be described in detail by way of examples and comparative examples, but is not intended to limit the invention.

(1) Weight average rubber particle size

It is obtained by the sodium alginate method described in "Rubber Age Vol. 88 p. 484 to 490 (1960) by E. Schmidt, P. H. Biddison". That is, the particle size of the cumulative weight fraction of 50% is obtained by using the weight ratio of the self-emulsified weight ratio to the cumulative weight fraction of the sodium alginate concentration by the difference in the particle size of the emulsified polybutadiene by the concentration of sodium alginate.

(2) graft ratio

Acetone was added to a predetermined amount (m) of the graft copolymer, refluxed for 3 hours, and the solution was centrifuged at 8800 r/min (10000 G) for 40 minutes, and then the insoluble portion was filtered, and the insoluble portion was subjected to 60 ° C. It was dried under reduced pressure for 5 hours, and the weight (n) was measured. The graft ratio is calculated by the following formula.

Graft ratio (%) = {[(n) - (m) × L] / [(m) × L]} × 100

Here, L is the rubber content of the graft copolymer.

(3) Reduced viscosity [η _sp /c]

200 ml of acetone was added to the sample 1 g, and the mixture was refluxed for 3 hours, and the solution was centrifuged at 8800 r/min (10000 G) for 40 minutes, and then the insoluble portion was filtered. The filtrate was concentrated on a rotary evaporator, and the precipitate (acetone-soluble portion) was dried under reduced pressure at 60 ° C for 5 hours, and then adjusted to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C), and measured using an Ubbelohde viscometer. [η _sp /c].

(4) Ultimate viscosity [η]

1 g of the sample was uniformly dissolved in 100 cm ^{3 of} dichloromethane, and the specific viscosity [η _sp ] was measured using a Ubbelohde viscometer. Further, the concentration was further changed, and the specific viscosity was measured in the same manner. The graphs of the plotted concentrations [c] and [η _sp /c] were extrapolated to the value of the zero side of the concentration as the ultimate viscosity [η]. That is, it is calculated as η=limη _sp /c(c→0).

(5) Tensile strength and tensile elongation

It was measured at a speed of 50 mm/min, 23 ° C, and 50% RH in accordance with ISO 527 (1993).

(6) Charpy's punching strength

It was measured in accordance with the provisions of ISO 179 (2000) under the conditions of a V-groove (residual width 8.0 mm), 23 ° C, and 50% RH.

(7) Surface gloss

It was measured under the conditions of an incident angle and a reflection angle of 60° in accordance with JIS Z 8741 (1997).

[Reference Example 1] Manufacturing method of graft copolymer (A)

In a nitrogen-substituted reactor, 120 parts by weight of pure water, 0.5 parts by weight of glucose, 0.5 parts by weight of sodium pyrophosphate, 0.005 parts by weight of ferrous sulfate, and 60 parts by weight (as a solid component) of polybutadiene latex were charged ( The weight average rubber particle diameter was 0.3 μm, and the gel content was 85%. The temperature in the reactor was raised to 65 ° C while stirring. A time point at which the internal temperature reached 65 ° C was started as a polymerization, and a mixture containing a monomer (30 parts by weight of styrene and 10 parts by weight of acrylonitrile) and 0.3 parts by weight of a tertiary dodecylmercaptan was continuously dropped over 5 hours. Simultaneously, an aqueous solution containing 0.25 parts by weight of cumene hydroperoxide, 2.5 parts by weight of potassium oleate, and 25 parts by weight of pure water was continuously dropped over 7 hours to complete the reaction. The obtained styrene copolymer latex was solidified with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain a graft copolymer (A). The graft ratio of the styrene-based graft copolymer (A) was 35%, and the reduction viscosity η _sp /c of the acetone-soluble portion was 0.35 dl/g.

[Reference Example 2] Manufacturing method of vinyl-based (co)polymer (B)

The continuous block polymerization apparatus is used, and the mixing of the copolymerization and the resin component is carried out as follows, wherein the continuous bulk polymerization apparatus comprises: a condenser of evaporative reflux having a monomer vapor and a complete 2 m ³ of a spiral ribbon blade Hybrid polymerization tank; single-axis extruder type preheater; and heating device with self-biaxial extruder type de-uniting machine and front-end unit connected in series to 1/3 long barrel Two-axis extruder type feeder.

First, a monomer mixture comprising 70.0 parts by weight of styrene, 30.0 parts by weight of acrylonitrile, 0.15 parts by weight of n-octyl mercaptan, and 0.01 parts by weight of 1,1-di(tri-butylperoxy)cyclohexane, The polymerization tank was continuously supplied at 150 kg/hr, and the polymerization temperature was maintained at 130 ° C and the internal pressure of the vessel was 0.08 MPa, and continuous block polymerization was carried out. The polymerization rate of the polymerization mixture exiting the polymerization tank is controlled to be between 74 and 76%. The obtained polymerization reaction product is subjected to a biaxial extrusion type deaerator, and the unreacted monomer is distilled and distilled from the ventilating port under reduced pressure, and the polymerization rate is set to be 99% or more, and is discharged into a strand shape to be cut. The granules were pelletized to obtain a vinyl (co)polymer (B). The reduced viscosity η _sp /c of the vinyl (co)polymer (B) was 0.53 dl/g.

[Reference Example 3] Polyethylene terephthalate resin (II)

Poly(ethylene terephthalate) resin (II)-1

Re-recycling granules of polyethylene terephthalate resin (manufactured by Xie Rong Industrial Co., Ltd.) were prepared.

Poly(ethylene terephthalate) resin (II)-2

TSB900 (manufactured by Toray Industries, Inc.) was prepared in which the intrinsic viscosity of the original particles of the polyethylene terephthalate resin was determined to be 0.90 at 25 ° C using an o-chlorophenol solvent.

[Reference Example 4] Acrylic acid ‧ styrene copolymer containing epoxy group (III)

Epoxy-containing acrylic acid ‧ styrene copolymer (III)-1

Acrylic ‧ styrene copolymer (trade name: ARUFON UG-4035, manufactured by Toagosei Co., Ltd.) containing methacrylic acid methacrylate, (meth) acrylate, and styrene as monomer units It contains an epoxy group having a weight average molecular weight of 11,000 and an epoxy price of 1.8 meq/g.

Epoxy-containing acrylic acid ‧ styrene copolymer (III)-2

Acrylic acid ‧ styrene copolymer (trade name: Joncryl ADR-4368, manufactured by Johnson Polymers Co., Ltd.) containing methacrylic acid methacrylate, (meth)acrylic acid, and styrene as monomer units An epoxy group having a weight average molecular weight of 7,000 and an epoxy value of 3.5 meq/g.

[Reference Example 5] Acryl group-containing acrylonitrile ‧ styrene copolymer (IV)

73 parts by weight of styrene, 26 parts by weight of acrylonitrile, and 1 part by weight of glycidyl methacrylate were suspension-polymerized to obtain an acrylonitrile ‧ styrene copolymer containing a bead epoxy group.

[Examples 1 to 6]

The graft copolymer (A), the vinyl (co)polymer (B), the polyethylene terephthalate resin (II), and the epoxy group-containing acrylic acid ‧ styrene copolymer (referred to as Reference Examples) III) The mixture of the blending ratios shown in Table 1 was used, and a thermoplastic resin composition obtained by melt-kneading and extruding at a cylinder set temperature of 260 ° C was used to prepare a thermoplastic resin composition obtained by using a 30 mm biaxial extruder. The composition was preliminarily dried in a hot air dryer at 105 ° C for 5 hours, and the electric injection molding machine SE50 manufactured by Sumitomo Heavy Industries, Ltd. was used at a cylinder temperature of 260 ° C and a mold temperature of 60 ° C as specified in ISO 3167 (2002). A multi-purpose test piece was formed into a shape (150 mm in total length, 10 mm in width of the test portion, and 4 mm in thickness), and tensile strength, tensile elongation, and Charpy impact strength were measured. Further, the gusset molded article (thickness: 3 mm) was also molded and used for measurement of surface glossiness.

[Comparative Examples 1 to 5]

The graft copolymer (A), the vinyl (co)polymer (B), the polyethylene terephthalate resin (II), and the epoxy group-containing acrylic acid ‧ styrene copolymer (referred to as Reference Examples) III), mixing was carried out at the mixing ratio shown in Table 2, and a pellet-shaped thermoplastic resin composition was produced in the same manner as in the Example. Further, in Comparative Example 5, the epoxy group-containing acrylonitrile ‧ styrene copolymer (IV) was used instead of the epoxy group-containing acrylonitrile styrene copolymer (III) in the formulation ratio shown in Table 2. With respect to the obtained thermoplastic resin composition, each physical property was measured in accordance with Examples 1 to 6.

From the results of Tables 1 and 2, the following matters are apparent.

The thermoplastic resin compositions of the present invention (Examples 1 to 6) were excellent in both mechanical strength and surface gloss.

On the other hand, in Comparative Example 1, the epoxy group-containing acrylic acid ‧ styrene copolymer (III) was not added, and the mechanical strength was poor as compared with each of Examples 2, 4 and 5. On the other hand, in Comparative Examples 3 and 4, the epoxy group-containing acrylic acid ‧ styrene copolymer (III) was added in a large amount, and the surface gloss was inferior to each of Examples 2 and 6.

In Comparative Example 2, the blending ratio of the polyethylene terephthalate resin (II) was large, and the mechanical strength was poor as compared with each of Examples 1 to 3. Further, in Comparative Example 5, an epoxy group-containing acrylonitrile ‧ styrene copolymer (IV) was used instead of the epoxy group-containing acrylic ‧ styrene copolymer (III), but with Examples 2, 4 and 5 In comparison, the surface gloss is poor.

[Examples 7 and 8, Comparative Examples 6 and 7]

The graft copolymer (A), the vinyl (co)polymer (B), the polyethylene terephthalate resin (II), and the epoxy group-containing acrylic acid ‧ styrene copolymer shown in the reference examples ( III), mixed with the blending ratio shown in Table 3, in the same manner as in the example, a pelletized thermoplastic resin composition was produced. Further, in Comparative Example 7, the epoxy group-containing acrylonitrile styrene copolymer (IV) was used instead of the epoxy group-containing acrylonitrile styrene copolymer (III) in the formulation ratio described in Table 3. With respect to the obtained thermoplastic resin composition, each physical property was measured in accordance with this example.

From the results of Table 3, the following matters are apparent.

The thermoplastic resin compositions of the present invention (Examples 7 and 8) were excellent in both mechanical strength and surface gloss.

On the other hand, in Comparative Example 6, the epoxy group-containing acrylic acid ‧ styrene copolymer (III) was not added, and the mechanical strength was poor as compared with each of Examples 7 and 8. Further, in Comparative Example 7, the epoxy group-containing acrylonitrile ‧ styrene copolymer (IV) was used instead of the epoxy group-containing acrylic ‧ styrene copolymer (III), but compared with Examples 7 and 8 The surface gloss is poor.

Industrial availability

Since the thermoplastic resin composition of the present invention is excellent in mechanical properties and surface glossiness, it can be used for various purposes such as electric ‧ electronic parts, automobile parts, machine parts, OA equipment, home electric appliances, and the like, and the like. . Specifically, for example, various gears, various housings, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, and variable capacitor housings can be cited. (variable capacitor case), optical pick-up, oscillator, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, Magnetic heads, power modules, housings, semiconductors, liquid crystals, FDD brackets, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc., electrical and electronic parts; VTR parts, TV frames, pedestals, TV parts such as back cavity, irons, hair dryers, electric cooker parts, microwave oven parts, audio parts, audio, laser discs (registered trademarks), sound machine parts such as optical discs, lighting parts, refrigerator parts, etc. Family ‧ affairs electrical parts represented by air conditioner parts, typewriter parts, word processor parts, etc.; office computer related parts, telephone related parts, True organs associated parts, photocopying and associate parts, jig wash, oil-free bearings, boat Various bearings such as tail bearings and underwater bearings; mechanical parts represented by motor parts, lighters, typewriters, etc.; optical machines, precision mechanical related parts represented by microscopes, binoculars, cameras, clocks, etc.; alternator terminals (alternator terminal), alternator connector, IC regulator, exhaust valve, etc.; fuel related ‧ exhaust system ‧ suction system various pipelines; intake nozzle exhaust pipe, intake manifold , fuel pump, engine cooling water joint, carburetor tube shaft, carburetor separator, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake washer wear sensor (brake pad Wear sensor), throttle position sensor, crankshaft position sensor, airflow meter, thermostat seat for air conditioner, warm air flow control valve, radiator motor brush holder, water pump blade Turbine blades, wiper motor related parts, distributors, starter switches, starter relays, transmission wiring harnesses, window brushing nozzles, air conditioning panel switching substrates, Fuel-related solenoid valve coil, fuse connector, H terminal (horn terminal), electrical component insulation board, stepping motor rotor, lamp socket, lamp reflector, lampshade, brake piston, solenoid rack (solenoid bobbin ), engine oil filter, ignition device shell, etc. Extremely useful for these various uses.

Claims (7)

A thermoplastic resin composition containing 0.01 to 1 part by weight of an epoxy group-containing acrylic acid with respect to 100 parts by weight of the resin composition containing the styrene resin (I) and the polyethylene terephthalate resin (II). Styrene-based copolymer (III). The thermoplastic resin composition of claim 1, wherein the epoxy group-containing acrylic acid ‧ styrene copolymer (III) has a weight average molecular weight of 2,000 to 20,000. The thermoplastic resin composition of claim 1 or 2 wherein the epoxy group-containing acrylic acid ‧ styrene copolymer (III) has an epoxy value of 0.5 to 4.0 (meq/g). The thermoplastic resin composition according to any one of claims 1 to 3, wherein the weight ratio of the styrene resin (I) and the polyethylene terephthalate resin (II) is from 50:50 to 99:1. . The thermoplastic resin composition according to any one of claims 1 to 4, wherein the styrene resin (I) contains a weight ratio of the graft copolymer (A) to the vinyl (co)polymer (B). a composition of a ratio of 10:90 to 50:50, wherein the graft copolymer (A) is selected from the group consisting of an aromatic vinyl monomer (b) and a vinyl cyanide monomer in the rubbery polymer (a). The monomer (c) and one or more monomers of the copolymerizable other vinyl monomer (d) are graft copolymerized, and the vinyl (co)polymer (B) is selected from the group consisting of aromatic vinyl monomers (b) And one or more monomers of the vinyl cyanide monomer (c) and the copolymerizable other vinyl monomer (d) are polymerized. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the polyethylene terephthalate resin (II) is a whole of a recycled material of a polyethylene terephthalate resin molded article or portion. A molded article obtained by molding a thermoplastic resin composition according to any one of claims 1 to 6.