KR101949555B1 - Thermoplastic resin composition and molded article of same - Google Patents
Thermoplastic resin composition and molded article of same Download PDFInfo
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- KR101949555B1 KR101949555B1 KR1020147018361A KR20147018361A KR101949555B1 KR 101949555 B1 KR101949555 B1 KR 101949555B1 KR 1020147018361 A KR1020147018361 A KR 1020147018361A KR 20147018361 A KR20147018361 A KR 20147018361A KR 101949555 B1 KR101949555 B1 KR 101949555B1
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
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- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
A thermoplastic resin composition comprising 0.01 to 1 part by weight of an acryl-styrenic copolymer (III) containing an epoxy group per 100 parts by weight of a resin composition comprising a styrene-based resin (I) and a polyethylene terephthalate resin (II) The molded article is excellent in mechanical characteristics and surface gloss.
Description
The present invention relates to a thermoplastic resin composition containing a styrene-based resin and a polyethylene terephthalate resin, and a molded product thereof.
Styrenic resins typified by ABS resins have excellent mechanical properties, molding processability and electrical insulation properties, and thus are used in a wide range of fields including home electrical appliances, OA appliances, and automobile parts.
On the other hand, polyethylene terephthalate (PET) resin, which is a polyester-based resin, is widely used for various bottles, food trays, sheets and the like because of its excellent mechanical strength, transparency and gas barrier properties.
Since the PET resin has such properties that the impact resistance is enhanced by stretching and the heat resistance is also increased by crystallization, the drawbacks such as low impact resistance are remarkable in the injection molding method, The use ratio as a product is very low.
In addition, since the interest in measures for environmental problems has increased recently, specifications for utilizing recycled resin such as Green Purchasing Law and EPEAT (American Electronics Standard) have been established regardless of the domestic and foreign countries, and recycled resin or recycled resin A demand for a resin composition is increasing. Among them, the waste amount of PET resin is increasing year by year, and the recovery and reuse of these wastes are attracting attention.
Therefore, if the disadvantage of the PET resin as the injection-molded product can be solved, not only the use of virgin material but also the use of recycled material can be expanded, and an increase in the amount of use can be expected.
As one of the means for improving the impact resistance, a polymer alloy polymerization with the above-mentioned ABS resin can be mentioned. Patent Document 1 discloses a composition and a production condition for improving impact resistance by blending an ABS resin with a recycled PET resin. However, it is known that the compatibility of the PET resin and the ABS resin is not better than originally, and therefore, the composition obtained by the method described in this patent document does not necessarily provide good impact resistance.
Therefore, research on improving the compatibility of an alloy composition of a PET resin and an ABS resin has been conducted for a long time. Patent Document 2 discloses an example of using an acrylonitrile-styrene copolymer having an epoxy group as a modifier. In Patent Document 3, a vinyl monomer having an epoxy group in addition to acrylonitrile and styrene is graft copolymerized with a diene rubber to improve compatibility Is proposed. However, in such means, improvement in mechanical strength can be achieved, but in some cases, crosslinked products are produced in the extruder or in the molding machine, and the surface gloss is impaired.
On the other hand, an acryl-styrenic copolymer containing an epoxy group is a copolymer comprising a recycled PET resin and a linear low density polyethylene resin (Patent Document 4), and an example added to a composition comprising a polylactic acid resin and an ABS resin (Patent Document 5) , There is no example added to improve compatibility and good surface gloss to a composition comprising a PET resin and an ABS resin.
It is an object of the present invention to provide a thermoplastic resin composition containing a styrene-based resin and a polyethylene terephthalate resin excellent in mechanical characteristics and surface gloss, and a molded product thereof, which overcomes the drawbacks of the prior art.
As a result of intensive investigations to solve the above problems, the inventors of the present invention have found that, with respect to 100 parts by weight of a resin composition comprising a styrene resin (I) and a polyethylene terephthalate resin (II), an acryl- , And 0.01 to 1 part by weight of the cohesive (III).
That is, the present invention relates to a thermoplastic resin composition and a molded article thereof as described in the following (1) to (7).
(1) A thermoplastic resin composition comprising 0.01 to 1 part by weight of an acryl-styrenic copolymer (III) containing an epoxy group per 100 parts by weight of a resin composition comprising a styrene resin (I) and a polyethylene terephthalate resin (II) Resin composition.
(2) The thermoplastic resin composition according to (1), wherein the acryl-styrenic copolymer (III) containing an epoxy group 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 value of the acryl-styrenic copolymer (III) containing an epoxy group is 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 type resin (I) and the polyethylene terephthalate resin (II) is 50:50 to 99: 1.
(5) The styrene-based resin (I) is obtained by copolymerizing the rubbery polymer (a) with one or more monomers selected from an aromatic vinyl monomer (b), a vinyl cyanide monomer (c) and other copolymerizable vinyl monomers (A) obtained by polymerizing a graft copolymer (A) graft-copolymerized with at least one monomer selected from the group consisting of an aromatic vinyl monomer (b), a vinyl cyanide monomer (c) and a copolymerizable other vinyl monomer A thermoplastic resin composition according to any one of (1) to (4), wherein the thermoplastic resin composition is a composition comprising a thermoplastic resin (B) polymer (B) in a weight ratio of 10:90 to 50:50.
(6) The thermoplastic resin composition according to any one of (1) to (5), wherein all or part of the recycled material of the polyethylene terephthalate resin molded article is used as the polyethylene terephthalate resin (II).
(7) A molded article obtained by molding the thermoplastic resin composition according to any one of (1) to (6).
According to the present invention, it is possible to obtain a thermoplastic resin composition comprising a styrene resin and a polyethylene terephthalate resin excellent in mechanical characteristics and surface gloss, and a molded article thereof.
Hereinafter, embodiments for carrying out the present invention will be described concretely.
The styrene-based resin (I) in the present invention is a vinyl-based (vinyl) monomer (a) comprising at least one monomer selected from the group consisting of an aromatic vinyl monomer (b), a vinyl cyanide monomer (c) and a copolymerizable other vinyl monomer ) Refers to the addition of the rubbery polymer (a) to the polymer (B) or the vinyl-based (co) polymer (B).
When the styrene type resin (I) is obtained by adding the rubbery polymer (a) to the vinyl type (co) polymer (B), from the viewpoint of the compatibility of the vinyl type (co) polymer (B) and the rubbery polymer A graft copolymer (A) obtained by graft-copolymerizing an aromatic vinyl monomer (b), a vinyl cyanide monomer (c) and at least one other monomer selected from a copolymerizable other vinyl monomer (d) (Co) polymer (B) comprising at least one monomer selected from an aromatic vinyl monomer (b), a vinyl cyanide monomer (c) and a copolymerizable other vinyl monomer (d) Do. Further, it is not necessary that all of the monomer mixture blended with the rubbery polymer (a) be grafted to the graft copolymer (A), and the monomer mixture of the monomer mixture is combined as a polymer not grafted There may be. However, the graft ratio is preferably 10 to 100%, more preferably 20 to 50%.
The blended amount of the rubbery polymer (a) used in the graft copolymer (A) is not particularly limited, 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 to be. The blending amount of the monomer mixture in the graft copolymer (A) is preferably 20 to 90 parts by weight, more preferably 30 to 80 parts by weight, still more preferably 35 to 65 parts by weight. By using the rubbery polymer (a) and the monomer mixture in this proportion, good impact resistance and molding processability can be obtained. The proportion of the monomer mixture to be compounded in the graft copolymer (A) is not particularly limited, but it is preferably 20 to 99% by weight for the aromatic vinyl monomer (b), 1 to 40% by weight for the vinyl cyanide monomer (c) And the other vinyl monomer (d) copolymerizable therewith is preferably used in a proportion of 0 to 79% by weight, and good impact resistance and moldability can be obtained.
The proportion of the monomer mixture blended in the vinyl-based (co) polymer (B) is not particularly limited, but preferably 20 to 99% by weight of the aromatic vinyl monomer (b), 1 to 40% by weight of the vinyl cyanide monomer %, And 0 to 79% by weight of other vinyl monomers copolymerizable therewith (d), and excellent impact resistance and molding processability can be obtained.
The blending ratio of the graft copolymer (A) and the vinyl-based (co) polymer (B) is preferably such that the weight ratio of (A) :( B) is from 10:90 to 50:50, 80 to 40: 60. If the proportion of the graft copolymer (A) is less than the above-mentioned range or the proportion of the vinyl-based (co) polymer (B) exceeds the above range, the impact strength tends to decrease. If the ratio of the graft copolymer (A) exceeds the above range, the flowability tends to decrease.
The reduced viscosity (? SP / c) of the acetone-soluble fraction of the graft copolymer (A) is not particularly limited, but is preferably 0.1 to 0.6 dl / g. Otherwise, the impact resistance tends to deteriorate, or the melt viscosity tends to rise and the moldability tends to deteriorate. More preferably 0.3 to 0.5 dl / g.
The reduced viscosity (? Sp / c) of the vinyl-based (co) polymer (B) is not particularly limited, but is preferably 0.1 to 0.6 dl / g. Otherwise, the impact resistance tends to deteriorate, or the melt viscosity tends to rise and the moldability tends to deteriorate. More preferably 0.3 to 0.5 dl / g.
The rubbery polymer (a) is not particularly limited, but a diene rubber, an acrylic rubber, an ethylene rubber, or the like can be used. Specific examples include polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), polyisoprene, poly (butadiene-butyl acrylate), poly (butadiene-methyl methacrylate) Propylene-diene rubber, poly (ethylene-isoprene), poly (ethylene-methyl acrylate), and the like. These rubbery polymers (a) may be used alone or as a mixture of two or more thereof. Among these rubbery polymers (a), polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile) and ethylene-propylene rubber are preferably used in terms of impact resistance.
The weight average particle diameter of the rubbery polymer (a) is not particularly limited, but is preferably 0.1 to 0.5 占 퐉 in view of the mechanical strength such as impact resistance and the balance of the appearance of the molded article. If it is less than 0.1 mu m, the impact strength of the obtained thermoplastic composition may be lowered, and if it exceeds 0.5 mu m, the appearance of the molded article may decrease. More preferably 0.15 to 0.4 mu m.
The aromatic vinyl monomer (b) used in the graft copolymer (A) and the vinyl-based (co) polymer (B) is not particularly limited and specific examples thereof include styrene,? -Methylstyrene, orthomethylstyrene, -t-butylstyrene, halogenated styrene, and the like, and they may be used alone or in combination of two or more. Of these, styrene and? -Methylstyrene are preferable, and styrene is particularly preferable.
The vinyl cyanide monomer (c) used in the graft copolymer (A) and the vinyl-based (co) polymer (B) is not particularly limited, but specific examples thereof include acrylonitrile and methacrylonitrile. Or two or more species can be used. Among them, acrylonitrile is preferable in terms of impact resistance.
(D) other copolymerizable monomers copolymerizable with the graft copolymer (A) and the vinyl-based (co) polymer (B) are not particularly limited and specific examples thereof include methyl (meth) acrylate, ethyl (Meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl -Unsaturated carboxylic acid esters such as chloroethyl, maleimide compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, unsaturated dicarboxylic acids such as maleic acid, and unsaturated dicarboxylic acids such as maleic anhydride. And unsaturated amide compounds such as acrylic acid, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, and maleic anhydride. A plurality of vinyl-based (co) polymers (B) may be used.
The production method of the graft copolymer (A) or the vinyl-based (co) polymer (B) is not particularly limited and may be any of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. The method of introducing the monomer is not particularly limited, and any method may be used in which all or part of the monomers are added, or a part or all of the monomers are added in portions.
Specific examples of the styrenic resin (I) used in the present invention include polystyrene, high impact polystyrene (HIPS), AS resin, AAS resin, AES resin, ABS resin, MAS resin, MABS resin, MBS resin, And alloys of these resins with other resins.
The polyethylene terephthalate resin (II) used in the present invention refers to a high molecular weight thermoplastic polyester resin having an ester bond in its main chain, in which terephthalic acid is used as an acid component and ethylene glycol is used as a glycol component, Isophthalic acid, adipic acid, oxalic acid, and the like as the glycol component, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol , Cyclohexanediol, etc., or long chain glycols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like may be used in an amount of 20 mol% or less.
The polyethylene terephthalate resin (II) in the present invention may be a virgin material that is not subjected to thermal history such as molding or may be a recycled material of a polyethylene terephthalate resin molded article (hereinafter referred to as a recycled material) , It is desirable to include the recycled material as a whole or a part from the viewpoint of resource protection. Specific examples of the recycled material include waste materials obtained by recovering molded articles molded at least once into plastic bottles or the like, and materials generated in the trimming process at the time of molding the sheet material. Specific examples of the shape of the recycled material include a flake, Or a pelletized product for removal of impurities. It is preferable that the recycled material does not contain a reinforcing material such as glass fiber.
The weight ratio of the styrene type resin (I) to the polyethylene terephthalate resin (II) in the resin composition comprising the styrene type resin (I) and the polyethylene terephthalate resin (II) in the present invention is not particularly limited, It is preferable that the styrene resin (I) and the polyethylene terephthalate resin (II) have a weight ratio of 50:50 to 99: 1, more preferably a weight ratio of 55 : 45 to 90: 10. If the ratio of the styrene resin (I) is less than the above-mentioned range or the proportion of the polyethylene terephthalate resin (II) exceeds the above range, the mechanical strength may be lowered.
The acrylic styrenic copolymer (III) containing an epoxy group in the present invention is not particularly limited as long as it has an epoxy group such as a (meth) acrylic ester monomer having an epoxy group, (meth) acrylic acid or the like Or a method of copolymerizing styrene with a monomer having no epoxy group such as (meth) acrylic acid, and then, an alcohol having an epoxy group in the carboxyl group of the (meth) acrylic acid unit in the copolymer is subjected to condensation reaction And then adding them.
Examples of the (meth) acrylic ester monomer having an epoxy group which can be used when copolymerizing an acryl-styrenic copolymer (III) having an epoxy group are glycidyl methacrylate, glycidyl acrylate and the like , Glycidyl methacrylate are preferable.
Specific examples of the monomer having no epoxy group such as (meth) acrylic acid include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (Meth) acrylic acid, (meth) acrylic acid, (meth) acrylic acid, and the like can be given as examples of the (meth) acrylic acid, Methyl (meth) acrylate, ethyl (meth) acrylate and n-butyl (meth) acrylate are preferably used. These may be used alone or in combination of two or more.
The weight average molecular weight of the acryl-styrenic copolymer (III) containing an epoxy group is preferably 2,000 to 20,000, more preferably 5,000 to 15,000 in terms of suppressing flowability and bleed-out. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
The epoxy styrenic copolymer (III) containing an epoxy group preferably has an epoxy value of 0.5 to 4.0 (meq / g), more preferably 1.0 to 3.5 (meq / g) from the viewpoints of mechanical strength and surface gloss . Also, the epoxy value referred to herein is a value measured by a hydrochloric acid dioxane method.
The polymerization method of the acryl-styrenic copolymer (III) containing an epoxy group is not particularly limited, and known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used. (Preferably 5 minutes to 30 minutes) in a short time (preferably 5 minutes to 30 minutes) under a pressurizing condition (preferably 1 MPa or more) is preferable because of the high polymerization rate, the polymerization initiator Chain transfer agent and solvent are not used.
The blending amount of the acryl-styrenic copolymer (III) containing an epoxy group used in the present invention is 0.01 to 1 part by weight based on 100 parts by weight of the resin composition comprising the styrene type resin (I) and the polyethylene terephthalate resin (II) , Preferably 0.03 to 0.7 part by weight, and more preferably 0.05 to 0.5 part by weight. If the addition amount of the acryl-styrenic copolymer (III) containing an epoxy group is less than the above range, the mechanical strength is not sufficient. On the contrary, if the amount exceeds the above range, the surface gloss of the obtained thermoplastic resin composition tends to deteriorate Which is undesirable.
The thermoplastic resin composition of the present invention is characterized in that it is excellent in surface gloss by blending (I) to (III). The surface gloss referred to herein is evaluated by numerical values measured in accordance with the provisions of JIS Z 8741 (1997), and the surface gloss (spots) described in Patent Document 4 (Japanese Patent Application Laid-Open No. 2005-200534) )) And the contents of evaluation are different. In the thermoplastic resin composition of the present invention, since it has a surface gloss of 90 or more, preferably 95 or more, it can be preferably used as an appearance product.
In addition, the thermoplastic resin composition of the present invention may contain various additives such as polyvinyl chloride, polyolefins such as polyethylene and polypropylene, polyamides such as nylon 6 and nylon 66, polybutylene terephthalate and polycycloolefins Fluorine-based resins such as polycarbonate and polytetrafluoroethylene, and various elastomers may be blended.
The thermoplastic resin composition of the present invention may further contain additives such as glass fiber, glass powder, glass beads, glass flake, alumina, alumina fiber, carbon fiber, graphite fiber, Inorganic fillers such as potassium titanate fiber, wollastonite, asbestos, hard clay, fired clay, talc, kaolin, mica, calcium carbonate, magnesium carbonate, aluminum oxide and minerals; hindered phenol- Antioxidants such as organic compounds, heat stabilizers such as phenol and acrylate, ultraviolet absorbers such as benzotriazole, benzophenone or salicylate, hindered amine light stabilizers, higher fatty acids and acidic esters, Acid amides, and higher alcohols, plasticizers such as montanic acid and salts thereof, esters thereof, half-esters thereof, stearyl alcohol , Coloring inhibitors such as stearamide and ethylene wax, various flame retardants, flame retarding additives, phosphites and hypophosphites, neutralizing agents such as phosphoric acid, monosodium phosphate, maleic anhydride and succinic anhydride, nucleating agents, amine-based, An antistatic agent such as an ether-based agent, and a coloring agent such as carbon black, pigment, dye, and the like.
The method for producing the thermoplastic resin composition of the present invention is not particularly limited and the components (I) to (III) and other components described above may be mixed with a V-type blender, a super mixer, a superplater and a Henschel mixer Or the like, but in many cases, the mixture is a mixture obtained by homogeneously melt-mixing the preliminary mixture. Such a mixture can be obtained by melting and kneading the preliminary mixture at a temperature of, for example, 230 to 300 캜, more preferably 250 to 285 캜, using a kneading means and pelletizing. Specific melting and kneading and pelletizing methods include a method of melting a resin composition by using various melting and mixing machines such as a kneader, a single screw, and a twin screw extruder, extruding the resin composition, and pelletizing the melt by a pelletizer .
The thermoplastic resin composition of the present invention obtained by the above method can be molded according to a known method used for molding a thermoplastic resin at present such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding and gas assist molding, The molding method itself is not particularly limited.
Example
Hereinafter, the present invention will be described in detail in Examples and Comparative Examples, but the present invention is not limited thereto.
(1) Weight average rubber particle diameter
"Rubber Age Vol. 484 to 490 (1960) by E. Schmidt, PH Biddison ". That is, the particle diameter of the cumulative weight fraction of 50% was determined from the weight percentage of the cream and the cumulative weight fraction of sodium alginate, using polybutadiene particle diameters different from each other by the concentration of sodium alginate.
(2) Graft rate
Acetone was added to a predetermined amount (m) of the graft copolymer and the mixture was refluxed for 3 hours. The solution was centrifuged at 8800 r / min (10000 G) for 40 minutes. The insoluble matter was filtered off, And the weight (n) was measured.
The graft ratio was calculated from the following formula.
The graft ratio (%) = {[(n) - (m) L] / [(m) L]} 100
Here, L is the rubber content of the graft copolymer.
(3) Reduction viscosity [? SP / c]
Add 200 ml of acetone to 1 g of the sample, reflux for 3 hours, centrifuge the solution at 8800 r / min (10000 G) for 40 minutes, and insoluble matter is filtered. The filtrate was concentrated using a rotary evaporator and the precipitate (acetone soluble fraction) was dried under reduced pressure at 60 DEG C for 5 hours and then adjusted to 0.4 g / 100 mL (methyl ethyl ketone, 30 DEG C) to obtain Ubbelohde ) [Η SP / c] was measured using a viscometer.
(4) Intrinsic viscosity [η]
1 g of the sample was homogeneously dissolved in 100 cm 3 of dichloromethane, and the specific viscosity (specific viscosity) [η SP ] was measured using a Ubeider viscometer. The value obtained by extrapolating the graph obtained by plotting the concentration [c] and [? SP / c] to the concentration zero side was regarded as the intrinsic viscosity [?] By changing the concentration and measuring the same non-viscosity. That is, it was calculated by? = Lim? SP / c (c? 0).
(5) Tensile strength, tensile elongation
Measured under conditions of a speed of 50 mm / min, 23 캜 and 50% RH in accordance with the provisions of ISO 527 (1993).
(6) Charpy impact strength
In accordance with ISO 179 (2000), V notches (the remaining width 8.0 mm) were measured at 23 DEG C and 50% RH.
(7) Surface glossiness
The measurement was made under the conditions of an incident angle and a reflection angle of 60 degrees in accordance with the provisions of JIS Z 8741 (1997).
[Reference Example 1] Production of graft copolymer (A)
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 of polybutadiene latex (weight average rubber particle diameter: 0.3 mu m, gel content: 85% (In terms of solid content) was added, and the temperature in the reactor was raised to 65 캜 while stirring. When the internal temperature reached 65 占 폚, a mixture consisting of monomer (30 parts by weight of styrene and 10 parts by weight of acrylonitrile) and 0.3 part by weight of t-dodecyl mercaptan was continuously added dropwise over 5 hours. Concurrently, 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 added dropwise over 7 hours to complete the reaction. The resulting styrene-based copolymer latex was solidified with sulfuric acid, neutralized with caustic soda, and then washed, filtered and dried to obtain a graft copolymer (A). The graft ratio of the styrene graft copolymer (A) was 35%, and the reduced viscosity? Sp / c of the acetone-soluble component was 0.35 dl / g.
[Referential Example 2] Production method of vinyl-based (co) polymer (B)
Evaporation of Monomer Steam A complete mixing type polymerization tank of 2 m < 3 > having a reflux condenser and a helical ribbon wing, a single screw extruder type preheater, and a barrel portion of 1/3 length from the tip of the twin screw extruder type demonomer and demonomer Copolymerization and mixing of resin components were carried out by using a continuous bulk polymerization apparatus comprising a twin screw extruder type feeder having a heating device connected in a tandem as follows.
First, a monomer mixture composed of 70.0 parts by weight of styrene, 30.0 parts by weight of acrylonitrile, 0.15 part by weight of n-octylmercaptan and 0.01 part by weight of 1,1-di (t-butylperoxy) cyclohexane was added at 150 kg / And continuously supplied into a polymerization vessel, and the polymerization was carried out at a polymerization temperature of 130 캜 and a polymerization internal pressure of 0.08 MPa for continuous bulk polymerization. The polymerization rate of the polymerization reaction mixture in the polymerization stage was controlled to be between 74 and 76%. The polymerization reaction product thus obtained was distilled off under reduced pressure from an unreacted monomer in a vent hole by a twin-screw extruder-type monomer unit, and the polymer was discharged into a strand with a polymerization degree of 99% or more of the external appearance, and pelletized by a cutter. (Co) polymer (B). The reduced viscosity? Sp / c of the vinyl-based (co) polymer (B) was 0.53 dl / g.
[Reference Example 3] Polyethylene terephthalate resin (II)
Polyethylene terephthalate resin (II) -1
(Manufactured by Kyoei Sangyo Co., Ltd.) of polyethylene terephthalate resin was prepared.
Polyethylene terephthalate resin (II) -2
The virgin pellet of the polyethylene terephthalate resin was prepared by using TSB900 (manufactured by Toray Industries, Inc.) having an intrinsic viscosity of 0.90 as measured at 25 DEG C using o-chlorophenol solvent.
[Reference Example 4] Acrylic-styrenic copolymer (III) containing an epoxy group [
Acrylic-styrenic copolymer (III) -1 containing an epoxy group
Styrene-based copolymer (trade name: ARUFON UG-1) containing an epoxy group having a weight average molecular weight of 11,000 and an epoxy value of 1.8 meq / g and containing glycidyl methacrylate, (meth) acrylic acid and styrene as monomer units, 4035, manufactured by Toagosei Co., Ltd.).
Acrylic-styrenic copolymer (III) -2 containing an epoxy group
Styrene copolymer (trade name: JONCRYL ADR-1) containing an epoxy group having a weight average molecular weight of 7,000 and an epoxy value of 3.5 meq / g and containing glycidyl methacrylate, (meth) acrylic acid and styrene as monomer units, 4368, a product of Johnson Polymers Ltd.).
[Reference Example 5] An acrylonitrile-styrene resin copolymer (IV) containing an epoxy group,
73 parts by weight of styrene, 26 parts by weight of acrylonitrile and 1 part by weight of glycidyl methacrylate were subjected to suspension polymerization to obtain an acrylonitrile-styrene resin copolymer containing an epoxy group on a bead.
[Examples 1 to 6]
(A), a vinyl-based (co) polymer (B), a polyethylene terephthalate resin (II) and an acryl-styrenic copolymer (III) containing an epoxy group in the mixing ratios shown in Table 1 Kneaded and extruded at a cylinder setting temperature of 260 ° C using a 30 mm twin screw extruder equipped with a vent to prepare a thermoplastic resin composition in the form of a pellet, and the obtained thermoplastic resin composition was preliminarily prepared in a hot air drier at 105 ° C for 5 hours Drying, Sumitomo Heavy Industries, Ltd. A multi-purpose specimen A (full length 150 mm, width 10 mm, thickness 4 mm) specified by ISO 3167 (2002) at a cylinder temperature of 260 ° C and a mold temperature of 60 ° C using a motorized injection molding machine SE50 , And tensile strength, tensile elongation, and Charpy impact strength were measured. In addition, a molded plate (3 mm in thickness) was molded and used for measurement of surface gloss.
[Comparative Examples 1 to 5]
(A), a vinyl-based (co) polymer (B), a polyethylene terephthalate resin (II) and an acryl-styrenic copolymer (III) containing an epoxy group were mixed at the blending ratios shown in Table 2 A thermoplastic resin composition in the form of pellets was prepared in the same manner as in Example. In Comparative Example 5, an acrylonitrile-styrene copolymer (IV) containing an epoxy group was used in a blending ratio shown in Table 2 in place of the acryl-styrene copolymer (III) containing an epoxy group. The obtained thermoplastic resin composition was measured for physical properties according to Examples 1 to 6.
From the results of Tables 1 and 2, the following facts became clear.
All of the thermoplastic resin compositions of the present invention (Examples 1 to 6) were excellent in balance of mechanical strength and surface gloss.
On the other hand, in Comparative Example 1, the acrylic styrenic copolymer (III) containing an epoxy group was not added, and the mechanical strengths were lower than those of Examples 2, 4 and 5, respectively. On the other hand, in Comparative Examples 3 and 4, the amount of the acrylic styrenic copolymer (III) containing an epoxy group was large, and the surface gloss was inferior to those of Examples 2 and 6, respectively.
In Comparative Example 2, the blending ratio of the polyethylene terephthalate resin (II) was large, and the mechanical strengths were lower than those of Examples 1 to 3, respectively. In Comparative Example 5, an acrylonitrile-styrene resin copolymer (IV) containing an epoxy group was used in place of the acryl-styrenic copolymer (III) containing an epoxy group. In comparison with Examples 2, 4 and 5 The surface gloss was poor.
[Examples 7 and 8, Comparative Examples 6 and 7]
The styrene-based copolymer (III) containing the graft copolymer (A), the vinyl-based (co) polymer (B), the polyethylene terephthalate resin (II) and the epoxy group shown in Reference Example was mixed Thus, a thermoplastic resin composition in the form of pellets was prepared in the same manner as in the above Examples. In Comparative Example 7, an acrylonitrile-styrene resin copolymer (IV) containing an epoxy group was used in a blending ratio shown in Table 3 in place of the acryl-styrene copolymer (III) containing an epoxy group. The obtained thermoplastic resin composition was measured for physical properties according to the above examples.
From the results in Table 3, the following facts became clear.
All of the thermoplastic resin compositions of the present invention (Examples 7 and 8) were excellent in balance of mechanical strength and surface gloss.
On the other hand, in Comparative Example 6, the acrylic styrenic copolymer (III) containing an epoxy group was not added, and the mechanical strength was lower than those of Examples 7 and 8, respectively. In Comparative Example 7, an acrylonitrile-styrene resin copolymer (IV) containing an epoxy group was used in place of the acryl-styrenic copolymer (III) containing an epoxy group. The castle was inferior.
(Industrial availability)
Since the thermoplastic resin composition of the present invention is excellent in mechanical properties and surface gloss, it can be used for a variety of uses such as housings for electric / electronic parts, automobile parts, machine parts, OA equipment, home appliances, have. More specifically, for example, various types of gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, varicain cases, optical pickups, Electricity represented by printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, · Audio equipment parts such as electronic parts, VTR parts, TV range, stand, TV cabinet parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio and laser discs (registered trademark) , Lighting parts, refrigerator parts, air conditioner parts, typewriter parts and word processor parts Related parts such as computer parts, telephone related parts, facsimile parts, copier related parts, various kinds of bearings such as cleaning jig, oilless bearing, stern bearing and underwater bearing, motor parts, lighter, typewriter, Various kinds of valves such as an alternator terminal, an alternator connector, an IC regulator, an exhaust gas valve, a fuel relation, an exhaust system, an intake system various pipes, an air intake nozzle snow, an optical device represented by a microscope, a binoculars, Air intake manifold, Fuel pump, Engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter , Thermostat base for air conditioner, heating warm air flow control valve Starter switch, starter relay, wire harness for transmission, wind washer nozzle, air-conditioner panel switch board, fuel-related electromagnetic valve coil, fuse holder, water pump impeller, turbine vane, wiper motor related parts, distributor, A lamp housing, a brake piston, a solenoid bobbin, an engine oil filter, an ignition device case, and the like, and it is very useful in these various applications.
Claims (7)
Wherein the weight ratio of the styrene type resin (I) and the polyethylene terephthalate resin (II) is 50:50 to 99: 1.
Wherein the acryl-styrenic copolymer (III) containing an epoxy group has a weight average molecular weight of 2,000 to 20,000.
Wherein an epoxy value of the acryl-styrenic copolymer (III) containing an epoxy group is 0.5 to 4.0 (meq / g).
Wherein the polyethylene terephthalate resin (II) is all or part of a recycled material of a molded product of polyethylene terephthalate resin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012043706 | 2012-02-29 | ||
| JPJP-P-2012-043706 | 2012-02-29 | ||
| PCT/JP2013/055329 WO2013129547A1 (en) | 2012-02-29 | 2013-02-28 | Thermoplastic resin composition and molded article of same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20140133498A KR20140133498A (en) | 2014-11-19 |
| KR101949555B1 true KR101949555B1 (en) | 2019-02-18 |
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| KR1020147018361A KR101949555B1 (en) | 2012-02-29 | 2013-02-28 | Thermoplastic resin composition and molded article of same |
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|---|---|
| JP (1) | JP5565523B2 (en) |
| KR (1) | KR101949555B1 (en) |
| CN (1) | CN104114635B (en) |
| MY (1) | MY167375A (en) |
| PH (1) | PH12014501843A1 (en) |
| TW (1) | TW201343763A (en) |
| WO (1) | WO2013129547A1 (en) |
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| JP2016132718A (en) * | 2015-01-19 | 2016-07-25 | 富士ゼロックス株式会社 | Resin composition and resin molding |
| KR20190035780A (en) * | 2016-09-01 | 2019-04-03 | 테크노 유엠지 가부시키가이샤 | Epoxy-modified vinyl copolymer, thermoplastic resin composition containing the same, and molded article thereof |
| EP3369797B1 (en) * | 2017-03-02 | 2021-01-06 | EKWB d.o.o. | Cooling liquid composition for a liquid cooling system for cooling a heat generating element arranged on a printed circuit board |
| KR20190055573A (en) * | 2017-11-15 | 2019-05-23 | 에스케이케미칼 주식회사 | Polyamide Resin Composition and Resin Product Comprising the Same |
| WO2024010749A1 (en) * | 2022-07-06 | 2024-01-11 | Kaneka Americas Holding, Inc. | Modifiers for polyesters that improve viscosity in melt |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003286382A (en) * | 2002-03-28 | 2003-10-10 | Toray Ind Inc | Sheetlike resin and molded article comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62285947A (en) * | 1986-06-04 | 1987-12-11 | Toray Ind Inc | Polyester resin composition |
| JPH075814B2 (en) | 1988-07-05 | 1995-01-25 | 東レ株式会社 | Fiber-reinforced thermoplastic resin composition |
| JPH05320487A (en) * | 1992-05-22 | 1993-12-03 | Sumitomo Bakelite Co Ltd | Thermoplastic resin composition |
| JPH07292183A (en) * | 1994-04-28 | 1995-11-07 | Daicel Chem Ind Ltd | Easily tearable film and its production |
| JP2001139782A (en) * | 1999-11-11 | 2001-05-22 | Aron Kasei Co Ltd | Polyester resin composition |
| JP2004067728A (en) | 2002-08-01 | 2004-03-04 | Umg Abs Ltd | Thermoplastic resin composition utilizing recycled polyethylene terephthalate resin material |
| JP4707955B2 (en) | 2004-01-15 | 2011-06-22 | フクビ化学工業株式会社 | Resin composition for molding material |
| US7999021B2 (en) * | 2005-08-04 | 2011-08-16 | Toray Industries, Inc. | Resin composition and molded article made thereof |
| JP2008106091A (en) | 2006-10-23 | 2008-05-08 | Sumitomo Bakelite Co Ltd | Resin composition containing polylactic acid |
| TWI432460B (en) * | 2010-07-08 | 2014-04-01 | Chi Mei Corp | Block copolymer and polymer composition made therefrom |
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- 2013-02-28 KR KR1020147018361A patent/KR101949555B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003286382A (en) * | 2002-03-28 | 2003-10-10 | Toray Ind Inc | Sheetlike resin and molded article comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104114635A (en) | 2014-10-22 |
| MY167375A (en) | 2018-08-16 |
| JP5565523B2 (en) | 2014-08-06 |
| WO2013129547A1 (en) | 2013-09-06 |
| PH12014501843B1 (en) | 2014-11-17 |
| PH12014501843A1 (en) | 2014-11-17 |
| KR20140133498A (en) | 2014-11-19 |
| CN104114635B (en) | 2015-09-09 |
| JPWO2013129547A1 (en) | 2015-07-30 |
| TW201343763A (en) | 2013-11-01 |
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