KR101480176B1 - Thermoplastic resin composition having improved flowability and heat resistance - Google Patents
Thermoplastic resin composition having improved flowability and heat resistance Download PDFInfo
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- KR101480176B1 KR101480176B1 KR20100139622A KR20100139622A KR101480176B1 KR 101480176 B1 KR101480176 B1 KR 101480176B1 KR 20100139622 A KR20100139622 A KR 20100139622A KR 20100139622 A KR20100139622 A KR 20100139622A KR 101480176 B1 KR101480176 B1 KR 101480176B1
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Abstract
The present invention relates to a thermoplastic resin composition having enhanced fluidity and heat resistance by containing a regenerated polyester resin in a specific weight portion.
Description
The present invention relates to a thermoplastic resin composition having enhanced fluidity and heat resistance. More specifically, the present invention relates to a thermoplastic resin composition having improved fluidity and heat resistance by incorporating a recycled polyester resin in a specific weight portion.
A mixture of an acrylonitrile-butadiene-styrene copolymer (ABS) resin and a polyethylene terephthalate (PET) resin is excellent in processability and mechanical strength and is widely used for manufacturing interior and exterior parts of electrical and electronic products and office automation equipment. Recently, as the interest in the environment has been increased, there is an increasing tendency to use recycled PET that is eco-friendly and can reduce carbon emissions.
However, since the ABS / PET blend itself is difficult to mix ABS and PET, a styrene-acrylonitrile (SAN) copolymer containing an epoxy group needs to be added. In this case, .
Also, in order to use ABS as a car interior, the heat resistance must be higher than 100 ° C. However, the ABS / PET alloy itself can not increase the heat resistance to more than 100 ° C.
Accordingly, there is a need to develop an ABS / PET thermoplastic resin composition having improved fluidity and heat resistance and being environmentally friendly.
It is an object of the present invention to provide a thermoplastic resin composition having improved fluidity and heat resistance.
Another object of the present invention is to provide an environmentally friendly thermoplastic resin composition.
The thermoplastic resin composition of the present invention comprises (A) a styrenic polymer containing an epoxy group comprising a vinyl copolymer containing an epoxy group and a rubber-reinforced styrenic copolymer resin; (B) a regenerated polyester resin; (C) polycarbonate; (D) an N-phenylmaleimide heat-resistant reinforcing agent; (E) a heat stabilizer; (A) + (B) + (C) + (D), wherein the recycled polyester resin is a recycled polyethylene terephthalate, , A melt flow index of 8-25 g / 10 min, and a heat resistance of 95-115 ° C.
In one embodiment, the intrinsic viscosity of the recycled polyethylene terephthalate may be 0.3-1.0 g / L.
In one embodiment, the content of hydroxy groups in the polycarbonate may be 0.1-8.0 wt%.
The present invention provides a thermoplastic resin composition having improved fluidity and heat resistance. Further, the present invention provides an environmentally friendly thermoplastic resin composition.
The thermoplastic resin composition of the present invention may have a fluidity, that is, a melt flow index of 8-25 g / 10 min. The melt flow index can be measured by a conventional method. For example, the pellet produced from the thermoplastic resin composition can be measured according to ASTM D1238. The flowability may preferably be 9-19 g / 10 min.
Further, the thermoplastic resin composition of the present invention may have a heat resistance of 95 to 115 占 폚. The heat resistance can be measured by a conventional method. For example, a 1/4 inch sample made of the thermoplastic resin composition can be measured according to ASTM D648. The heat resistance may preferably be 95-110 占 폚, more preferably 102-108 占 폚.
(A) a styrenic polymer containing an epoxy group
In the styrenic polymer containing an epoxy group, the epoxy group may be contained in an amount of 0.001-5.0 mol%. Within this range, compatibility with PET is improved and mechanical strength is improved.
The styrenic polymer containing an epoxy group may be contained in an amount of 30-87 parts by weight based on 100 parts by weight of a base resin composed of a styrenic polymer containing an epoxy group, a recycled polyester resin, a polycarbonate and an N-phenylmaleimide heat-resistant reinforcing agent . Within the above range, it is advantageous in heat resistance. Preferably 35-68 parts by weight.
The styrenic polymer containing an epoxy group may be composed of (A1) a vinyl copolymer containing an epoxy group and (A2) a rubber-reinforced styrene copolymer resin. The content ratio of (A1) to (A2) in the styrenic polymer is not particularly limited. For example, it may be composed of (A1) 5-100 wt% of a vinyl copolymer containing an epoxy group and (A2) 0-95 wt% of a rubber-reinforced styrene copolymer resin. Preferably A1) 5-15% by weight of a vinyl copolymer containing an epoxy group and (A2) 85-95% by weight of a rubber-reinforced styrene copolymer resin.
(A1) a vinyl copolymer containing an epoxy group
The vinyl copolymer containing an epoxy group is prepared by polymerizing a monomer mixture composed of an unsaturated epoxy compound (A11) containing an epoxy group and a vinyl compound (A12), and a copolymer in which an unsaturated epoxy group is present in the styrene- Resin.
In the vinyl copolymer containing an epoxy group, the content ratio of the (A11) unsaturated epoxy compound containing an epoxy group to the (A12) vinyl compound is not particularly limited. Preferably, it may be composed of 0.001-5 mol% of an unsaturated epoxy compound (A11) containing an epoxy group and 95-99.999 mol% of a vinyl compound (A12).
The vinyl copolymer containing (A1) epoxy group is preferably 1 to 10 parts by weight of (A) the styrenic polymer containing an epoxy group.
(A11) an unsaturated epoxy compound containing an epoxy group
The unsaturated epoxy compound containing an epoxy group may be represented by the following general formula (1).
≪ Formula 1 >
Wherein R 1 , R 2 , R 3 , R 6 , R 7 and R 8 are each independently selected from the group consisting of H, a C 1-12 alkyl group or an unsaturated alkyl group, a C 6 -C 14 aryl group, a C 1-12 saturated or unsaturated alkyl group A substituted or unsubstituted C6-C14 aryl group, Y is an ether group (-O-), a carboxy group (-O (C = O) -, - (C = O) O-) (-O-) or a carboxy group (-O (C = O) -, - (C = O) - or a C 6-14 arylene group or a C 6-12 aryl group substituted with a C 1-12 saturated or unsaturated alkyl group, O) O), R 4 and R 5 are each independently of the other a C 1 -C 12 alkylene, a C 6 -C 14 arylene, or a C 6 -C 14 saturated or unsaturated alkyl group substituted with a C 1-12 saturated or unsaturated alkyl group And Y is (R4-Y-R5) when Y is an alkylene group of C1-C12, an aryl group of C6-C14, or a C6-C14 arylene group substituted by a C1-12 saturated or unsaturated alkyl group, Lt; / RTI >
In the above, the C1-12 alkyl group or the C1-C12 alkylene group may preferably be a C1-C6 alkyl group or an alkylene group, more preferably a C1-C4 alkyl group or an alkylene group.
In the above, the C6-C14 aryl group or the C6-C14 arylene group may preferably be a C6-C10 aryl group or an arylene group.
Examples of the unsaturated epoxy compound include glycidyl (meth) acrylate, epoxyalkyl acrylate, allyl glycidyl ether, aryl glycidyl ether, butadiene monoxide, vinyl glycidyl ether, glycidyl itaconate But are not limited thereto. The unsaturated epoxy compounds may be used alone or in combination of two or more.
The unsaturated epoxy compound may be added in an amount of 0.001-5 mol%, preferably 0.3-3 mol%, of the mixture of monomers constituting the vinyl copolymer containing an epoxy group. Within this range, the effect of improving the impact strength is good and gelation phenomenon does not occur at the time of extrusion.
(A12) Vinyl compound
The vinyl-based compound includes an aromatic vinyl-based monomer and a monomer polymerizable with the aromatic vinyl-based monomer.
The aromatic vinyl monomer may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene But are not limited thereto. The aromatic vinyl monomer may be used alone or in a mixture thereof.
The aromatic vinyl-based monomer and the polymerizable monomer may be a saturated nitrile-based monomer such as acrylonitrile, an unsaturated nitrile-based monomer such as methacrylonitrile, or a mixture of two or more thereof. Preferably acrylonitrile is preferred.
The ratio of the aromatic vinyl monomer and the aromatic vinyl monomer to the copolymerizable monomer may be determined according to the ratio and compatibility of the monomers other than the rubber in the rubber-reinforced styrenic copolymer resin. Preferably, the total content of the aromatic vinyl monomer and the aromatic vinyl monomer is 40-90 wt% and 10-60 wt%, respectively. Within this range, the viscosity does not increase sharply so that the workability of the final product is not deteriorated and the strength is not lowered.
The vinyl-based compound may further include a monomer capable of imparting processability and heat resistance. Examples of the monomer include (meth) acrylic acid, alkyl methacrylate having 1 to 4 carbon atoms, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) (Meth) acrylate, N-substituted maleimide, maleic acid, fumaric acid, itaconic acid and anhydrides thereof, dimethylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, vinylimidazole, But are not limited to, vinyl pyrrolidone, vinyl caprolactam, vinyl carbazole, vinyl aniline, (meth) acrylamide.
The monomer capable of imparting processability and heat resistance may be added in an amount of 0 to 30% by weight, preferably 1 to 20% by weight, more preferably 2 to 15% by weight, of the total vinyl compound.
(A2) Rubber-reinforced styrene-based copolymer resin
The rubber-reinforced styrene-based copolymer resin is a polymer in which a rubber-like polymer is dispersed in the form of particles in a matrix (continuous phase) composed of an aromatic vinyl-based copolymer. And adding an aromatic vinyl monomer and optionally a vinyl-based monomer copolymerizable with the monomer to the rubber-like polymer and polymerizing them.
The rubber-reinforced styrene-based resin can be produced by a known polymerization method including emulsion polymerization, suspension polymerization, bulk polymerization and the like. Usually, a styrene-based graft copolymer resin alone or a styrene-based graft copolymer resin and a styrene-based copolymer resin are mixed and extruded. In the case of bulk polymerization, a rubber-reinforced styrene-based copolymer resin can be produced only by a one-step reaction process without separately preparing a styrene-based graft copolymer resin and a styrene-based copolymer resin.
The rubber content of the rubber-reinforced styrene-based resin is preferably 5-30% by weight of the rubber-reinforced styrene-based resin. Within the above range, the impact reinforcing effect is effective within a range not significantly lowering the fluidity of the resin.
The rubber-like particle size in order to exhibit appropriate physical properties in the alloying of the rubber-reinforced styrene resin and the recycled polyester resin can be 0.1-6.0 mu m in Z-average. Preferably, the rubber-like particle size may range from 0.25 to 3.5 占 퐉 in terms of Z-average.
Examples of the rubber-reinforced styrene resin include acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-acrylic rubber-styrene copolymer resin (AAS), acrylonitrile-ethylene propylene rubber- AES).
The rubber-reinforced styrene-based resin can be produced by using (A21) a styrene-based graft resin alone or (A21) a styrene-based graft resin and (A22) a styrene-based copolymer resin. It is preferable to blend them in consideration of their compatibility.
The rubber-reinforced styrene-based resin may be a mixture of (A21) 20-100% by weight of styrene-based graft resin and (A22) 0-80% by weight of styrene-based copolymer resin, but is not limited thereto.
(A2) The rubber-reinforced styrene-based resin is preferably 30 to 70 parts by weight of the styrene-based polymer (A) containing an epoxy group.
(A21) The styrene-based graft copolymer resin
The styrene-based graft copolymer resin can be produced by adding an aromatic vinyl-based monomer capable of graft polymerization to a rubber-like polymer and a monomer copolymerizable with the aromatic vinyl-based monomer.
Examples of the rubber polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), and saturated rubbers in which hydrogen is added to the diene rubbers, isoprene rubbers, Acrylic rubbers such as acrylic acid and ethylene / propylene / diene monomer terpolymers (EPDM). Preferably, polybutadiene rubber among diene rubbers is preferable.
As the rubber polymer, 5-65% by weight of the styrene-based graft copolymer resin is suitable. In consideration of the impact strength and appearance at the time of preparing the graft copolymer, the average size of the rubber particles is suitably from 0.1 to 4 탆.
The aromatic vinyl monomers that can be graft-polymerized in the rubber are styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, di Bromostyrene, and vinylnaphthalene. Styrene is preferably used. The aromatic vinyl-based monomer is suitably 30 to 94% by weight of the styrene-based graft copolymer resin.
Examples of the monomer copolymerizable with the aromatic vinyl monomer include unsaturated nitrile such as acrylonitrile and unsaturated nitrile such as methacrylonitrile, or a mixture of two or more thereof. Preferably acrylonitrile is preferred. The copolymerizable monomer is suitably 1-40 wt% of the graft copolymer resin.
And may further include a monomer which adds toughness and heat resistance at the time of producing the styrene-based graft copolymer. For example, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be further added. These monomers may be added in an amount of 0 to 15% by weight in the copolymer resin.
(A22) The styrene-based copolymer resin
The styrenic copolymer resin can be produced by polymerizing an aromatic vinyl monomer other than the rubber polymer among the components of the styrene-based graft copolymer and a monomer copolymerizable with the aromatic vinyl monomer.
The aromatic vinyl monomers used in the styrene-based copolymer resin include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, Dibromostyrene, vinylnaphthalene, and the like. Styrene is preferably used. The aromatic vinyl-based monomer is suitably 60-90 wt% of the styrenic copolymer resin.
Examples of the monomer copolymerizable with the aromatic vinyl monomer include unsaturated nitrile such as acrylonitrile and unsaturated nitrile such as methacrylonitrile, or a mixture of two or more thereof. Preferably acrylonitrile is preferred. The copolymerizable monomer is suitably 10-40 wt% of the styrenic copolymer resin.
Monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be further added to the styrenic copolymer resin for processability and heat resistance. These monomers may be added in an amount of 0-15 wt% of the copolymer resin.
(B) Recycled polyester resin
The regenerated polyester resin is not particularly limited. For example, in the recycled polyester resin, the polyester resin is preferably a polyester resin obtained by copolymerizing terephthalic acid, isophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, Naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, aromatic dicarboxylic acid in which a carboxyl group is substituted with a dimethyl group Dimethyl-1,2-naphthalate, which is an alkyl ester of naphthalenedicarboxylic acid, dimethyl-1,5-naphthalate, dimethyl-1,7-naphthalate, dimethyl- Dimethyl-2,6-naphthalate, dimethyl-2,7-naphthalate or a mixture thereof, ethylene glycol having 2 to 12 carbon atoms as a diol, 1,2-butanediol -Pro Propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1, 2-dimethyl- 5-pentanediol, 1,6-hexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, or a mixture thereof. Methods of condensation are commonly known to those skilled in the art.
Preferably, the polyester resin in the reclaimed polyester resin may include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and allyl mixed therewith. More preferably, polyethylene terephthalate is preferable.
In the recycled polyester resin, the polyester resin may be given an inorganic particle according to the use. Examples thereof include, but are not limited to, titanium dioxide (TiO 2 ), silicon dioxide (SiO 2 ), aluminum hydroxide (Al (OH) 3 ) and the like.
The recycled polyester resin preferably has an intrinsic viscosity of 0.3 to 1.0 g / L, preferably 0.4 to 1.0 g / L, and more preferably 0.7 to 1.0 g / L. Within the above range, the resin composition of the present invention can be easily produced with good impact strength.
The recycled polyester resin can be produced by re-extruding a commercially available polyester resin under ordinary conditions. Or obtained by a PET bottle, a polyester pressure product, or an article of manufacture, and then subjected to appropriate processing to lower the molecular weight or viscosity.
The recycled polyester resin may be contained in an amount of 1-30 parts by weight based on 100 parts by weight of a base resin composed of a styrenic polymer containing an epoxy group, a recycled polyester resin, polycarbonate and an N-phenylmaleimide heat-resistant reinforcing agent. If it is less than 1 part by weight, the fluidity and appearance are poor. If it is more than 30 parts by weight, the heat resistance becomes poor. Preferably 20-30 parts by weight.
(C) Polycarbonate
The polycarbonate can be prepared by reacting a diphenol represented by the following formula (2) with phosgene, halogen formate or carbonic acid diester.
(2)
(Wherein A represents a single bond, C1-C5 alkylene, C1-C5 alkylidene, C5-C6 cycloalkylidene, -S- or -SO2-).
Specific examples of the diphenols of formula (2) include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,3-dihydroxyphenyl) 5-dichloro-4-hydroxyphenyl) -propane, and the like, but are not limited thereto. Of these, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro- Hydroxyphenyl) -cyclohexane, and the like, and 2,2-bis- (4-hydroxyphenyl) -propane, also referred to as bisphenol-A, is most preferred.
In addition, compounds such as resorcinol and hydroquinone may be used as the above diphenol compounds.
The polycarbonate resin may be a homopolymer using one dihydric phenolic compound or a copolymer using two or more dihydric phenolic compounds or a mixture thereof.
The weight average molecular weight of the polycarbonate resin is 5,000-200,000 g / mol, preferably 15,000-100,000 g / mol.
The polycarbonate resin may have the form of a linear polycarbonate resin, a branched polycarbonate resin, a copolymer thereof or a mixture thereof, or a polyester carbonate copolymer resin.
The linear polycarbonate resin is preferably a bisphenol A-based polycarbonate resin, and the branched polycarbonate resin is obtained by reacting a polyfunctional aromatic compound such as trimellitic anhydride and trimellitic acid with a dihydroxyphenol and a polycarbonate precursor Can be manufactured. The polyester carbonate copolymer resin can be prepared by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor.
The polycarbonate resin may be one in which the content of the hydroxyl group in the polycarbonate resin is reduced. For example, the content of the hydroxyl group may be 0.1-10 wt%. Within the above range, the styrene-based polymer containing an epoxy group is not reacted and the fluidity is not deteriorated. A method for reducing the hydroxyl group content in the polycarbonate resin is as follows.
The end-blocked polycarbonate resin of the present invention is characterized in that a carbonic acid diester and an aromatic carbonate derivative represented by the following formula (3) are transesterified with divalent phenol.
(3)
Wherein R < 1 > is a t-butyl group or a p-cumyl group.
The aromatic carbonate derivative compound may be added before the start of the transesterification reaction or may be introduced in the transesterification reaction and proceed in situ.
The dihydric phenol is used in a molar ratio of 0.85 to 1.2, preferably 0.9 to 1.1, to the mixed carbonate monomer comprising the carbonate diester and the aromatic carbonate derivative compound. When used in the above molar ratio, it is preferable for increasing the molecular weight.
The mixed carbonate monomer is composed of 60 to 95 mol% of carbonic acid diester and 5 to 40 mol% of aromatic carbonate derivative compound. The above range is preferable in terms of the reaction rate and physical properties.
In the embodiment of the present invention, the ester exchange reaction may be carried out at a reduced pressure at 160 to 300 ° C, preferably 200 to 300 ° C, more preferably 220 to 260 ° C. In order to reduce the reaction rate and the side reaction in the temperature range
desirable.
In addition, it is preferable that the transesterification reaction is conducted for at least 10 minutes or more, preferably 15 minutes to 24 hours, more preferably 15 minutes to 3 hours under reduced-pressure conditions of 1 torr or less in order to reduce the reaction rate and the side reaction.
The polycarbonate resin may be contained in an amount of 2 to 20 parts by weight based on 100 parts by weight of a base resin comprising a styrenic polymer containing an epoxy group, a recycled polyester resin, polycarbonate and an N-phenylmaleimide heat-resistant reinforcing agent. Within the above range, the mechanical strength is excellent and the workability is good.
(D) N-phenylmaleimide-based heat enhancer
N-phenylmaleimide-based heat reinforcing agents refer to terpolymers of styrene, N-phenylmaleimide and maleic anhydride. Preferably, the N-phenylmaleimide heat-resistant reinforcing agent comprises 44-50 wt% of styrene, 45-55 wt% of N-phenylmaleimide, and 1-5 wt% of maleic anhydride. Preferably 45% by weight of styrene, 50% by weight of N-phenylmaleimide and 5% by weight of maleic anhydride.
The N-phenylmaleimide heat-resistant reinforcing agent is a yellow powder having a glass transition temperature of 194-198 DEG C, a weight average molecular weight of 50,000-300,000 g / mol and a flowability (260 DEG C / 10kg) of 2.4-4.4 g / 10 min .
The N-phenylmaleimide heat-resistant reinforcing agent may be contained in an amount of 10-30 parts by weight based on 100 parts by weight of a base resin comprising an epoxy group-containing styrenic polymer, regenerated polyester resin, polycarbonate and N-phenylmaleimide heat-resistant reinforcing agent . Within the above range, heat resistance is not lowered, and there is no problem in extrusion and flowability. Preferably 20-30 parts by weight.
(E) Heat stabilizer
The heat stabilizer serves to inhibit or block the thermal decomposition of the composition when the resin composition is mixed or molded at a high temperature.
The heat stabilizer is not particularly limited. For example, a phosphite type, a tinmarate type or an aluminosilicate type can be used.
The heat stabilizer may be contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of a base resin composed of a styrenic polymer containing an epoxy group, a regenerated polyester resin, polycarbonate and an N-phenylmaleimide heat-resistant reinforcing agent. Within this range, thermal stability is improved. Preferably 0.1-0.5 parts by weight.
(F) Lubricant
The lubricant serves to lubricate a metal surface in contact with the resin composition during processing, molding, or extrusion of the resin composition to help flow.
There are no particular restrictions on lubricants. For example, olefin-based, metal stearate-based or amide-based ones can be used.
The lubricant may be contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of a base resin comprising a styrenic polymer containing an epoxy group, a recycled polyester resin, polycarbonate and an N-phenylmaleimide heat-resistant reinforcing agent. Within this range, the workability is improved. Preferably 0.1-0.5 parts by weight.
The resin composition of the present invention may further comprise at least one additive selected from the group consisting of an impact modifier, a dye, a pigment, a releasing agent, a dispersant, an antistatic agent, a weather stabilizer, an inorganic filler, have.
The resin composition of the present invention can be prepared by a known method. For example, after the components of the present invention and the additives are mixed, they may be melt-extruded in an extruder and produced in the form of pellets.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.
Production Example 1: Preparation of a vinyl copolymer (epoxy-containing SAN) containing an epoxy group
100 parts by weight of a monomer mixture consisting of 2 mol% of glycidyl methacrylate, 70 parts of styrene and 30 parts of acrylonitrile, and 100 parts by weight of deionized water, 0.2 parts by weight of azobisisobutyronitrile, 0.4 parts by weight of tricalcium phosphate, and 0.2 parts by weight of n-octylmercaptan were added. The temperature was raised to 80 ° C for 60 minutes, and then maintained at 80 ° C for 180 minutes to prepare a styrene-acrylonitrile copolymer resin containing an epoxy group. This was washed with water, dehydrated and dried to prepare a styrene-acrylonitrile copolymer resin (epoxy-containing SAN) containing an epoxy group in a powder state.
Production Example 2: Production of rubber-reinforced styrene-based copolymer resin
(1) Production of styrene-based graft copolymer resin (g-ABS)
To a mixture containing 50 parts by weight of a butadiene rubber latex solid, 36 parts by weight of styrene, 14 parts by weight of acrylonitrile and 150 parts by weight of deionized water, 1.0 part by weight of potassium oleate, 0.4 part by weight of cumene hydroperoxide, 0.4 part by weight of glucose, 0.01 part by weight of sulfuric acid ferrous hydrate, and 0.3 part by weight of sodium pyrophosphate were added. And reacted at 75 캜 for 5 hours to prepare a graft copolymer resin. To the resulting resin solids was added 0.4 part by weight of sulfuric acid and solidified to prepare a powdered grafted acrylonitrile-butadiene-styrene copolymer (g-ABS).
(2) Production of styrene-based copolymer resin (SAN)
0.2 part by weight of azobisisobutyronitrile, 0.4 part by weight of tricalcium phosphate and 0.2 parts by weight of n-octylmercaptan were added to a mixture of 75 parts by weight of styrene, 25 parts by weight of acrylonitrile and 120 parts by weight of deionized water, The temperature was raised to 80 캜 for 90 minutes, and then maintained for 180 minutes to prepare a styrene copolymer resin. This was washed with water, dehydrated and dried to prepare a powdered styrene acrylonitrile copolymer resin (SAN).
Production Example 3: Preparation of recycled polyethylene terephthalate (PET)
Polyethylene terephthalate (A1100, manufactured by Anychem) was re-extruded at 250 占 폚 to prepare a recycled polyethylene terephthalate. The intrinsic viscosity of the prepared recycled polyethylene terephthalate was 0.74 g / L.
Specific specifications of each component used in the following examples and comparative examples are as follows.
1. Vinyl Copolymer Containing Epoxy Group: The epoxy-containing SAN prepared in Preparation Example 1
2. Rubber-reinforced styrenic copolymer resin: The g-ABS and SAN prepared in Production Example 2
3. Recycled polyester resin: The recycled PET resin prepared in Production Example 3
4. Polycarbonate: Bisphenol-A system (SC-1190, Cheil Industries) (hydroxyl group content: 0.8%)
5. N-Phenylmaleimide heat reinforcing agent: DNAKA-IP (MS-NB) (Japan DNAKA)
6. Heat stabilizer: Phosphite type (IGANOX1076, CIBA)
7. Lubricant: STEARATE series (LEBAX-140B, Lion Chem)
Examples 1-6
The respective components of the resin composition were mixed in the amounts shown in Table 1 below and mixed uniformly in a blender. The obtained mixture was extruded at 240 DEG C in a conventional twin-screw extruder at a screw speed of 250 rpm and a mixture feed rate of 50 kg / hr to produce pellets. The prepared pellets were dried at 100 ° C for 4 hours, and then specimens were prepared in a 6 oz extruder under conditions of a molding temperature of 240 ° C and a mold temperature of 70 ° C.
Comparative Example 1-2
The pellets were prepared in the same manner as in Example 1-6 except that the respective components of the resin composition were mixed in the amounts shown in Table 2 below.
Experimental Example : Measurement of Physical Properties of Specimen
The following properties of the specimens prepared in the Examples and Comparative Examples were measured and the results are shown in Table 3 below.
≪ Method for measuring physical properties &
1. Melt Flow Index (MFI): The pelletized resin extruded according to ASTM D1238 was evaluated at a load of 10 kg at 250 캜.
2. Heat resistance (HDT): According to ASTM D348, a 1/4-inch specimen was subjected to a load of 18.5 kg / cm 2 . The final results were evaluated by the average of five specimens.
3. Spiral test: The injection length of a helical injection was measured after a spiral injection molding with a thickness of 2 mm and a width of 10 mm was injected at a injection temperature of 150 ° C., an injection pressure of 1200 bar, and an injection speed of 8 cm / sec.
4. Impact strength: A notch was applied to the specimen according to ASTM D256. The final test results were calculated as the average of the five test results.
5. Appearance: The visual appearance and gloss of the specimen exterior were visually evaluated. The evaluation criteria are as follows:
◎: No FLOW MARK
○: FLOW MARK can be identified
X: FLOW MARK
(g / 10 min)
(mm)
As mentioned above, the thermoplastic resin composition of the present invention has improved both the melt flow index and the impact strength by incorporating the regenerated polyethylene terephthalate in a specific amount. On the other hand, Comparative Example 1-2 containing less than 1 part by weight of the recycled polyethylene terephthalate had poor melt flow index and impact strength.
Claims (13)
(B) a regenerated polyester resin;
(C) polycarbonate;
(D) an N-phenylmaleimide heat-resistant reinforcing agent;
(E) a heat stabilizer; And
(F) a thermoplastic resin composition comprising a lubricant,
The recycled polyester resin is recycled polyethylene terephthalate
30 to 87 parts by weight of (A), 1 to 30 parts by weight of (B), (C), and (C) of 100 parts by weight of the base resin composed of (A) + ) Is 2-20 parts by weight, and (D) is 10-30 parts by weight,
Wherein the melt flow index according to ASTM D1238 of the thermoplastic resin composition is 8-25 g / 10 min.
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| KR101593732B1 (en) * | 2012-12-28 | 2016-02-12 | 제일모직주식회사 | Thermoplastic resin composition and article produced therefrom |
| KR102167672B1 (en) * | 2019-08-26 | 2020-10-19 | 주식회사 휴비스 | Recycle polyester shaped fiber with enhanced shape stability, and the preparing thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003138125A (en) * | 2001-11-05 | 2003-05-14 | Mitsubishi Chemicals Corp | Aromatic polycarbonate resin composition |
| JP2006169460A (en) * | 2004-12-20 | 2006-06-29 | Toray Ind Inc | Thermoplastic resin composition and molded products thereof |
| KR100779519B1 (en) * | 2005-06-16 | 2007-11-28 | 주식회사 엘지화학 | Thermoplastic resin composition having improved gloss at metal deposition, scratching-resistance and heat-resistance |
| KR20100122303A (en) * | 2009-05-12 | 2010-11-22 | 주식회사 엘지화학 | Thermoplastic abs resin composition containing recycled resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003138125A (en) * | 2001-11-05 | 2003-05-14 | Mitsubishi Chemicals Corp | Aromatic polycarbonate resin composition |
| JP2006169460A (en) * | 2004-12-20 | 2006-06-29 | Toray Ind Inc | Thermoplastic resin composition and molded products thereof |
| KR100779519B1 (en) * | 2005-06-16 | 2007-11-28 | 주식회사 엘지화학 | Thermoplastic resin composition having improved gloss at metal deposition, scratching-resistance and heat-resistance |
| KR20100122303A (en) * | 2009-05-12 | 2010-11-22 | 주식회사 엘지화학 | Thermoplastic abs resin composition containing recycled resin |
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