KR101480180B1 - Polycarbonate resin composition having high gloss and molded articles thereof - Google Patents
Polycarbonate resin composition having high gloss and molded articles thereof Download PDFInfo
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- KR101480180B1 KR101480180B1 KR20110147849A KR20110147849A KR101480180B1 KR 101480180 B1 KR101480180 B1 KR 101480180B1 KR 20110147849 A KR20110147849 A KR 20110147849A KR 20110147849 A KR20110147849 A KR 20110147849A KR 101480180 B1 KR101480180 B1 KR 101480180B1
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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Abstract
The high-gloss polycarbonate resin composition of the present invention comprises (A) a polycarbonate-based resin; (B) an aromatic or aliphatic (meth) acrylate resin; (C) a rubber-modified vinyl-based graft copolymer resin; (D) phosphorus flame retardant; And (E) an alkaline earth metal salt having a density of 2.7 to 5.5 g / cm 3 and a refractive index of 1.6 or more; And a control unit.
Description
The present invention relates to a high-gloss polycarbonate resin composition. More specifically, the present invention relates to a high-gloss polycarbonate resin composition having excellent physical properties such as scratch resistance, rigidity and gloss.
PC / ABS alloy resin can be used for both heat resistance and impact strength of polycarbonate (PC) and acrylonitrile-butadiene-styrene (ABS) It has processing characteristics and mechanical properties. In addition, it exhibits excellent physical properties compared to ABS and can be used for various purposes because it can reduce cost compared to PC. In particular, the halogen-free NH (non halogen) -PC / ABS resin does not cause environmental pollution and has a low human hazard, and thus can be used in various electronic products and automobile parts such as TV housings, monitor housings, Notebook batteries, door handles, bumpers, and instrument panels.
The alloys used in the above applications are required to have high gloss and high impact properties. Especially, polycarbonate is vulnerable to scratches, and therefore scratch resistance is also required.
In the case of conventional high alloyed alloy, RHCM9 Rapid heat cycle molding , etc., is the main method, but there are limitations such as mold price and injection time. In the case of an alloy requiring high impact / high rigidity, there is a method of increasing the content of rubber, but it is difficult to ensure high gloss and high appearance.
In addition, when an acrylic resin is blended to exhibit scratch resistance, impact resistance and heat resistance are deteriorated.
An object of the present invention is to provide a polycarbonate resin composition having a physical property balance excellent in impact strength, heat resistance, mechanical properties, rigidity, flame retardancy, scratch resistance and gloss.
Another object of the present invention is to provide a polycarbonate resin composition and a molded product thereof which are excellent in impact strength, heat resistance, mechanical properties, rigidity, flame retardancy, scratch resistance and glossiness and can be suitably applied to housings or parts of electrical and electronic products .
One aspect of the present invention relates to a high-gloss polycarbonate resin composition. The high-gloss polycarbonate resin composition comprises (A) a polycarbonate-based resin; (B) an aromatic or aliphatic (meth) acrylate resin; (C) a rubber-modified vinyl-based graft copolymer resin; (D) phosphorus flame retardant; And (E) an alkaline earth metal salt having a density of 2.7 to 5.5 g / cm 3 and a refractive index of 1.6 or more.
In an embodiment, the polycarbonate resin composition comprises (A) 30 to 98% by weight of a polycarbonate resin; (B) 1 to 80% by weight of an aromatic or aliphatic (meth) acrylate resin; And (C) 1 to 30% by weight of a rubber-modified vinyl-based graft copolymer resin; (D) 1 to 30 parts by weight of a phosphorus-based flame retardant, based on 100 parts by weight of the base resin containing (A) + (B) + (C) And (E) 1 to 10 parts by weight of an alkaline earth metal salt having a density of 2.7 to 5.5 g / cm 3 and a refractive index of 1.6 or more.
The aromatic or aliphatic (meth) acrylate resin (B) may have a refractive index of 1.50 to 1.579.
(B1) 5 to 100% by weight of an aromatic or aliphatic (meth) acrylate represented by the following formula (1) or (2); And (b2) 0 to 95% by weight of a monofunctional unsaturated monomer, or a mixture of these copolymers:
[Chemical Formula 1]
Wherein R 1 is hydrogen or a methyl group, m is an integer of 0 to 10, and Y is a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, Selected)
(2)
(Wherein R 1 is hydrogen or a methyl group, m is an integer of 0 ~ 10, Z is oxygen (O) or sulfur (S), Ar is a cycloalkyl group and a C 6 unsubstituted or substituted with a carbon number of 5-10 A substituted or unsubstituted aryl group having 1 to 20 carbon atoms).
The monofunctional unsaturated monomer is preferably an alkyl (meth) acrylate having 1 to 10 carbon atoms; Unsaturated group-containing carboxylic acid; Acid anhydrides; Hydroxyl group-containing (meth) acrylates; (Meth) acrylamide, unsaturated naphthyl, aromatic vinyl monomers and the like can be used.
The aromatic or aliphatic (meth) acrylate resin (B) may have a glass transition temperature of 50 ° C to 110 ° C and a weight average molecular weight of 3,000 to 300,000 g / mol.
The rubber-modified vinyl-based graft copolymer resin (C) may have a shell structure formed by grafting an unsaturated monomer on a rubber core, and the unsaturated monomer may include an alkyl (meth) acrylate having 1 to 10 carbon atoms.
The rubber-modified vinyl-based graft copolymer resin (C) is a first rubber-modified vinyl-based graft copolymer in which a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer is grafted to (C1) a diene rubber; And (C2) a second rubber-modified vinyl-based graft copolymer in which a monomer mixture comprising an aromatic vinyl monomer and an alkyl (meth) acrylate having 1 to 10 carbon atoms is grafted on the diene rubber.
The phosphorus flame retardant (D) may contain a bisphenol unit.
The (E) alkaline earth metal salt may have an average particle size of 0.5 to 3 탆.
Another aspect of the present invention relates to a molded article molded from the resin composition. In embodiments, the molded article has a 1/8 "thick Izod impact strength of 4 to 80 kgf / cm2 according to ASTM D256, a 60 degree gloss measured with a Gardner Gloss meter of a 1/8" thick specimen according to ASTM D523, %, And the 1/16 "thickness flame retardancy can be V-0 according to the UL 94 V flame retardant specification.
The present invention relates to a polycarbonate resin composition and a molded article thereof which have a physical property balance excellent in impact strength, heat resistance, mechanical properties, rigidity, flame retardancy, scratch resistance and glossiness and which can be suitably applied to housings or parts of electrical and electronic products The present invention provides the effect of the present invention.
As used herein, unless otherwise specified, "(meth) acrylic" means that both "acrylic" and "methacrylic" are possible. For example, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.
The high-gloss polycarbonate resin composition of the present invention comprises (A) a polycarbonate-based resin; (B) an aromatic or aliphatic (meth) acrylate resin; (C) a rubber-modified vinyl-based graft copolymer resin; (D) phosphorus flame retardant; And (E) an alkaline earth metal salt having a density of 2.7 to 5.5 g / cm 3 and a refractive index of 1.6 or more.
(A) a polycarbonate resin
The polycarbonate resin (A) can be produced by reacting a dihydric phenol compound with phosgene in the presence of a molecular weight modifier and a catalyst according to a conventional production method. In another embodiment, the polycarbonate resin may be prepared by using an ester interchange reaction of a dihydroxy phenolic compound and a carbonate precursor such as diphenyl carbonate.
In the process for producing the polycarbonate resin (A), bisphenol-based compounds can be used as the dihydric phenol compounds, and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) Can be used. At this time, the bisphenol A may be partially or wholly replaced by other dihydric phenol compounds. Examples of other dihydric phenolic compounds that can be used include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Halogenated bisphenol such as bis (4-hydroxyphenyl) ketone or bis (4-hydroxyphenyl) ether or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) .
However, the type of the dihydroxy phenol compound that can be used for the production of the polycarbonate resin (A) is not limited thereto, and any polycarbonate resin (A) may be used in combination with any dihydroxy phenol compound Can be manufactured.
The polycarbonate resin (A) may be a homopolymer using one dihydric phenolic compound, a copolymer using two or more dihydric phenolic compounds, or a mixture thereof.
In general, the polycarbonate resin (A) may be in the form of a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin. The polycarbonate resin The linear polycarbonate resin, the branched polycarbonate resin, or the polyester carbonate copolymer resin may all be used.
As the linear polycarbonate resin (A), for example, a bisphenol A-based polycarbonate resin can be used. As the branched polycarbonate resin, for example, trimellitic anhydride or trimellitic acid Of a polyfunctional aromatic compound with a dihydroxy phenolic compound and a carbonate precursor may be used. As the polyester carbonate copolymer resin, for example, those prepared by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor may be used. In addition, conventional linear polycarbonate resin, branched polycarbonate resin or polyester carbonate copolymer resin can be used without limitation.
The weight average molecular weight of the polycarbonate resin used in the present invention (M w) is preferably of 10,000 ~ 200,000 g / mol, more preferably 15,000 ~ 80,000 g / mol.
In the specific examples, the polycarbonate resin (A) may be used alone or in combination of two or more kinds having different molecular weights.
For example, the polycarbonate resin (A) may be a mixture of a polycarbonate (a1) having a weight average molecular weight of 25,000 to 35,000 g / mol and a polycarbonate (a2) having a weight average molecular weight of 20,000 to 30,000 g / mol .
In concrete examples, a polycarbonate (a1) having a fluidity of 5 to 15 g / 10 min and a polycarbonate (a2) having a fluidity of 27 to 33 g / 10 min can be used in accordance with ISO 1133 standard (300 ° C under a load of 1.2 kg) .
In the present invention, the polycarbonate resin (A) is used in an amount of 10 to 98% by weight, preferably 50 to 95% by weight, more preferably 50 to 95% by weight in the base resin containing (A) + (B) Is 60 to 94% by weight. And has excellent mechanical properties and scratch resistance properties in the above range.
(B) an aromatic or aliphatic (meth) acrylate resin
The aromatic or aliphatic (meth) acrylate resin (B) of the present invention comprises (b1) 5 to 100% by weight of an aromatic or aliphatic (meth) acrylate; And (b2) 0 to 95% by weight of a monofunctional unsaturated monomer.
(b1) an aromatic or aliphatic (meth) acrylate
The aromatic or aliphatic (meth) acrylate (b1) has a self-refractive index ranging from 1.50 to 1.579 and may include a structure represented by the following formula (1) or (2).
[Chemical Formula 1]
Wherein R 1 is hydrogen or a methyl group, m is an integer of 0 to 10, and Y is a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, Selected)
Preferably, Y may be a cyclohexyl group, a phenyl group, a methylphenyl group, a methylethylphenyl group, a methoxyphenyl group, a propylphenyl group, a cyclohexylphenyl group, a chlorophenyl group, a bromophenyl group or a benzylphenyl group.
(2)
(Wherein R 1 is hydrogen or a methyl group, m is an integer of 0 ~ 10, Z is oxygen (O) or sulfur (S), Ar is a cycloalkyl group and a C 6 unsubstituted or substituted with a carbon number of 5-10 A substituted or unsubstituted aryl group having 1 to 20 carbon atoms).
Preferably, Ar may be a cyclohexyl group, a phenyl group, a methylphenyl group, a methylethylphenyl group, a methoxyphenyl group, a cyclohexylphenyl group, a chlorophenyl group, a bromophenyl group or a benzylphenyl group.
Examples of the aromatic or alicyclic methacrylate include cyclohexyl methacrylate, phenoxy methacrylate, 2-ethylphenoxy methacrylate, benzyl methacrylate, phenyl methacrylate, 2-ethylthiophenyl methacrylate Phenyl phenyl methacrylate, 2-phenylphenyl methacrylate, 2-methylphenyl ethyl methacrylate, 2-3-methylphenyl ethyl methacrylate, 2-4- Methylphenyl ethyl methacrylate, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1-methylethyl) Ethyl methacrylate, 2- (4-chlorophenyl) ethyl methacrylate, 2- (4-chlorophenyl) ethyl methacrylate, 2- Methacrylate, 2- (4-bromophenyl) ethyl methacrylate, 2- (3-phenylphenyl) ethyl methacrylate And methacrylic acid such as 2- (4-benzylphenyl) ethyl methacrylate, and the like, but are not limited thereto. These may be used alone or in combination of two or more.
The aromatic or aliphatic (meth) acrylate (b1) may be contained in an amount of 5 to 100% by weight of the aromatic or aliphatic (meth) acrylate resin (B). Preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and most preferably 35 to 65% by weight. And has a better physical property balance of refractive index and heat resistance within the above range.
(b2) monofunctional unsaturated monomer
The monofunctional unsaturated monomer (b2) of the present invention is a monomer containing one unsaturated group, for example, an alkyl (meth) acrylate having 1 to 10 carbon atoms; Unsaturated group-containing carboxylic acid; Acid anhydrides; Hydroxyl group-containing (meth) acrylates; (Meth) acrylamide, unsaturated naphthyl, aromatic vinyl monomers, and the like. These may be used alone or in combination of two or more.
Specific examples include acrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, Acrylate, methacrylamide, acrylonitrile, methacrylonitrile, allyl glycidyl ether, glycidyl ether, glycidyl ether, glycidyl ether, glycidyl ether, Dime methacrylate, styrene, alpha-methyl styrene, and the like. Of these, alkyl (meth) acrylates having 1 to 8 carbon atoms are preferred, and alkyl (meth) acrylates having 1 to 4 carbon atoms are more preferred. In this case, excellent scratch resistance can be achieved.
In the present invention, the monofunctional unsaturated monomer (b2) unit may be contained in an amount of 0 to 95% by weight of the aromatic or aliphatic (meth) acrylate resin (B). And preferably 20 to 80% by weight. Within the above range, the balance of scratch resistance, fluidity, transparency and flame retardancy can be obtained.
The aromatic or aliphatic (meth) acrylate resin (B) can be produced by conventional polymerization methods, for example, bulk polymerization, emulsion polymerization or suspension polymerization. Preferably by suspension polymerization.
In an embodiment, the aromatic or aliphatic (meth) acrylate resin (B) is at least one aromatic or aliphatic (meth) acrylate (b1) having the structure of Formula 1 or 2 and the monofunctional unsaturated monomer (b2) May be prepared by polymerizing the monomer mixture.
The aromatic or aliphatic (meth) acrylate resin (B) may have a glass transition temperature of 50 ° C to 110 ° C. There is an advantage of scratch resistance in the above range.
In an embodiment, the aromatic or aliphatic (meth) acrylate resin (B) may have a weight average molecular weight of 3,000 to 300,000 g / mol. Within the above range, flame retardancy can be maintained and scratch resistance can be improved, and resin fluidity and transparency are excellent.
The aromatic or aliphatic (meth) acrylate resin (B) may have a refractive index of 1.50 to 1.579, preferably 1.50 to 1.57. And has excellent transparency and compatibility in the above range.
The aromatic or aliphatic (meth) acrylate resin (B) is used in an amount of 1 to 80% by weight, preferably 10 to 70% by weight, of the base resin containing (A) + (B) And preferably 20 to 60% by weight. In the above range, it has a physical property balance of excellent mechanical properties, scratch resistance and transparency.
(C) a rubber-modified vinyl-based graft copolymer resin
The rubber-modified vinyl-based graft copolymer resin (C) used in the present invention has a structure in which a shell is formed by grafting an unsaturated monomer to the core structure of rubber, and serves as an impact modifier in the resin composition. In an embodiment, the unsaturated monomer may include alkyl (meth) acrylates having 1 to 10 carbon atoms.
The rubber is preferably prepared by polymerizing one or more rubber monomers selected from the group consisting of a diene rubber having 4 to 6 carbon atoms, an acrylate rubber, and a silicone rubber. The silicone rubber may be used alone, It is more preferable to use the late rubber in combination because of its structural stability.
As the diene rubber, a butadiene rubber, an isoprene rubber, a styrene-butadiene rubber, and an ethylene-propylene-diene terpolymer (EPDM) may be used.
Examples of the acrylate rubber include acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) (Meth) acrylate such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, , 1,4-butylene glycol di (meth) acrylate, allyl (meth) acrylate, triallyl cyanurate and the like.
The silicone rubber is prepared from a cyclosiloxane. Specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenyl Cyclotetrasiloxane, and octaphenylcyclotetrasiloxane can be produced from at least one selected from the group consisting of cyclopentasiloxane, cyclotetrasiloxane, and octaphenylcyclotetrasiloxane. In this case, a curing agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane or tetraethoxysilane can be further used.
The rubber is preferably contained in an amount of 50 to 90 parts by weight, preferably 60 to 85 parts by weight, based on 100 parts by weight of the rubber-modified vinyl-based graft copolymer resin (C) according to the present invention. When the rubber is contained in an amount of 50 to 90 parts by weight, compatibility with a resin is excellent, and as a result, excellent impact reinforcing effect can be obtained.
The average particle diameter of the rubber is 0.05 to 1 占 퐉, preferably 0.1 to 0.5 占 퐉. It is possible to have excellent appearance characteristics while maintaining an appropriate impact strength in the above range.
Examples of the unsaturated monomer grafted on the rubber include an alkyl (meth) acrylate having 1 to 12 carbon atoms, an acid anhydride, and an alkyl or phenyl nucleus substituted maleimide having 1 to 12 carbon atoms, an unsaturated nitrile, and an aromatic vinyl compound One or more selected unsaturated compounds may be used.
Preferably, the grafted unsaturated monomer includes an alkyl (meth) acrylate having 1 to 12 carbon atoms.
Specific examples of the alkyl (meth) acrylate include methyl methacrylate, ethyl methacrylate, and propyl methacrylate, among which methyl methacrylate is preferably used.
Examples of the acid anhydride include carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, and the like.
Examples of the unsaturated nitrile include acrylonitrile and methacrylonitrile.
Examples of the aromatic vinyl compound include styrene, alpha methyl styrene, and the like.
The grafted unsaturated monomer may be contained in an amount of 5 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 15 to 35 parts by weight, based on 100 parts by weight of the core-shell graft copolymer according to the present invention . In this range, compatibility with the resin is excellent, and as a result, excellent impact reinforcing effect can be exhibited.
Preferably, the rubber-modified vinyl-based graft copolymer resin (C) may be a mixture of two or more rubber-modified vinyl-based graft copolymers having different shell components. In the specific example, the rubber-modified vinyl-based graft copolymer resin (C) is obtained by copolymerizing (C1) a first rubber-modified vinyl-based graft copolymer resin in which a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer is grafted coalescence; And (C2) a second rubber-modified vinyl-based graft copolymer in which a monomer mixture comprising an aromatic vinyl monomer and an alkyl (meth) acrylate having 1 to 10 carbon atoms is grafted on the diene rubber.
The rubber-modified vinyl-based graft copolymer resin (C) according to the present invention is used in an amount of 1 to 30% by weight, preferably 3 to 20% by weight, of the base resin containing (A) + (B) %, More preferably 5 to 15 wt%. The impact resistance can be obtained within the above range, and mechanical strength such as tensile strength, flexural strength and flexural modulus can be improved, and a balance of physical properties such as transparency and scratch resistance can be obtained.
(D) Phosphorous flame retardant
Phosphate, phosphonate, phosphinate, phosphine oxide, phosphazene, metal salts thereof and the like can be used as the phosphorus flame retardant which can be used in the present invention. , Preferably a phosphate-based compound, and more preferably an aromatic phosphate ester compound which is a kind of phosphate compound.
The aromatic phosphoric acid ester compound may have a structure represented by the following formula (2).
(2)
Wherein R1, R2, R4, and R5 are each independently an C6-C20 aryl group or a C1-C10 alkyl substituted aryl group, R3 is a resorcinol, a hydroquinol, a bisphenol- Lt; / RTI > and n is 0-5.
I) when n is 0, the aromatic phosphoric ester compound is selected from the group consisting of triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, triazyl phosphate, tri (2,4,6-trimethylphenyl) (2,6-ditertiary butylphenyl) phosphate, tri (2,6-ditertiarybutylphenyl) phosphate and the like, and ii) when n is 1, resorcinol bis (diphenylphosphate), hydroquinol bis (2, 6-dimethylphenylphosphate), etc., and iii) when n is 2 or more, Or more can be present in the form of a mixture of oligomeric forms. The above-mentioned compounds alone or in a mixture of two or more are applicable.
Preferably, the phosphorus flame retardant (D) contains a resorcinol unit, more preferably RDP (resorcinol bis (diphenyl phosphate)). As described above, when a resorcinol structure is contained, it is possible to further improve the properties such as scratch resistance and impact strength, as well as to exhibit better flame retardancy.
The aromatic phosphoric acid ester compound may be used alone or in combination with other phosphorus flame retardants.
The phosphorus flame retardant (D) is used in an amount of from 1 to 30 parts by weight, preferably from 5 to 25 parts by weight, more preferably from 10 to 30 parts by weight, per 100 parts by weight of the base resin containing (A) + (B) To 20 parts by weight. And has excellent flame retardancy, scratch resistance, impact strength and thermal stability in the above range.
(E) alkaline earth metal salt
In the present invention, by applying the alkaline earth metal salt, it is possible to improve the gloss while imparting high impact and high rigidity. Unlike ordinary inorganic fillers, alkaline earth metal salts have excellent dispersibility and can impart excellent transparency, appearance, and gloss to resins.
Preferably, the alkaline earth metal salt has a density of 2.7 to 5.5 g / cm < 3 >. Excellent dispersibility, impact strength, gloss and appearance can be obtained in the above range. Preferably from 3.5 to 5.2 g / cm < 3 >, more preferably from 4.0 to 5 g / cm < 3 >.
The alkaline earth metal salt may have a refractive index of 1.6 or more, preferably 1.61 to 1.67. And has excellent appearance and impact strength in the above range.
As the alkaline earth metal salt, BaSO 4, CaCO 3, etc. may be used, and BaSO 4, spherical CaCO 3 and the like may be used. These may be used alone or in combination of two or more. Particularly, it is preferable that the aspect ratio is 0.9 to 1.1.
The alkaline earth metal salt (E) may have an average particle size of 0.5 to 5 mu m, preferably 0.7 to 1.5 mu m. Has excellent dispersibility, appearance, transparency and impact resistance in the above range.
The alkaline earth metal salt (E) is used in an amount of 1 to 10 parts by weight, preferably 2 to 8 parts by weight, more preferably 3 to 10 parts by weight, per 100 parts by weight of the base resin containing (A) + (B) To 7.5 parts by weight. It has good physical properties such as dispersibility, appearance, rigidity and impact resistance in the above range.
The resin composition of the present invention may contain a flame retardant, a surfactant, a nucleating agent, a coupling agent, Additives such as fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, inorganic additives, colorants, stabilizers, lubricants, antistatic agents, pigments, dyes and flame retardants have. These additives may be used alone or in combination of two or more.
The resin composition of the present invention can be produced by a known method for producing a resin composition. For example, after the components of the present invention and other additives are mixed at the same time, they may be melt-extruded in an extruder and produced in the form of pellets. These pellets can be used to produce plastic injection and compression molded articles.
Another aspect of the present invention provides a molded article obtained by molding the polycarbonate resin composition. The polycarbonate resin composition of the present invention is excellent in impact strength, heat resistance, mechanical properties, rigidity, flame retardancy, scratch resistance and gloss, and therefore can be suitably applied to products requiring such physical properties. In particular, it can be widely applied to exterior materials and parts of various electric and electronic products, automobile parts, building materials, interior goods, toys, household goods and the like.
Another aspect of the present invention relates to a molded article molded from the resin composition. In embodiments, the molded article has a 1/8 "thick Izod impact strength of 4 to 80 kgf / cm2 according to ASTM D256, a 60 degree gloss measured with a Gardner Gloss meter of a 1/8" thick specimen according to ASTM D523, %, And the 1/16 "thickness flame retardancy can be V-0 according to the UL 94 V flame retardant specification.
In an embodiment, the molded article has a 1/8 "thick Izod impact strength of 5 to 80 kgf / cm2 according to ASTM D256, a 60 degree gloss measured with a Gardner Gloss meter of a 1/8" thick specimen according to ASTM D523, %, And the 1/16 "thickness flame retardancy can be V-0 according to the UL 94 V flame retardant specification.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples. The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.
Example
The specifications of each component used in the following examples and comparative examples are as follows.
(A) a polycarbonate resin
(A1) PC-1: A melt index MI (300 占 폚, 1.2 kg, ISO 1133) of 8 g / 10 min was used.
(A2) PC-2: Melt index MI (300 DEG C, 1.2 kg, ISO 1133) of 19 g / 10 min was used.
(B) an aromatic or aliphatic (meth) acrylate resin
A refractive index of 1.530 and a weight average molecular weight of 35,000 g / mol were prepared by a conventional suspension polymerization method using 30% by weight of a phenyl methacrylate monomer having a refractive index of 1.570 and 70% by weight of a methacrylate monomer.
(C) a rubber-modified vinyl-based graft copolymer resin
(C1) g-ABS: 60 parts by weight of a butadiene rubber having an average particle diameter of 0.31 mu m and 40 parts by weight of a vinyl-based polymer composed of 75% by weight of styrene and 25% by weight of acrylonitrile were emulsion- -ABS. ≪ / RTI >
(C2) MBS (manufacturer: R & H)
BTA-731 manufactured by R & H Co., Ltd. having an average particle diameter of 100 nm of a rubbery polymer was used.
(D) Phosphorous flame retardant: CR 733S manufactured by Daihachi,
RDP (resorcinol bis (diphenyl phosphate)) was used.
(E) an alkaline earth metal salt;
(e1) BaSO4: BaSO4, manufactured by Sachtleben, having a density of 4.5 g / cm3, a refractive index of 1.64 and an average particle size of 0.8 탆 was used.
(e2) CaCO3: WHISCAL A having a density of 2.71 g / cm3, a particle diameter of 20 to 30 탆, a refractive index of 1.64 and an acicular shape, manufactured by MARUO Calcium CO, LTD was used.
(F1) Talc: UPN HS-T0.5 manufactured by Hayashi with a particle diameter of 4.1 mu m was used
(F2) Mica: 45 탆 SUZORITE 200-HK manufactured by ZEMEX Industrial Minerals was used.
Example 1 to 5 and Comparative Example 1-2
After adding each of the above components in the amounts shown in Table 1, 0.4 parts by weight of Teflon, 0.2 parts by weight of antioxidant IRGANOX 245, CIBA and 100 parts by weight of (B) + (C) (LEBAX-140B, manufactured by Lion Chem Co., Ltd.) were added, and the mixture was melt-kneaded and extruded to produce pellets. At this time, extrusion was performed at an extrusion temperature of 250 ° C. using a twin-screw extruder having L / D = 29 and 45 mm in diameter, and the phosphorus flame retardant was side-fed.
(weight%)
(weight%)
Property evaluation
(1) IZOD impact strength (kgf / cm 2): Measured according to ASTM D256 (specimen thickness 1/8 ").
(2) Melt flow index (MI) (g / 10 min): The melt flow index was measured at 220 캜 and 10 kg according to ISO 1133.
(3) Vickers softening temperature (VST) (占 폚): The softening temperature of the bezel (占 폚) was measured under a load of 5 kg according to ISO R306.
(4) Gloss (unit:%): Measured at 60 degrees with a Gardner gloss meter of a 1/8 "thick specimen according to ASTM D523.
(5) Flame retardancy: The flame retardancy of a 1.5 mm thick (1/16 ") specimen was measured according to the UL94 flame retardance specification.
(6) Scratch resistance (unit: 占 퐉): Measured by Ball-type Scratch Profile (BSP) test. In the BSP test, scratches of 10 to 20 mm in length were applied at a scratch speed of 75 mm / min under a load of 1000 g using a spherical tip having a diameter of 0.7 mm on the surface of L90 mm × W 50 mm × t 2.5 mm. The profile of the applied scratch was measured using a contact surface profile analyzer (XP-1) of Ambios Co., Ltd. Scratch width as a measure of scratch resistance 2 ㎛ Diameter of the metal Stylus tip Respectively.
As shown in Table 2, it can be confirmed that Examples 1 to 5 are excellent in impact strength, heat resistance, mechanical properties, flame retardancy, scratch resistance and gloss. On the contrary, the heat resistance and gloss of Comparative Example 1 were lowered, and the impact strength and glossiness of Comparative Example 2 were remarkably decreased.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (13)
(B) an aromatic or aliphatic (meth) acrylate resin;
(C) a rubber-modified vinyl-based graft copolymer resin;
(D) phosphorus flame retardant; And
(E) BaSO 4 having a density of 2.7 to 5.5 g / cm 3 and a refractive index of 1.6 or more;
And a high-gloss polycarbonate resin composition.
(A) 30 to 98% by weight of a polycarbonate resin;
(B) 1 to 80% by weight of an aromatic or aliphatic (meth) acrylate resin; And
(C) 1 to 30% by weight of a rubber-modified vinyl-based graft copolymer resin;
With respect to 100 parts by weight of the base resin containing (A) + (B) + (C)
(D) 1 to 30 parts by weight of phosphorus flame retardant; And
(E) 1 to 10 parts by weight of BaSO 4 having a density of 2.7 to 5.5 g / cm 3 and a refractive index of 1.6 or more.
[Chemical Formula 1]
Wherein R 1 is hydrogen or a methyl group, m is an integer of 0 to 10, and Y is a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, Selected)
(2)
(Wherein R 1 is hydrogen or a methyl group, m is an integer of 0 ~ 10, Z is oxygen (O) or sulfur (S), Ar is a cycloalkyl group and a C 6 unsubstituted or substituted with a carbon number of 5-10 A substituted or unsubstituted aryl group having 1 to 20 carbon atoms).
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| KR20110147849A KR101480180B1 (en) | 2011-12-30 | 2011-12-30 | Polycarbonate resin composition having high gloss and molded articles thereof |
| PCT/KR2012/006630 WO2013100303A1 (en) | 2011-12-30 | 2012-08-21 | High-gloss polycarbonate-based resin composition and article moulded therefrom |
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| FR3053349B1 (en) * | 2016-06-29 | 2020-06-19 | Arkema France | COMPOSITION COMPRISING A THERMOPLASTIC POLYMER, A MULTI-PHASE POLYMER AND A (METH) ACRYLIC POLYMER, ITS PREPARATION METHOD AND ITS USE |
| JP6954119B2 (en) * | 2016-09-01 | 2021-10-27 | 三菱ケミカル株式会社 | Polycarbonate resin composition and its molded article |
| KR102063375B1 (en) * | 2016-11-02 | 2020-01-07 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
| US10280302B2 (en) | 2016-11-02 | 2019-05-07 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article produced therefrom |
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| JP2006257126A (en) * | 2005-03-15 | 2006-09-28 | Teijin Chem Ltd | Flame-retardant aromatic polycarbonate resin composition |
| KR20080061627A (en) * | 2006-12-28 | 2008-07-03 | 제일모직주식회사 | Polycarbonate resin composition and plastic article |
| KR20100073548A (en) * | 2008-12-23 | 2010-07-01 | 제일모직주식회사 | High heat-resistant, scratch-resistant and flameproof thermoplastic resin composition |
| KR20120055277A (en) * | 2010-11-23 | 2012-05-31 | 제일모직주식회사 | High gloss and high impact resistance polycarbonate resin composition having good surface property and molded article using the same |
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|---|---|---|---|---|
| JP2006257126A (en) * | 2005-03-15 | 2006-09-28 | Teijin Chem Ltd | Flame-retardant aromatic polycarbonate resin composition |
| KR20080061627A (en) * | 2006-12-28 | 2008-07-03 | 제일모직주식회사 | Polycarbonate resin composition and plastic article |
| KR20100073548A (en) * | 2008-12-23 | 2010-07-01 | 제일모직주식회사 | High heat-resistant, scratch-resistant and flameproof thermoplastic resin composition |
| KR20120055277A (en) * | 2010-11-23 | 2012-05-31 | 제일모직주식회사 | High gloss and high impact resistance polycarbonate resin composition having good surface property and molded article using the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019132584A1 (en) * | 2017-12-29 | 2019-07-04 | 롯데첨단소재(주) | Thermoplastic resin composition and molded product formed therefrom |
| KR20190081630A (en) * | 2017-12-29 | 2019-07-09 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
| KR102007100B1 (en) * | 2017-12-29 | 2019-08-02 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
| CN111615538A (en) * | 2017-12-29 | 2020-09-01 | 乐天化学株式会社 | Thermoplastic resin composition and molded article formed therefrom |
| US11732128B2 (en) | 2017-12-29 | 2023-08-22 | Lotte Chemical Corporation | Thermoplastic polycarbonate resin composition and molded product formed therefrom |
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