KR101795134B1 - Polycarbonate resin composition and molded article using thereof - Google Patents
Polycarbonate resin composition and molded article using thereof Download PDFInfo
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- KR101795134B1 KR101795134B1 KR1020150061318A KR20150061318A KR101795134B1 KR 101795134 B1 KR101795134 B1 KR 101795134B1 KR 1020150061318 A KR1020150061318 A KR 1020150061318A KR 20150061318 A KR20150061318 A KR 20150061318A KR 101795134 B1 KR101795134 B1 KR 101795134B1
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
- C08K3/10—Metal 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
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/62—Mechanical aspects
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Abstract
The present invention relates to a polycarbonate resin composition and a molded article using the polycarbonate resin composition, which comprises: (A) a polycarbonate resin; (B) a modified acrylic copolymer resin; (C) a metal compound; And (D) an impact modifier.
According to the present invention, by adding the modified acrylic copolymer resin, the metal compound and the impact modifier to the polycarbonate resin at an optimum ratio, excellent plating adhesion, impact resistance and scratch resistance can be simultaneously achieved.
Description
The present invention relates to a polycarbonate resin composition and a molded article using the polycarbonate resin composition. More particularly, the present invention relates to a polycarbonate resin composition having excellent plating adhesion, impact resistance and scratch resistance, and a molded article using the same.
Since the thermoplastic resin has a lower specific gravity than glass or metal and has mechanical properties such as excellent moldability and impact resistance, plastic products using such a thermoplastic resin can quickly replace the existing glass or metal areas including electric and electronic products and automobile parts . Recently, researches have been made on techniques for forming a desired pattern at a desired position by introducing a material capable of imparting processability such as direct plating or laser molding to an thermoplastic resin as an additive.
Particularly, the polycarbonate resin is excellent in mechanical strength, flame retardancy, transparency and weather resistance, and is an engineering plastic excellent in impact resistance, thermal stability, self-extinguishing property and dimensional stability, and is widely used in various fields of electric and electronic products, . However, the polycarbonate resin is disadvantageous in that its scratch resistance is poor due to its low surface hardness.
On the other hand, an acrylic resin typified by a polymethyl methacrylate resin having excellent scratch resistance is excellent in transparency, weather resistance, mechanical strength, surface gloss and adhesive force, but has a disadvantage that impact resistance is very weak.
In general, in order to improve the scratch resistance of plastics, a hard-coating (coating process) is used in which a resin-based inorganic material is doped on a final injection-molded resin surface and then cured on the surface using heat or ultraviolet rays. . However, since such a hard coating takes a long time in the process, it is not only costly for the manufacturer but also causes environmental problems, the demand of the unpainted resin which can improve the scratch resistance without additional hard coating process .
An object of the present invention is to provide a polycarbonate resin composition excellent in plating adhesion, impact resistance and scratch resistance by adding a modified acrylic copolymer resin, a metal compound and an impact modifier to a polycarbonate resin and a molded article using the same.
It is another object of the present invention to provide a polycarbonate resin composition and a molded article using the polycarbonate resin composition, which can minimize or eliminate the hard coating process as the resin composition itself has improved scratch resistance.
In order to achieve the above object, the polycarbonate resin composition according to the present invention comprises (A) a polycarbonate resin; (B) a modified acrylic copolymer resin; And (C) a metal compound.
The polycarbonate resin composition may further comprise (D) an impact modifier.
Wherein the polycarbonate resin composition comprises 60 to 85% by weight of the polycarbonate resin (A); 10 to 25% by weight of the modified acrylic copolymer resin (B); And 1 to 18% by weight of the metal compound (C).
The modified acrylic copolymer resin (B) and the metal compound (C) may be contained in a weight ratio of 2: 1 to 3: 1.
The modified acrylic copolymer resin (B) is a polymer of a monomer mixture comprising an aromatic or alicyclic methacrylate monomer, a monofunctional acrylic monomer copolymerizable therewith, a (meth) acrylic monomer having a flexible structure, and a branched structure- Or a mixture of these polymers. The modified acrylic copolymer resin (B) may have a weight average molecular weight of 100,000 to 5,000,000. Also, the modified acrylic copolymer resin (B) may be copolymerized with a mixture of phenyl methacrylate and methyl methacrylate with butyl methacrylate and divinyltetramethyldisiloxane.
The metal compound (C) of the present invention may include at least one of a metal oxide, a heavy metal complex oxide or a copper salt.
The metal oxide may be a metal oxide spinel. The metal oxide spinel may be selected from copper oxide, zinc oxide, tin oxide, magnesium oxide, aluminum oxide, gold oxide, silver oxide, and combinations thereof.
The heavy metal complex oxide may be a heavy metal complex oxide spinel represented by the following general formula (1).
[Chemical Formula 1]
AB 2 O 4
Wherein A is at least one element selected from the group consisting of chromium, iron, aluminum, nickel, manganese, molybdenum, antimony, bismuth, It is a comment.
In the metal compound (C), the copper salt may be at least one of copper hydroxide phosphate, copper phosphate, copper sulfate, or cuprous thiocyanate Lt; / RTI >
The impact modifier (D) of the present invention may be a core-shell type.
The core-shell structure may be formed by polymerizing a monomer selected from the group consisting of a dienic monomer, an acrylic monomer, a silicone monomer, a styrenic monomer, and combinations thereof; (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composites such as ethylene / propylene rubber, butadiene / styrene rubber, acrylonitrile / butadiene rubber, polyisoprene rubber, ethylene-propylene- , An unsaturated compound selected from the group consisting of an acrylic monomer, an aromatic vinyl monomer, an unsaturated nitrile monomer, a reactive monomer, a polymer formed from at least one of these monomers, and a combination thereof, is added to the rubber, Grafted < / RTI > copolymer.
The molded article comprising the polycarbonate resin composition of the present invention comprises the above polycarbonate resin composition of the present invention. The molded article is obtained by injecting a flat plate specimen having a thickness of 1 mm, a width of 5 cm and a length of 5 cm, Aging for 8 hours, activating the surface of the specimen in the form of a stripe with a laser, conducting electroless copper plating to a thickness of 35 mu m, peeling strength measured by a tensile tester, Can be 1.10 to 1.15 N / mm (adhesion force / plating line width).
The molded product may have an impact strength of 50 to 70 kgf cm / cm measured by making a notch on an Izod specimen having a thickness of 1/8 in accordance with ASTM D4812.
In addition, the molded product may have a scratch width of 220 to 240 탆 measured by a contact type surface profiler analyzer after scratching a specimen of 2.5 mm in thickness at a load of 1 kg.
The polycarbonate resin composition according to the present invention can simultaneously achieve excellent impact resistance, plating adhesion, and scratch resistance by adding a modified acrylic copolymer resin, a metal compound and an impact modifier to polycarbonate resin at an optimum content ratio .
Further, by adding a modified acrylic copolymer resin and a metal compound to the polycarbonate resin, there is an advantage that the scratch resistance can be improved within a range that does not impair the inherent impact resistance of the polycarbonate.
Further, by the combination of the optimum constituent components, it is possible to realize an excellent scratch resistance which can eliminate or minimize the hard coating process which is additionally performed after injection molding.
In addition, by improving the scratch resistance, the hard coating process can be minimized, thereby reducing manufacturing time and manufacturing cost of the product and minimizing environmental problems.
Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.
Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.
The present invention relates to a polycarbonate resin composition and a molded article using the same.
First, the polycarbonate resin composition according to the present invention comprises (A) a polycarbonate resin; (B) a modified acrylic copolymer resin; And (C) a metal compound.
Each component constituting the polycarbonate resin composition according to one embodiment of the present invention will be described in detail.
(A) Polycarbonate resin
The polycarbonate resin (A) according to an embodiment of the present invention may be any polycarbonate resin, and may be manufactured according to a conventional manufacturing method. For example, the polycarbonate resin may be prepared by reacting a dihydric phenolic compound with phosgene in the presence of a molecular weight modifier and a catalyst, or by reacting a dihydric phenolic compound with a carbonate precursor such as diphenyl carbonate . ≪ / RTI >
As the dihydric phenol compound, a bisphenol compound may be used. Preferably, 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 bisphenols such as bis (4-hydroxyphenyl) ketone or bis (4-hydroxyphenyl) ether and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) And the present invention is not limited thereto. These dihydroxy phenolic compounds may be used alone or in admixture of two or more.
The polycarbonate resin of the present invention may be a homopolymer using one dihydric phenolic compound or a copolymer using two or more dihydric phenolic compounds or a mixture thereof.
Typically, the polycarbonate resin may have the form of a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin. The polycarbonate resin to be used in the present invention is not limited to a specific form, and a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin may all be used.
As the linear polycarbonate resin, a bisphenol A-based polycarbonate resin may be used, but is not limited thereto. As the branched polycarbonate resin, those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride or trimellitic acid with a dihydroxy phenolic compound and a carbonate precursor may be used, but the present invention is not limited thereto. As the polyester carbonate copolymer resin, those prepared by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor may be used, but the present invention is not limited thereto. The linear polycarbonate resin, the branched polycarbonate resin and the polyester carbonate copolymer resin may be used alone or in combination of two or more.
The polycarbonate resin may have a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol, but is not limited thereto.
The polycarbonate resin (A) of the present invention is contained in 100% by weight of a polycarbonate resin composition comprising a polycarbonate resin (A), a modified acrylic copolymer resin (B) and a metal compound (C) % ≪ / RTI > by weight. Preferably, it may be 65 to 80% by weight. Within this range, excellent adhesion and scratch resistance due to mixing with other components can be maintained while maintaining good mechanical properties including physical properties, i.e., impact strength, as the base resin.
(B) a modified acrylic copolymer resin
The modified acrylic copolymer resin (B) of the present invention comprises (b1) an aromatic or alicyclic methacrylate monomer, (b2) a monofunctional acrylic monomer copolymerizable therewith, (b3) a (meth) acrylic monomer having a flexible structure, and b4) a polymer of a monomer mixture comprising branch structure-forming monomers or a mixture of these polymers.
Specifically, the modified acrylic copolymer resin (B) may be prepared by copolymerizing a mixture of phenyl methacrylate and methyl methacrylate with butyl methacrylate and divinyltetramethyldisiloxane.
The modified acrylic copolymer resin (B) may have a weight average molecular weight of 100,000 to 5,000,000. The modified acrylic copolymer resin which is out of the above range has a problem that the compatibility with the polycarbonate resin is remarkably lowered.
The modified acrylic copolymer resin (B) may have a refractive index of 1.495 to 1.570. The modified acrylic copolymer resin (B) can be polymerized by conventional bulk, emulsion and suspension polymerization methods and can be easily carried out by a person having ordinary skill in the art to which the present invention belongs.
The aromatic or alicyclic methacrylate (b1) may be used alone or as a mixture with a copolymerizable monofunctional acrylic monomer (b2), and the refractive index of the mixture may be in the range of 1.495 to 1.570 .
The aromatic or alicyclic methacrylate monomer (b1) has a structure represented by the following general formula (2) or (3).
(2)
(Wherein m is an integer of 0 to 10 and X is a group consisting of a cyclohexyl group, a phenyl group, a methylphenyl group, a methylethylphenyl group, a methoxyphenyl group, a cyclohexylphenyl group, a chlorophenyl group, a bromophenyl group, / RTI >
(3)
(Wherein m is an integer of 0 to 10, Y is oxygen (O) or sulfur (S), Ar is a cyclohexyl group, a phenyl group, a methylphenyl group, a methylethylphenyl group, a methoxyphenyl group, a cyclohexylphenyl group, , A bromophenyl group, a phenylphenyl group, and a benzylphenyl group)
Examples of the aromatic or alicyclic methacrylate (b1) include cyclohexyl methacrylate, phenoxy methacrylate, phenoxyethyl methacrylate, 2-ethylphenoxy methacrylate, 2-ethylthiophenyl methacrylate , 2-ethylaminophenyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, Methylphenyl ethyl methacrylate, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1-methylethyl) phenyl) Ethyl methacrylate, 2- (4-methoxyphenyl) ethyl methacrylate, 2- (4-cyclohexylphenyl) ethyl methacrylate, 2- -Chlorophenyl) ethyl methacrylate, 2- (4-chlorophenyl) ethyl methacrylate Ethyl methacrylate, 2- (4-bromophenyl) ethyl methacrylate, 2- (3-phenylphenyl) ethyl methacrylate and 2- (4-benzylphenyl) ethyl methacrylate. It is not. These may be used alone or in combination of two or more.
Specific examples of the monofunctional acrylic monomer (b2) copolymerizable with the aromatic or alicyclic methacrylate monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, 2 May be selected from the group consisting of ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate, acrylic acid, methacrylic acid, maleic anhydride and the like, But they may be used singly or in combination of two or more.
In the present invention, the (meth) acrylic monomer (b3) having a flexible segment is composed of t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and a compound represented by the following formula And the like.
[Chemical Formula 4]
(Wherein m is an integer of 3 to 18, and X and Y are a methyl group or a hydrocarbon group)
The amount of the (meth) acrylic monomer (b3) having a flexible structure is 0.1 to 40% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight. When the content is less than 0.1% by weight, the flexible structure is hardly formed and the impact improving effect is insufficient. When the content is more than 40% by weight, the properties of the acrylic resin as a base are deteriorated. When the acrylic resin is applied to improve the scratch resistance of the polycarbonate resin with good impact resistance, the acrylic itself is very brittle, so that the impact resistance inherent in the polycarbonate resin is greatly reduced. However, when a (meth) acrylic monomer having a flexible structure is applied according to the present invention, the molecular weight itself becomes very large due to the above-mentioned flexible structure, and the soft structure plays a role of providing a soft structure, The strength is very good.
In one embodiment, the (meth) acrylic monomer (b3) having a flexible segment may be represented by the following structure (5).
[Chemical Formula 5]
(Wherein m is an integer of 3 to 9, and X and Y are a methyl group or a hydrocarbon group)
In another embodiment, the (meth) acrylic monomer (b3) having a flexible segment may be represented by the following formula (6).
[Chemical Formula 6]
(Wherein m is an integer of 10 to 18, and X and Y represent a methyl group or a hydrocarbon group)
In another embodiment, the (meth) acrylic monomer (b3) having a flexible segment may be one comprising the structure represented by the formula (5) and the structure represented by the structure represented by the formula (6).
The (meth) acrylic monomer (b3) having a flexible segment is preferably selected from the group consisting of butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, stearyl (meth) acrylate, and lauryl (meth) acrylate, and more preferably butyl (meth) acrylate.
The branched structure-forming monomer (b4) used in the present invention is a monomer having two or more polymerizable unsaturated groups capable of radical polymerization, and may be used alone or as a mixture of two or more thereof. The number of functional groups of the branched structure-forming monomer may be selected from 2 to 8 functionalities, and the modified acrylic copolymer may be prepared by a branched structure-forming monomer having such a multifunctional group.
Examples of the branch structure-forming monomer (b4) include silane or siloxane compounds having two or more polymerizable unsaturated groups capable of radical polymerization, allyl compounds, (meth) acrylic monomers, aromatic monomers, vinyl group-containing monomers and allyl compounds .
Specifically, a silane or siloxane compound containing an unsaturated hydrocarbon group-containing silicone-based monomer such as divinyltetramethyldisiloxane or tetramethyltetravinylcyclotetrasiloxane; Allyl compounds including diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, and triallyl trimellitate; (Poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol propane tri (Meta) acrylate containing (poly) alkylene glycol di (meth) acrylate including pentaerythritol tetra (meta) acrylate, pentaerythritol penta (meth) acrylate and glycerol tri (meth) Acrylic monomers; Aromatic monomers including divinylbenzene; 1,4-divinylbenzene, 1,4-divinyloxybutane, and vinyl group-containing monomers including divinyl sulfone may be used, but are not limited thereto. These may be used alone or in combination of two or more.
The branched structure forming monomer (b4) is contained in an amount of 0.001 to 10% by weight, preferably 0.01 to 7% by weight, more preferably 0.1 to 5% by weight. When the content is less than 0.001% by weight, it is difficult to form a sufficient branched structure. When the content is more than 10% by weight, problems may occur during processing due to viscosity increase.
The modified acrylic copolymer resin (B) of the present invention may contain 10 to 100 parts by weight of a polycarbonate resin (A), a modified acrylic copolymer resin (B) and a metal compound (C) To 25% by weight. Preferably, it may be from 15 to 20% by weight. If it is less than 10% by weight, the scratch resistance effect is insignificant. If it exceeds 25% by weight, the impact strength is lowered, and it is difficult to maintain the impact resistance.
(C) a metal compound
The metal compound (C) of the present invention is a substance having activity against induced emission light which can impart plating adhesion and scratch resistance to a polycarbonate resin composition, and enables direct plating or laser molding.
Herein, the induced emission light means the light amplified by induction emission of radiation, and the induced emission light may be ultraviolet ray of 100 to 400 nm wavelength, visible light of 400 to 800 nm wavelength or infrared ray of 800 to 25,000 nm wavelength Preferably an X-ray, a gamma ray or a particle beam (an electron beam, an alpha -particle beam or a beta -particle beam), and more preferably an infrared ray with a wavelength of 1,064 nm.
The metal compound (C) may be located on the surface of the polycarbonate resin composition when exposed to the stimulated emission light to activate the metal atom contained in the metal compound as a nucleating agent. Accordingly, the region exposed to the induced emission light is activated by the metal compound and the region not exposed to the induced emission light does not activate the metal atom, so that the region exposed to the induced emission light can form a conductive structure.
The metal compound (C) may be a metal oxide, a heavy metal complex oxide, or a copper salt, or a mixture of two or more thereof.
The metal oxide may be a metal oxide spinel.
Specifically, the metal oxide spinel may be a copper oxide, a zinc oxide, a tin oxide, a magnesium oxide, an aluminum oxide, a gold oxide, or a silver oxide, and may be used in combination of two or more kinds.
The heavy metal complex oxide may be a heavy metal complex oxide spinel expressed by the following formula (1).
[Chemical Formula 1]
AB 2 O 4
Wherein A is at least one element selected from the group consisting of chromium, iron, aluminum, nickel, manganese, molybdenum, antimony, bismuth, It is a comment.
The heavy metal complex oxide spinel is a compound of Formula 1, wherein A provides a monovalent cation component of a metal oxide cluster and B provides a monovalent cation component of a metal cation cluster. In one embodiment, the metal oxide clusters comprising A have a tetrahedral structure, and the metal oxide clusters comprising B may have octahedral clusters.
The heavy metal complex oxide spinel of Formula 1 has a structure in which oxygen is arranged in a cubic closest packing, B is in a gap in an octahedral shape, and A is contained in a gap in a slope.
Specific examples of the heavy metal complex oxide spinel include magnesium aluminum oxide (MgAl 2 O 4 ), zinc aluminum oxide (ZnAl 2 O 4 ), iron aluminum oxide (FeAl 2 O 4 ), copper iron oxide (CuFe 2 O 4 ) chromium oxide (CuCr 2 O 4), manganese iron oxide (MnFe 2 O 4), nickel iron oxide (NiFe 2 O 4), titanium iron oxide (TiFe 2 O 4), iron chromium oxide (FeCr 2 O 4), magnesium Chromium oxide (MgCr 2 O 4 ) or the like can be used. In the present invention, copper chromium oxide (CuCr 2 O 4 ) is particularly preferable. In some cases, two or more of them may be used in combination.
Next, the copper salt may be copper hydroxide phosphate, copper phosphate, copper sulfate, cuprous thiocyanate, or the like, For example, copper hydroxide phosphate may be used. In some cases, two or more of them may be used in combination.
The copper hydroxide phosphate is a compound having copper phosphate and copper hydroxide bonded thereto. Specifically, Cu 3 (PO 4 ) 2 .2Cu (OH) 2 or Cu 3 (PO 4 ) 2 Cu (OH) 2, and the like.
The metal compound (C) may have a form coated on a metal oxide, a heavy metal complex oxide or a copper salt, such as a mica, talc or titanium oxide, or in any other form. The mica, talc or titanium oxide may be coated or bonded to the surface of the metal compound in an amount of 10 to 40 parts by weight based on 100 parts by weight of the metal compound.
The metal compound (C) is introduced into the polycarbonate resin (A) at an optimum ratio together with the modified acrylic copolymer resin (B), thereby giving the polycarbonate resin composition excellent plating adhesion and scratch resistance .
Preferably, the modified acrylic copolymer resin (B) and the metal compound (C) are contained in a weight ratio of 2: 1 to 3: 1. When the weight ratio is 1: 1, the content of the modified acrylic copolymer resin (B) is low and the scratch resistance is decreased. When the weight ratio is 4: 1, the content of the modified acrylic copolymer resin (B) there is a problem.
When the metal compound (C) of the present invention is used, a polycarbonate resin can be patterned in a desired pattern by induced emission light. Since the chemical used in the electroplating is not used, the process can be reduced. There is an advantage that it can be minimized.
The metal compound (C) may be contained in an amount of 1 to 18% by weight within 100% by weight of a polycarbonate resin composition comprising a polycarbonate resin (A), a modified acrylic copolymer resin (B) and a metal compound (C) By weight, preferably 1 to 15% by weight. If the content is less than 1 wt%, plating itself may not be attained. If the content is more than 18 wt%, there is no problem with the plating itself, but the plating adhesion is significantly reduced.
(D) Impact reinforcement
In the present invention, the polycarbonate resin composition may further comprise an impact modifier (D), and the impact resistance may be improved by imparting additional impact strength to the polycarbonate resin composition.
The impact modifier may be a core-shell graft copolymer having a core-shell structure.
The core-shell graft copolymer serves to increase the impact resistance of the polycarbonate resin, and has a structure in which an unsaturated compound is grafted to the core of the rubber to form a hard shell.
The rubber may be a rubbery polymer obtained by polymerizing a monomer selected from the group consisting of a diene monomer, an acrylic monomer, a silicone monomer, a styrene monomer, and a combination thereof; (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composites such as ethylene / propylene rubber, butadiene / styrene rubber, acrylonitrile / butadiene rubber, polyisoprene rubber, ethylene-propylene- Among them, a rubber polymer polymerized with a diene monomer, or a rubber polymer polymerized with a diene monomer and at least one monomer selected from the group consisting of an acrylic monomer, a silicone monomer and a styrene monomer, May be used.
Examples of the diene-based monomer include butadiene and isoprene. Of these, butadiene can be preferably used.
Examples of the acrylic monomer include alkyl (meth) acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, Acrylate. Wherein said alkyl means C 1 to C 10 alkyl. At this time, an ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, allyl methacrylate, triallyl cyanurate May be used.
Examples of the silicon-based monomer include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane , And these may be used singly or in combination of two or more. At this time, a curing agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane or tetraethoxysilane can be used.
The styrene-based monomer may be selected from the group consisting of styrene, C 1 to C 10 alkyl-substituted styrene, halogen-substituted styrene, and combinations thereof.
Specific examples of the rubbery polymer polymerized with the diene-based monomer include polybutadiene and the like. Specific examples of the rubber polymer in which the diene monomer and at least one monomer among the acrylic monomer, the silicone monomer and the styrene monomer are polymerized with each other include copolymers of butadiene and alkyl (meth) acrylate, butadiene, alkyl (meth) acrylate And copolymers of cyclosiloxane. The rubbery polymers may be used alone or in combination of two or more.
The average particle diameter of the rubber may be 0.1 to 1 占 퐉.
The rubber may be included in an amount of 20 to 80% by weight based on the total amount of the core-shell graft copolymer. When the rubber is included in the above range, the impact reinforcing effect and the heat resistance can be maximized and the fluidity can be remarkably improved.
The unsaturated compound grafted onto the core of the rubber may be selected from the group consisting of an acrylic monomer, an aromatic vinyl monomer, an unsaturated nitrile monomer, a reactive monomer, a polymer formed from at least one of these monomers, and a combination thereof.
The acrylic monomer may be selected from the group consisting of alkyl (meth) acrylates, (meth) acrylic esters, and combinations thereof. At this time, as for the alkyl means an alkyl of C 1 to C 10, wherein the (meth) Specific examples of the acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate. Of these, methyl (meth) acrylate can be preferably used.
The aromatic vinyl monomer may be selected from the group consisting of styrene, C 1 to C 10 alkyl-substituted styrene, halogen-substituted styrene, and combinations thereof. Specific examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.
The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.
Examples of the reactive monomer include maleic anhydride, C 1 to C 10 alkyl or phenyl nucleus-substituted maleimide.
The impact modifier is preferably an impact reinforcing agent having a structure in which a shell made of methyl methacrylate (MMA) encapsulates a core composed of butadiene (BD) and ethyl acrylate (EA) have.
The impact modifier (D) of the present invention may be contained in an amount of 1 to 7 parts by weight based on 100 parts by weight of the sum of the polycarbonate resin (A), the modified acrylic copolymer resin (B) and the metal compound (C). When the amount is less than 1 part by weight, the impact resistance is difficult to develop. When the amount is more than 7 parts by weight, the impact resistance is increased but the scratch resistance is difficult to exhibit.
The polycarbonate resin composition of the present invention may further comprise an additive. The additive may be selected from the group consisting of an antibacterial agent, a releasing agent, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, a dye, an inorganic additive, a surfactant, A filler, a plasticizer, an impact modifier, an admixture, a colorant, a stabilizer, a lubricant, an antistatic agent, a pigment, a flame retardant and a mixture thereof.
The additive may be included in an amount of 0 to 15 parts by weight based on 100 parts by weight of the polycarbonate resin composition.
Further, selection and addition of such additives can be easily carried out by a person having ordinary skill in the art to which the present invention belongs.
Next, the polycarbonate resin composition of the present invention can be produced by a known method for producing a resin composition. For example, the components of the present invention and other additives may be simultaneously mixed and then melt-extruded in an extruder to produce pellets. The pellets can be used to produce injection and compression molded articles.
Further, the polycarbonate resin composition of the present invention is excellent in plating adhesion, impact resistance and scratch resistance, and can be used for molding various products. In particular, it can be widely applied to industrial fields such as various electric / electronic products, vehicle parts, and the like.
The molding method may be applied by extrusion, injection molding, casting or the like, but is not limited thereto and can be easily carried out by a person having ordinary skill in the art to which the present invention belongs.
In addition, a molded article containing the polycarbonate resin composition of the present invention is produced by ejecting flat plate specimens having a thickness of 1 mm, a width of 5 cm and a length of 5 cm, aging at room temperature for 6 to 8 hours, The surface of the specimen was activated and the electroless plating of copper was carried out to a thickness of 35 mu m and then the peel strength measured by a tensile tester was 0.50 to 1.20 N / mm (adhesion force / plating line width) have. Preferably, it may be 1.10 to 1.15 N / mm.
The molded product may have an impact strength of 45 to 75 kgf cm / cm measured by making a notch on a 1/8 "thick Izod specimen according to the evaluation method defined in ASTM D4812. Preferably, 50 to 70 kgf cm / cm.
The molded article may also have a scratch width of 210 to 280 탆 as measured by a contact type surface profiler analyzer after scratching the specimen surface with a load of 1 kg on a 2.5 mm thick specimen. Preferably, it may be 220 to 240 mu m.
Through several experiments, it was confirmed that the polycarbonate resin composition of the present invention belonging to the scope of the present invention realizes excellent plating adhesion, impact resistance and scratch resistance at the same time, and that the metal circuit patterning and the like are efficiently realized .
Hereinafter, the results of experiments conducted to demonstrate the superiority of the polycarbonate resin composition of the present invention.
The specifications of the polycarbonate resin (A), the modified acrylic copolymer resin (B), the metal compound (C) and the impact modifier (D) used in Examples and Comparative Examples of the present invention are as follows.
(A) Polycarbonate resin
K-1300WP, a high viscosity polycarbonate having a weight average molecular weight of 36,000 g / mol and a bisphenol-A type linear polycarbonate resin, TEIJIN CHEMICAL Co., Ltd. was used.
(B) a modified acrylic copolymer resin
A modified acrylic copolymer resin having a weight average molecular weight of 100,000 to 5,000,000 and a copolymer of phenyl methacrylate and methyl methacrylate copolymerized with butyl methacrylate and divinyltetramethyldisiloxane was used.
(C) a metal compound
In Examples and Comparative Examples of the present invention, Black 1G, a copper chrome oxide of SHEPHERD Co., Ltd., was used.
(D) Impact reinforcement
An impact modifier having a core-shell structure composed of butadiene, ethyl acrylate (EA) core and methyl methacrylate (MMA) shell of MITSUBISHI RAYON CORPORATION (MRC) was used.
The polycarbonate resin compositions of Examples and Comparative Examples were prepared in accordance with the component content ratios described in Table 1 below. The content of each component (A), (B) and (C) is expressed as% by weight, and the content of (D) B) and (C), based on 100 parts by weight of the sum.
Each component was added in accordance with the contents of Table 1 below, dry blended, and processed at a nozzle temperature of 230 to 240 캜 by a twin-screw extruder having a diameter of 45 mm to produce pellets. The prepared pellets were dried at 90 ° C for 3 hours or longer, and then prepared by injection of test specimens for evaluation.
Copolymer resin
The adhesion strength, impact resistance and scratch resistance of the specimens obtained from the compositions shown in Table 1 were evaluated in the following manner. The results are shown in Table 2 below.
Property evaluation method
(1) Adhesion of plating: The peel strength of the specimen was measured by a tensile tester, and the adhesion strength was evaluated by the average adhesion force (N) / plating line width (mm). That is, a flat plate specimen having a thickness of 1 mm, a width of 5 cm and a length of 5 cm was injected and aged at room temperature for 6 to 8 hours to activate the surface of the specimen in a stripe form with a laser, And the peel strength as measured by a tensile tester was expressed as N / mm (adhesion force / plating line width).
(2) Impact resistance: A notch was formed on a 1/8 "thick Izod specimen according to the evaluation method described in ASTM D4812, and the impact strength was measured.
(3) Scratch resistance: The specimens were evaluated by Ball-type Scratch Profile (BSP) test. The BSP test was performed by applying a scratch with a length of 10 to 20 mm at a constant load and speed to the resin surface and then measuring the profile of the applied scratch through a surface profile analyzer to determine the scratch width and scratch depth Scratch depth from scratch depth, scratch range, and scratch area.
The surface profile analyzer, which measures the scratch profile, can be both contact and non-contact, provides a profile of scratches through surface scanning with a metal stylus tip with a diameter of 1 to 2 micrometers in contact, Includes microscopes and optical analyzers such as AFM.
In the present invention, a contact type surface profile analyzer (XP-1) manufactured by Ambios was used, and a tip of a metal stylus having a diameter of 2 mu m was used. The scratch width (占 퐉) which is a measure of scratch resistance was determined from the measured scratch profile. At this time, scratch resistance is increased as the measured scratch width is decreased.
In the scratch measurement, the applied load was 1 kg, the scratch speed was 75 mm / min, and the metal tip generating the scratch was a spherical tip having a diameter of 0.7 mm. The specimen used for measuring the scratch resistance was a 2.5 mm thick specimen.
no
Notched IZOD (kgf cm / cm)
As shown in Table 2, the polycarbonate resin compositions according to Examples 1 and 2 are superior in both plating adhesion, impact strength, and scratch resistance in comparison with Comparative Examples 1 to 7. That is, the polycarbonate resin compositions of Examples 1 and 2, to which the modified acrylic copolymer resin (B), the metal compound (C) and the impact modifier (D) were added to the polycarbonate resin (A) The IZOD impact strength was 50 or more, and thus it was confirmed that the impact resistance required for the jacket of the electric / electronic product was maintained. In addition, the BSP test showed that the scratch width was measured to be 240 탆 or less, which indicates pencil hardness H level, indicating excellent scratch resistance that allows removal or minimization of the additional hard coating process after injection molding .
On the other hand, in each of Comparative Examples, in Comparative Example 1 in which the modified acrylic copolymer resin (B) was not added, the impact resistance was increased, but the BSP measurement value was increased and the scratch resistance was lowered. ) Was excessively added in Comparative Example 7, the scratch resistance was increased by decreasing the BSP measurement value, but it was confirmed that the impact resistance was remarkably lowered due to the decrease of the impact strength.
Compared with Examples 1 and 2, in Comparative Examples 2 and 3, in which the content of the impact modifier (D) was low, the impact resistance was remarkably low due to the remarkable decrease in impact strength, In the case of Comparative Example 4 in which the content of the reinforcing agent (D) is high, the impact resistance is increased, but the scratch resistance is reduced by increasing the BSP measurement value.
Compared with Examples 1 and 2, in Comparative Example 5 in which the content of the metal compound (C) was low, plating itself was not performed, and in Comparative Example 6 in which the content of the metal compound (C) was excessive, But it was confirmed that the adhesion of the plating was remarkably deteriorated to the extent that it could not be applied to actual products.
Therefore, through the above experiment, it has been proved that the critical combination capable of simultaneously realizing the plating adhesion, the impact resistance and the scratch resistance, which are remarkably excellent in the optimum combination and optimal content ratio of the constituents of the present invention.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is clear that the present invention can be suitably modified and applied in the same manner. Therefore, the above description does not limit the scope of the present invention, which is defined by the limitations of the following claims.
Claims (18)
(B) a modified acrylic copolymer resin; And
(C) a metal compound,
The modified acrylic copolymer resin (B) may be a polymer of a monomer mixture comprising an aromatic or alicyclic methacrylate monomer, a monofunctional acrylic monomer copolymerizable therewith, a (meth) acrylic monomer having a flexible structure, and a branched structure- Polymer,
Wherein the modified acrylic copolymer resin (B) and the metal compound (C) are contained in a weight ratio of 2: 1 to 3: 1.
The polycarbonate resin composition further comprises (D) an impact modifier.
The polycarbonate resin composition may contain,
60 to 85% by weight of the polycarbonate resin (A);
10 to 25% by weight of the modified acrylic copolymer resin (B); And
And 1 to 18% by weight of the metal compound (C).
The modified acrylic copolymer resin (B) has a weight average molecular weight of 100,000 to 5,000,000.
The modified acrylic copolymer resin (B) is obtained by copolymerizing a mixture of phenyl methacrylate and methyl methacrylate with butyl methacrylate and divinyltetramethyldisiloxane.
Wherein the metal compound (C) comprises at least one of a metal oxide, a heavy metal complex oxide or a copper salt.
Wherein the metal oxide is a metal oxide spinel.
Wherein the metal oxide spinel is selected from copper oxide, zinc oxide, tin oxide, magnesium oxide, aluminum oxide, gold oxide, silver oxide, and combinations thereof.
Wherein the heavy metal complex oxide is a heavy metal complex oxide spinel represented by the following Formula 1:
[Chemical Formula 1]
AB 2 O 4
Wherein B is at least one element selected from the group consisting of chromium, iron, aluminum, nickel, manganese, molybdenum, antimony, bismuth, or tin, wherein A is cadmium, chromium, manganese, nickel, zinc, copper, cobalt, iron, being).
Wherein the copper salt is at least one of copper hydroxide phosphate, copper phosphate, copper sulfate or cuprous thiocyanate.
Wherein the impact modifier (D) is a core-shell structure.
The core-shell structure
A rubbery polymer obtained by polymerizing a monomer selected from the group consisting of a diene monomer, an acrylic monomer, a silicone monomer, a styrene monomer, and a combination thereof; (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composites such as ethylene / propylene rubber, butadiene / styrene rubber, acrylonitrile / butadiene rubber, polyisoprene rubber, ethylene-propylene- ≪ RTI ID = 0.0 > and / or < / RTI >
Wherein the unsaturated compound is grafted with an unsaturated compound selected from the group consisting of an acrylic monomer, an aromatic vinyl monomer, an unsaturated nitrile monomer, a reactive monomer, a polymer formed from one or more monomers thereof, and a combination thereof.
The molded product was prepared by injecting a flat plate specimen having a thickness of 1 mm, a width of 5 cm and a length of 5 cm, aging at room temperature for 6 to 8 hours, activating the surface of the specimen in a stripe form by laser, And the peel strength measured by a tensile tester is 1.10 to 1.15 N / mm (adhesion force / plating line width) after the plating to a thickness of 35 탆.
The molded article has a notch formed on a 1/8 "thick Izod specimen according to ASTM D4812, and has an impact strength of 50 to 70 kgf / cm.
Wherein the molded article has a scratch width of from 220 to 240 탆 measured by a contact type surface profiler analyzer after scratching the specimen with a load of 1 kg on a specimen having a thickness of 2.5 mm.
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| KR20200113681A (en) | 2019-03-26 | 2020-10-07 | 주식회사 케이에이피에스 | Polycabonate plate with improved scratch resistance and method of manufacturing the same |
| KR20200113683A (en) | 2019-03-26 | 2020-10-07 | 주식회사 케이에이피에스 | Polycabonate plate with improved scratch resistance and method of manufacturing the same |
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| KR102117741B1 (en) * | 2017-12-31 | 2020-06-01 | 롯데첨단소재(주) | Thermoplastic resin composition for plating |
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| KR102008585B1 (en) | 2017-12-18 | 2019-08-07 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
| KR20200113681A (en) | 2019-03-26 | 2020-10-07 | 주식회사 케이에이피에스 | Polycabonate plate with improved scratch resistance and method of manufacturing the same |
| KR20200113683A (en) | 2019-03-26 | 2020-10-07 | 주식회사 케이에이피에스 | Polycabonate plate with improved scratch resistance and method of manufacturing the same |
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