KR20060074462A - Thermoplastic resin composition with good adhesion of metal plate and high impact strength - Google Patents
Thermoplastic resin composition with good adhesion of metal plate and high impact strength Download PDFInfo
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Abstract
본 발명에 따른 도금밀착성 및 내충격성이 우수한 열가소성 수지 조성물은 (A) (a1) 고무 평균 입자 직경이 0.08 이상 0.2 미만 ㎛인 소입경 그라프트 아크릴로니트릴-부타디엔 스티렌(ABS) 공중합체 수지 1∼20 중량%와 (a2) 고무 평균 입자직경이 0.2 이상 0.5 이하 ㎛인 대입경 그라프트 아크릴로니트릴-부타디엔 스티렌(ABS) 공중합체 수지 80∼99 중량%로 구성된 아크릴로니트릴-부타디엔 스티렌(ABS) 수지 20∼80 중량%; 및 (B) 스티렌-아크릴로니트릴 (SAN) 공중합체 수지 80∼20 중량%로 이루어진 것을 특징으로 한다.The thermoplastic resin composition excellent in the plating adhesion and impact resistance according to the present invention includes (A) (a1) a small particle size graft acrylonitrile-butadiene styrene (ABS) copolymer resin having a rubber average particle diameter of 0.08 or more but less than 0.2 µm. Acrylonitrile-butadiene styrene (ABS) consisting of 80 to 99% by weight of 20% by weight and (a2) large particle size graft acrylonitrile-butadiene styrene (ABS) copolymer resin having an average particle diameter of 0.2 to 0.5 μm 20 to 80 wt% resin; And (B) 80 to 20% by weight of styrene-acrylonitrile (SAN) copolymer resin.
도금용 열가소성 수지, ABS 수지, 스티렌계 수지, 도금밀착강도, 내충격성Plating thermoplastic resin, ABS resin, styrene resin, adhesion strength, impact resistance
Description
발명의 분야Field of invention
본 발명은 열가소성 수지조성물에 관한 것이다. 보다 구체적으로 본 발명은 디엔계 그라프트 공중합체의 고무 평균입자 크기가 0.08 이상 0.2 미만 ㎛ 인 소입경 그라프트 ABS 공중합체 수지가 배합되어 도금 밀착성 및 내충격성이 우수한 열가소성 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic composition in which a small particle size graft ABS copolymer resin having a rubber average particle size of a diene graft copolymer of 0.08 or more and less than 0.2 μm is blended to provide excellent plating adhesion and impact resistance.
발명의 배경Background of the Invention
아크릴로니트릴-부타디엔 스티렌 공중합체 수지(이하 "ABS 수지"라 함)는 부타디엔계 고무질 중합체 존재하의 방향족 비닐화합물로서 대표적인 스티렌 단량체와 불포화니트릴 혼합물 중 아크릴로니트릴 단량체를 유화중합법에 의해 그라프트 중합하여 제조되며, 사용되는 고무질 중합체와 그라프트 중합체, 및 매트릭스 중합 체의 물성을 조절하여 목적하는 수지를 얻는다. 이렇게 제조된 ABS 수지는 내충격성, 내화학성, 내약품성, 내열성 및 기계적 강도가 우수하고 성형가공이 용이하여 자동차 부품, 전기전자 부품, 일반잡화 등에 광범위 하게 사용되고 있다.Acrylonitrile-butadiene styrene copolymer resin (hereinafter referred to as "ABS resin") is an aromatic vinyl compound in the presence of a butadiene-based rubbery polymer, and is a graft polymerization of a typical styrene monomer and an acrylonitrile monomer in an unsaturated nitrile mixture by emulsion polymerization. It is prepared by adjusting the physical properties of the rubbery polymer, graft polymer, and matrix polymer used to obtain the desired resin. The ABS resin thus prepared is widely used in automobile parts, electrical and electronic parts, general goods, etc. because of excellent impact resistance, chemical resistance, chemical resistance, heat resistance, and mechanical strength, and easy molding processing.
플라스틱 도금은 ABS 수지 제품의 상업화에 뒤이어 곧바로 ABS 수지 도금 제품의 상업화로 급속히 진전되었다. 가볍고 디자인 설계가 용이하면서 외관이 미려한 ABS 수지에 대한 도금은 다른 수지, PP나 엔지니어링플라스틱에 대한 도금의 기본 틀이 되었다. 플라스틱에 일단 귀금속인 팔라듐(Pd) 또는 은(Ag)을 흡착한 뒤, 이 귀금속 핵을 중심으로 차아인산소다(Sodium Hypophosphite) 또는 보레인(Borane)과 같은 환원제의 존재 하에 니켈 또는 구리 용액에 넣으면 환원작용에 의한 석출이 시작되고, 그 뒤는 환원된 니켈 또는 구리 자신이 촉매로 되어 지속적인 도금이 가능하게 된다.Plastic plating rapidly progressed to the commercialization of ABS resin plating products immediately following the commercialization of ABS resin products. Lightweight, easy to design and beautifully plated, ABS plating has become the basis for plating on other resins, PP or engineering plastics. Once the plastic is adsorbed with palladium (Pd) or silver (Ag), which is a noble metal, it is placed in a nickel or copper solution around the noble metal nucleus in the presence of a reducing agent such as sodium hypophosphite or borane. Precipitation by reduction is initiated, followed by reduced nickel or copper itself as a catalyst, allowing for continuous plating.
상기의 과정을 자기촉매환원도금 (Auto-Catalitic Metal Deposition)또는 무전해 도금 과정 이라고 하는데 이러한 과정에 의해 플라스틱은 도체화 된다. 통상 0.1 ∼ 1.0 ㎛ 두께의 니켈 또는 구리의 전도성박막이 생기며 금속과 같이 다룰 수가 있게 되어 이후 전기 도금이 가능하게 된다. 이러한 무전해(화학)도금은 전기도금에서와 같이 부위별 전류 밀도차에 의한 두께 불균일 문제가 없이 균일한 두께도금이 가능하여 근래에 무전해 도금 단독의 제품이 늘고 있다.The above process is called auto-catalytic metal deposition or electroless plating, and the plastic is conductorized by this process. Usually, a conductive thin film of nickel or copper having a thickness of 0.1 to 1.0 μm is formed and can be treated like a metal, thereby enabling electroplating. Such electroless (chemical) plating is capable of uniform thickness plating without the problem of thickness unevenness due to the current density difference of each part as in the electroplating, and the products of electroless plating alone are increasing in recent years.
귀금속을 안정하게 표면에 흡착하게 해주는 전처리 공정은 수지 표면에 대한 요철화가 수반되는데, 식각(Etching)공정이라고 한다. 그런데 ABS 수지는 스티렌-아크릴로니트릴 공중합체 수지에 비하여, 부타디엔 고무(Butadiene Rubber)가 에칭 제(Etchant)인 크롬산, 황산에 의해 산화됨으로써 앵커홀을 제공하여, 귀금속인 팔라듐의 안정한 흡착을 보장할 뿐 아니라 앵커홀에 박힌 형태의 금속막이 갖는 기계적인 고정(Anchor)효과 때문에 일반적인 플라스틱 수지에 비하여 높은 밀착력을 가지게 된다. 이러한 높은 도금 밀착력을 갖는 ABS 수지의 특징이 ABS 수지의 상업화를 통한 플라스틱 도금의 활발한 전개를 가져온 가장 큰 원인이다.The pretreatment process to stably adsorb the precious metal on the surface involves the unevenness of the resin surface, which is called an etching process. However, ABS resin provides buttock hole by oxidizing butadiene rubber with etch acid, chromic acid and sulfuric acid, compared to styrene-acrylonitrile copolymer resin to ensure stable adsorption of noble metal palladium. In addition, due to the mechanical anchoring effect of the metal film embedded in the anchor hole, it has a high adhesive strength compared to the general plastic resin. The characteristic of ABS resin with high plating adhesion is the biggest cause of active development of plastic plating through commercialization of ABS resin.
특히, ABS 수지가 라디에터 그릴 등 자동차 외장용 부품으로 사용되어질 때는 CASS(Cupper accerated salt spray) 시험, 내냉열 실험 등을 통과할 수 있는 밀착력을 가지고 있어야 한다. In particular, when ABS resin is used for automotive exterior parts such as radiator grille, it must have adhesion to pass cup accerated salt spray (CAS) test and cold / heat test.
따라서 사용되고 있는 도금용 ABS는 보다 높은 밀착강도가 요구되고 있으며, 수지의 고무함량, 식각액의 농도, 식각 시간, 사출 성형시 잔류 응력 등이 밀착강도에 영향을 주는 요인으로 작용한다. 이에 본 발명자는 상기의 알려진 요인 이외에 유화중합법에 의해 제조된 그라프트 공중합체 g-ABS의 크기 분포가 소입경 g-ABS 함량이 증가할수록 밀착강도가 우수함을 발견하였다. Therefore, the used ABS for plating is required to have a higher adhesion strength, the rubber content of the resin, the concentration of the etching solution, the etching time, the residual stress during the injection molding acts as a factor affecting the adhesion strength. Thus, the present inventors found that the size distribution of the graft copolymer g-ABS prepared by the emulsion polymerization method is excellent as the small particle size g-ABS content increases in addition to the above known factors.
또한, 일반적으로 도금 후 충격강도는 도금 전에 비하여 저하되는데, 이 때문에 금속 도금(Metal plating) 이전의 사출품에서 충분한 충격강도를 갖는 것이 필요하다. 따라서 소입경 그라프트 중합 g-ABS 수지 입자의 크기는 충격강도가 크게 저하되지 않는 범위에서 밀착강도를 증대시키는 것이 중요하다 할 수 있다. 이에, 본 발명자는 적절한 소입경 그라프트 ABS 의 혼합 및 단독 사용으로 충격강도의 큰 저하 없이 도금 밀착강도를 증대시킬 수 있는 수지조성물을 발견하고 본 발명을 완성하게 되었다. Also, in general, the impact strength after plating is lower than before plating, and therefore, it is necessary to have sufficient impact strength in the injection molded product before metal plating. Therefore, the size of the small particle graft polymerization g-ABS resin particles may be important to increase the adhesion strength in a range in which the impact strength does not significantly decrease. Accordingly, the present inventors have found a resin composition capable of increasing the plating adhesion strength without a significant decrease in the impact strength by mixing and using a suitable small particle size graft ABS, and completed the present invention.
본 발명의 목적은 도금 밀착 강도가 우수한 열가소성 수지조성물을 제공하기 위한 것이다.An object of the present invention is to provide a thermoplastic resin composition having excellent plating adhesion strength.
본 발명의 다른 목적은 충격 강도가 우수한 열가소성 수지조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a thermoplastic resin composition having excellent impact strength.
본 발명의 또 다른 목적은 소량의 첨가제만으로도 겔 발생이 적은 열가소성 수지조성물을 제공하기 위한 것이다.Still another object of the present invention is to provide a thermoplastic resin composition with low gel generation even with a small amount of additives.
본 발명의 상기 및 기타 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.
The above and other objects of the present invention can be achieved by the present invention described below.
발명의 요약Summary of the Invention
본 발명의 도금용 열가소성 수지 조성물은 (A) (a1) 고무 평균 입자 직경이 0.08이상 0.2미만 ㎛인 그라프트 아크릴로니트릴-부타디엔 스티렌(ABS) 공중합체 수지 1∼20 중량%와 (a2) 고무 평균 입자 직경이 0.2이상 0.5이하 ㎛인 그라프트 아크릴로니트릴-부타디엔 스티렌(ABS) 공중합체 수지 80∼99 중량%로 구성된 아크릴로니트릴-부타디엔 스티렌(ABS) 수지 20∼80 중량%; 및 (B) 스티렌-아크릴로니트릴(SAN) 공중합체 수지 80∼20 중량%로 이루어진다The thermoplastic resin composition for plating of the present invention is (A) (a1) 1 to 20% by weight of graft acrylonitrile-butadiene styrene (ABS) copolymer resin having a rubber average particle diameter of 0.08 to less than 0.2 µm and (a2) rubber 20 to 80% by weight of acrylonitrile-butadiene styrene (ABS) resin composed of 80 to 99% by weight of graft acrylonitrile-butadiene styrene (ABS) copolymer resin having an average particle diameter of 0.2 to 0.5 or less; And (B) 80 to 20% by weight of styrene-acrylonitrile (SAN) copolymer resin.
본 발명의 g-ABS 수지 조성물은 코어(core)가 고무질 중합체이고 쉘(shell) 이 방향족 스티렌 단량체 및 아크릴로 니트릴 단량체인 코어(core)-쉘(shell)형의 공중합체이다. The g-ABS resin composition of the present invention is a core-shell copolymer in which the core is a rubbery polymer and the shell is an aromatic styrene monomer and an acrylonitrile monomer.
발명의 구체예에 대한 상세한 설명Detailed Description of the Invention
(A) 아크릴로니트릴-부타디엔 스티렌(ABS) 수지(A) Acrylonitrile-butadiene styrene (ABS) resin
본 발명의 ABS 수지는 폴리부타디엔계 고무질 중합체의 존재 하에 스티렌 같은 방향족 비닐화합물 단량체와 아크릴로니트릴과 같은 불포화니트릴 화합물 단량체를 그라프트 중합하여 제조되며, 괴상중합, 괴상·현탁중합, 유화중합법 등에 의하여 제조될 수 있다.The ABS resin of the present invention is prepared by graft polymerization of an aromatic vinyl compound monomer such as styrene and an unsaturated nitrile compound monomer such as acrylonitrile in the presence of a polybutadiene-based rubbery polymer, a bulk polymerization, a bulk polymerization suspension, an emulsion polymerization method, or the like. It can be manufactured by.
상기 (A) 수지는 입자 직경이 상이한 두 종류의 ABS 공중합체 수지, 즉 (a1) 과 (a2)로 이루어지는데, 그 각각은 모두 고무질 중합체 30∼70 중량%에 방향족 비닐 단량체 60∼80 중량% 및 불포화니트릴 단량체 20∼40 중량%로 이루어진 단량체 혼합물 70∼30 중량%를 그라프트 중합하여 제조되는 것이 바람직하다.The resin (A) is composed of two kinds of ABS copolymer resins having different particle diameters, that is, (a1) and (a2), each of which is 30 to 70% by weight of the rubbery polymer and 60 to 80% by weight of the aromatic vinyl monomer. And 70 to 30% by weight of a monomer mixture consisting of 20 to 40% by weight of unsaturated nitrile monomers.
고무질 중합체가 30 중량%미만이면 도금공정 중 저 엣칭에 의하여 밀착강도 불량이 발생하며, 70 중량%초과이면 과다 엣칭에 의하여 밀착 강도가 저하된다. 또한, 적절한 성형품의 가공을 위해서 방향족 비닐 단량체 및 불포화니트릴 단량체의 함량은 위 제시된 함량으로 규정한다. If the rubbery polymer is less than 30% by weight, poor adhesion strength occurs due to low etching during the plating process, and if it exceeds 70% by weight, the adhesion strength decreases due to excessive etching. In addition, the contents of the aromatic vinyl monomer and the unsaturated nitrile monomer are defined in the amounts given above for the processing of a suitable molded article.
(a1) 소입경 그라프트 공중합체 수지(a1) Small particle size graft copolymer resin
상기 소입경 그라프트 ABS 공중합체 수지의 고무질 중합체는 평균입자 직경 이 0.08 이상 0.2 미만 ㎛인 부타디엔계 고무 라텍스인 것이 바람직하다. The rubbery polymer of the small particle size graft ABS copolymer resin is preferably butadiene-based rubber latex having an average particle diameter of 0.08 or more and less than 0.2 µm.
고무입경이 0.08 ㎛ 미만인 경우에는 충격강도가 저하되는 단점이 있다.If the rubber particle diameter is less than 0.08 μm, the impact strength is lowered.
본 발명에서는 고무입경이 0.08 ㎛ 이상 0.2 ㎛ 미만인 그라프트 아크릴로니트릴-부타디엔 스티렌(ABS) 공중합체 수지 1∼20 중량%를 사용하며 바람직하게는 10∼20 중량%를 사용한다. 상기 소입경 그라프트 공중합체 수지(a1)를 20 중량% 초과하여 사용시에는 물성 저하가 나타난다. In the present invention, 1 to 20% by weight of graft acrylonitrile-butadiene styrene (ABS) copolymer resin having a rubber particle diameter of 0.08 μm or more and less than 0.2 μm is used, and preferably 10 to 20% by weight. When the small particle size graft copolymer resin (a1) is used in excess of 20% by weight, physical property decreases.
(a2) 대입경 그라프트 공중합체 수지(a2) Large particle size graft copolymer resin
상기 대입경 그라프트 ABS 공중합체 수지의 고무질 중합체는 평균입자직경이 0.2이상 0.5이하 ㎛인 부타디엔계 고무라텍스인 것이 바람직하다. 0.5초과 ㎛ 부타디엔계 고무라텍스의 사용의 경우에는 엣칭과정중 엥커홀의 크기가 과다하게 커져서 밀착강도의 저하를 나타낸다. The rubbery polymer of the large-diameter graft ABS copolymer resin is preferably a butadiene-based rubber latex having an average particle diameter of 0.2 to 0.5 µm. In the case of the use of more than 0.5 μm butadiene-based rubber latex, the size of the anchor hole becomes excessively large during the etching process, indicating a decrease in adhesion strength.
본 발명에서는 고무입경이 0.2 ㎛ 이상 0.5 ㎛ 미만인 그라프트 아크릴로니트릴-부타디엔 스티렌(ABS) 공중합체 수지 80∼99 중량%를 사용하며, 바람직하게는 80∼90 중량%를 사용한다. 상기 대입경 그라프트 공중합체 수지(a2)를 80 중량% 미만 사용시에는 물성 저하가 나타난다.In the present invention, 80 to 99% by weight of graft acrylonitrile-butadiene styrene (ABS) copolymer resin having a rubber particle diameter of 0.2 μm or more and less than 0.5 μm is used, and preferably 80 to 90% by weight. When the large-diameter graft copolymer resin (a2) is used in less than 80% by weight, physical property decreases.
본 발명에서 사용되는 (A) 아크릴로니트릴-부타디엔 스티렌(ABS) 수지는 전체수지 중 20∼80 중량%로 사용되는 것이 바람직하며, 상기 (a1) 소입경 그라프트 공중합체 수지 1∼20 중량%, 상기 (a2) 대입경 그라프트 공중합체 수지 80∼99 중 량%;로 구성되어 질 수 있다. 대입경 그라프트 공중합체(a2) 단독으로 사용시에는 밀착강도 증대의 효과를 볼 수 없기 때문에 소입경 그라프트 공중합체를 혼합 사용하도록 한다. (A) Acrylonitrile-butadiene styrene (ABS) resin used in the present invention is preferably used in 20 to 80% by weight of the total resin, (a1) Small particle size graft copolymer resin 1 to 20% by weight , (A2) 80 to 99% by weight of the large particle size graft copolymer resin; may be composed. When using the large-diameter graft copolymer (a2) alone, the effect of increasing the adhesion strength is not seen, so that the small-diameter graft copolymer is mixed.
(B) 스티렌-아크릴로니트릴(SAN) 공중합체 수지(B) styrene-acrylonitrile (SAN) copolymer resin
본 발명에서 사용되는 스티렌-아크릴로니트릴(SAN) 공중합체 수지(이하 "SAN" 수지라 함)는 스티렌 단량체와 아크릴로니트릴 단량체를 현탁중합 또는 괴상중합하여 제조될 수 있다. 본 발명의 SAN 공중합체 수지는 아크릴로 니트릴 함량이 15∼40 중량%이고, 중량 평균 분자량이 70,000∼300,000 정도인 SAN 수지를 사용한다. 아크릴로 니트릴 함량이 지정범위 보다 적거나 많을 시에는 미성형 등 성형불량을 초래할 수 있다. The styrene-acrylonitrile (SAN) copolymer resin (hereinafter referred to as "SAN" resin) used in the present invention may be prepared by suspension polymerization or bulk polymerization of a styrene monomer and an acrylonitrile monomer. The SAN copolymer resin of the present invention uses a SAN resin having an acrylonitrile content of 15 to 40% by weight and a weight average molecular weight of about 70,000 to 300,000. If the acrylonitrile content is less or more than the specified range, it may cause molding failure such as unmolding.
본 발명에서는 상기 SAN 공중합체 수지가 특히 괴상중합법으로 제조된 것이 가장 바람직하다. 이는 SAN 공중합체 수지를 괴상중합으로 제조할 경우, 첨가제의 함량이 적어도 만족하는 물성을 얻을 수 있으며, 겔 발생도 적기 때문이다. 중합 제조공정 중에 첨가되는 첨가제 함량이 많을 경우, 사출 성형시에 성형품에 기포발생과 같은 외관 불량이 발생하고, 또한 SAN 공중합체 수지에 겔이 포함되어 있을 경우에는 최종 성형품의 표면이 돌출되어 성형품의 품질을 저하시키는 문제점이 있다. 따라서 첨가제 함량이 적고 겔 발생이 적은 괴상중합법으로 제조된 SAN 공중합체 수지를 사용한다. 본 발명의 SAN 공중합체 수지는 전체 수지 중 20∼80 중량%를 구성한다. 이 범위외의 SAN을 사용시에는 성형불량의 원인이 될 수 있다. In the present invention, it is most preferable that the SAN copolymer resin is particularly prepared by a bulk polymerization method. This is because when the SAN copolymer resin is prepared by bulk polymerization, physical properties at least satisfying the content of the additive can be obtained, and gel generation is less. When the additive content is high during the polymerization manufacturing process, appearance defects such as bubbles are generated in the injection molding, and when the SAN copolymer resin contains gel, the surface of the final molded product protrudes There is a problem of degrading the quality. Therefore, SAN copolymer resin prepared by the bulk polymerization method with low additive content and low gel generation is used. SAN copolymer resin of this invention comprises 20 to 80 weight% of all the resin. Using SAN outside this range may cause mold defects.
본 발명은 상기 구성요소 외에도 필요에 따라 내부활제, 외부활제, 충격보강제, 산화방지제 등의 다른 첨가제를 적정한 양으로 첨가할 수 있다. In addition to the above components, the present invention may add other additives such as internal lubricants, external lubricants, impact modifiers, antioxidants, and the like, in appropriate amounts.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허 청구 범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
하기의 실시예 및 비교실시예에서 사용된 그라프트 공중합체 수지, SAN 공중합체 수지의 사양은 다음과 같다.Specifications of the graft copolymer resin and the SAN copolymer resin used in the following Examples and Comparative Examples are as follows.
(A1) 소입경 그라프트 공중합체 수지 (A1) small particle size graft copolymer resin
평균 고무입자직경이 0.12 ㎛인 고무질 중합체 50 중량%와 아크릴로니트릴 15 중량%, 스티렌 35 중량%를 사용하여 통상의 유화 그라프트 중합법에 의해 제조된 소입경 그라프트 ABS 공중합체 수지를 사용하였다.A small particle size graft ABS copolymer resin prepared by a conventional emulsion graft polymerization method using 50% by weight of a rubbery polymer having an average rubber particle diameter of 0.12 μm, 15% by weight of acrylonitrile, and 35% by weight of styrene was used. .
(A2) 대입경 그라프트 공중합체 수지 (A2) Large Particle Graft Copolymer Resin
평균 고무입자직경이 0.31 ㎛인 고무질 중합체 45 중량%와 아크릴로니트릴 17 중량%, 스티렌 38 중량%를 사용하여 통상의 유화 그라프트 중합법에 의해 제조된 대입경 그라프트 ABS 공중합체 수지를 사용하였다.A large particle size graft ABS copolymer resin prepared by a conventional emulsion graft polymerization method using 45% by weight of a rubbery polymer having an average rubber particle diameter of 0.31 μm, 17% by weight of acrylonitrile and 38% by weight of styrene was used. .
(B) SAN 공중합체 수지 (B) SAN copolymer resin
아크릴로니트릴 28 중량%이고, 중량평균 분자량이 90,000 인 SAN 공중합체 수지를 사용하였다. A SAN copolymer resin having 28% by weight of acrylonitrile and a weight average molecular weight of 90,000 was used.
실시예 1∼3 및 비교실시예 1∼3Examples 1-3 and Comparative Examples 1-3
기초수지인 그라프트 공중합체 수지, SAN 공중합체 수지에 각 구성성분을 하기의 표 1과 같은 함량으로 투입하여, 열안정제, 충격보강제 및 활제를 첨가한 후 용융, 혼련 압출하여 펠렛을 제조하였다. 이때 압출은 L/D=29, 직경 45 ㎜ 인 이축압출기를 사용하였으며 실린더 온도는 220 ℃로 설정하였다. Each component was added to the graft copolymer resin and the SAN copolymer resin, which are basic resins, in the amounts shown in Table 1 below, and thermal pellets, impact modifiers, and lubricants were added, followed by melting and kneading extrusion to prepare pellets. At this time, the extrusion was used L / D = 29, 45 mm diameter twin screw extruder and the cylinder temperature was set to 220 ℃.
상기 제조된 펠렛으로 물성시편을 사출성형 하였으며 사각 시편 ( 10㎜ × 10 ㎜ × 3 ㎜ )을 통상의 도금 과정을 거쳐 시편으로 만들었다. 도금 공정에 특별한 제한은 없으며 하기와 같은 ABS 수지 도금의 일반적인 방법에 따라 제조하였다.The physical specimens were injection molded using the prepared pellets, and rectangular specimens (10 mm × 10 mm × 3 mm) were made into specimens through a conventional plating process. There is no particular limitation on the plating process and it was prepared according to the general method of ABS resin plating as follows.
먼저, 55℃에서 5분간 계면활성제를 처리하여 오일을 제거하고, 65℃에서 15분간 에칭제인 무수크롬산-황산을 사용하여 부타디엔을 산화시켰다. 그런 다음, 25℃에서 25초간 염산수용액을 처리하여 잔류 크롬산을 제거하였으며, 30℃에서 2분간 팔라듐-주석 촉매를 사용하여 팔라듐의 앵커홀 흡착을 도모하였다. 활성화단계는 55℃에서 2분간 진행되어 황산수용액을 이용하여 주석을 제거하였고, 황산 니켈을 이용하여 30℃에서 5분간 무전해 도금을 실시하였다. 무전해 도금 후 실시된 전기 도금에서는 구리, 니켈 및 크롬을 사용하였으며, 황산구리를 이용한 구리 전기 도금은 25℃에서 35분간 3A/d㎡으로 진행하였다. 그리고 황산니켈을 사용한 니켈 전기도금은 55℃에서 15분간 3A/d㎡으로 진행하였으며, 무수크롬산액을 사용한 크롬 전기도금은 55℃에서 3분간 15/d㎡으로 진행하였다.First, the oil was removed by treating the surfactant at 55 ° C. for 5 minutes, and the butadiene was oxidized using chromic anhydride-sulfuric acid as an etchant at 65 ° C. for 15 minutes. Then, the remaining chromic acid was removed by treating the aqueous hydrochloric acid solution at 25 ° C. for 25 seconds, and anchor hole adsorption of palladium was carried out using a palladium-tin catalyst at 30 ° C. for 2 minutes. The activation step was performed at 55 ° C. for 2 minutes to remove tin using an aqueous sulfuric acid solution, and electroless plating was performed at 30 ° C. for 5 minutes using nickel sulfate. In electroplating performed after electroless plating, copper, nickel, and chromium were used, and copper electroplating using copper sulfate was performed at 25 ° C. for 3 minutes at 3 A / dm 2. Nickel electroplating using nickel sulfate proceeded at 3 A / dm 2 for 15 minutes at 55 ° C., and chromium electroplating using chromic anhydride solution proceeded to 15 / dm 2 at 55 ° C. for 3 minutes.
도금층의 두께는 구리 도금층 25∼27 ㎛, 니켈 도금층 10∼11 ㎛, 크롬 도금층 0.4∼0.5 ㎛로 총 36∼38㎛ 의 두께로 균일하게 도금하였다. 이상의 결과는 하기 표 1에 나타내었다.The thickness of the plating layer was uniformly plated in a thickness of 36 to 38 µm in total, 25 to 27 µm in the copper plating layer, 10 to 11 µm in the nickel plating layer, and 0.4 to 0.5 µm in the chromium plating layer. The above results are shown in Table 1 below.
밀착강도 측정은 상기 도금된 시편 ( 100㎜ × 100㎜ × 3㎜ )의 전면부를 10 ㎜ 폭의 흠집을 내고 Pull Gage를 이용하여 수직 방향으로 80 ㎜ 가량 박리하면서 얻어진 강도 값을 g 단위로 표시하였다. 시험 횟수는 시편당 3회 실시하여 그 평균값을 밀착강도로 하였다. Adhesion strength measurement indicated the strength value obtained in g units by scratching the front part of the plated specimen (100 mm × 100 mm × 3 mm) by 10 mm width and peeling it about 80 mm in the vertical direction using a pull gage. . The number of tests was carried out three times per specimen and the average value was taken as the adhesion strength.
충격강도는 충격적인 하중에 의해서 재료를 파괴하는 데 필요한 에너지를 재료의 단위 면적, 또는 단위 폭으로 나눈 수치를 말하며, ASTM D 256의 Notch IZOD 방법으로 시험실시하여 재료의 흡수에너지를 충격면의 폭으로 나눈 값(ft-lb/in)으로 나타내었다. Impact strength is the value obtained by dividing the energy required to destroy the material by the impact load divided by the unit area or the unit width of the material.It is tested by the Notch IZOD method of ASTM D 256 and the absorbed energy of the material is determined by the width of the impact surface. Divided values (ft-lb / in).
상기 표1의 결과로부터 평균입자직경이 0.12 ㎛ 인 고무질 중합체로부터 중합된 소입경 그라프트 ABS 공중합체 수지를 1∼20 중량% 혼합 사용하였을 때 충격강도의 저하없이 밀착강도의 향상되었다. 대입경 그라프트 ABS 공중합체(a2)만을 사용한 비교실시예 1은 밀착강도가 저하되었고, 소입경 그라프트 공중합체 수지(a1)을 30 중량% 사용한 비교실시예 2는 밀착강도는 우수하나 충격강도가 매우 하락하였으며, 소입경 그라프트 ABS 공중합체만을 사용한 비교실시예 3은 밀착강도는 매우 우수하나, 충격강도가 지나치게 낮은 값을 보임으로써 실용성이 없음을 알 수 있었다. From the results of Table 1, when the small particle size graft ABS copolymer resin polymerized from a rubbery polymer having an average particle diameter of 0.12 μm was used in an amount of 1 to 20% by weight, the adhesion strength was improved without decreasing the impact strength. The comparative example 1 using only the large-diameter graft ABS copolymer (a2) had a lower adhesive strength, and the comparative example 2 using the small-diameter graft copolymer resin (a1) 30% by weight had excellent adhesive strength but had an impact strength. Was very decreased, Comparative Example 3 using only a small particle size graft ABS copolymer is very good adhesion strength, but the impact strength was too low, it can be seen that there is no practical use.
본 발명은 디엔계 그라프트 공중합체의 고무 평균입자 크기가 0.08 이상 0.2 미만 ㎛ 인 소입경 그라프트 ABS 공중합체 수지가 배합되어 사출품의 우수한 외관을 형성하게 하고, 우수한 내충격성을 유지하면서 동시에 도금 밀착성 및 내충격성이 우수한 열가소성 수지조성물을 제공하는 발명의 효과를 갖는다.In the present invention, a small particle size graft ABS copolymer resin having a rubber average particle size of 0.08 or more and less than 0.2 μm of a diene graft copolymer is blended to form an excellent appearance of an injection molded product, while simultaneously maintaining excellent impact resistance and plating. The invention has the effect of providing a thermoplastic resin composition having excellent adhesion and impact resistance.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
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