KR101009660B1 - Shortening Process High Coloring Surface Composition - Google Patents
Shortening Process High Coloring Surface Composition Download PDFInfo
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- KR101009660B1 KR101009660B1 KR1020100104835A KR20100104835A KR101009660B1 KR 101009660 B1 KR101009660 B1 KR 101009660B1 KR 1020100104835 A KR1020100104835 A KR 1020100104835A KR 20100104835 A KR20100104835 A KR 20100104835A KR 101009660 B1 KR101009660 B1 KR 101009660B1
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Abstract
본 발명은 본 출원인에 의해 선출원되어 등록된 '사출부품에 착색이 용이한 1액형 선처리제 조성물(등록번호 : 제10-0983806호)'을 개량한 단축공정 고착색 표면처리제 조성물에 관한 것으로써, 구체적으로는 아크릴변성 폴리올레핀 수지, 용제형 아크릴 화합물, 염화폴리올레핀 그라프트 중합물을 주성분으로 사용하여 사출부품과 착색코팅제간의 응집력을 높이고 접착강도 증진을 위해 접착 증진제, 충전제를 사용하고 여기에 광 및 산소에 의한 변색을 방지하기 위해 첨가되는 첨가제를 첨가하며 초기 접촉성, 젖음성 및 프라이머의 용해도를 향상시킬 수 있는 2종 이상의 저독성 유기용제를 사용한 단축공정 고착색 표면처리제 조성물에 관한 것이다.
본 발명에 따르면, 착색코팅제 도포 부위 내변색성이 향상될 뿐만 아니라 사출부품과 착색코팅제 간의 부착성이 우수해져, 종래의 공정과는 달리 세척제 처리, UV형 선처리제 및 UV 조사 등의 복잡한 전처리공정을 생략할 수 있고, 또한 이로 인해 경비절감 및 공정 간소화 그리고 작업장의 환경을 개선할 수 있을 뿐만 아니라 이에 더하여 착색 코팅제의 조성 성분에 관계 없이 안정된 부착성을 나타낼 수 있다.The present invention relates to a shortened process high-colored surface treatment agent composition which is improved from the one-part pretreatment composition (registration number: No. 10-0983806) that is easy to color on the injection part registered and filed by the applicant. Specifically, acrylic modified polyolefin resin, solvent-type acrylic compound, and chlorinated polyolefin graft polymer are used as main components to increase cohesion between injection part and coloring coating agent and to improve adhesion strength. The present invention relates to a short-term process high-colored surface treatment agent composition using two or more low-toxic organic solvents which may add an additive added to prevent discoloration and improve initial contactability, wettability, and solubility of a primer.
According to the present invention, not only the discoloration resistance of the color coating agent coating site is improved, but also the adhesion between the injection part and the coloring coating agent is excellent, and a complicated pretreatment process such as cleaning agent treatment, UV type pretreatment agent and UV irradiation, unlike the conventional process Can be omitted, and this can also reduce costs, simplify the process and improve the environment of the workplace, in addition to exhibit a stable adhesion irrespective of the composition of the coloring coating.
Description
본 발명은 단축공정 고착색 표면처리제 조성물에 관한 것으로써, 더욱 상세하게는 아크릴변성 폴리올레핀 수지, 용제형 아크릴 화합물 그리고 염화폴리올레핀 그라프트 중합물을 주성분으로 사용하고 이에 접착 증진제, 충전제 및 광 및 산소에 의한 변색을 방지하기 위해 첨가되는 첨가제를 첨가하며 2종 이상의 저독성 유기용제를 사용함으로써, 착색코팅제 도포 부위 내변색성이 향상될 뿐만 아니라 사출부품과 착색코팅제 간의 부착성이 우수해져, 종래의 공정과는 달리 세척제 처리, UV형 선처리제 및 UV 조사 등의 복잡한 전처리공정을 생략할 수 있고, 또한 이로 인해 경비절감 및 공정 간소화 그리고 작업장의 환경을 개선할 수 있을 뿐만 아니라 이에 더하여 착색 코팅제의 조성 성분에 관계 없이 안정된 부착성을 나타내는 것을 특징으로 하는 단축공정 고착색 표면처리제 조성물에 관한 것이다.
The present invention relates to a short-acting high-color surface treatment agent composition, and more particularly, using an acrylic modified polyolefin resin, a solvent-type acrylic compound and a chlorinated polyolefin graft polymer as a main component, and using an adhesion promoter, a filler and light and oxygen. By using additives added to prevent discoloration and using two or more low-toxic organic solvents, the discoloration resistance of the color coating agent application area is not only improved, but also the adhesion between the injection part and the color coating agent is excellent. Otherwise, complex pretreatment processes such as detergent treatment, UV type pretreatment and UV irradiation can be omitted, which also reduces costs, simplifies the process and improves the working environment, as well as the composition of the coloring coating. Characterized by exhibiting stable adhesion without Process and relates to the coloring surface treatment composition.
일반적으로 성형품을 제조할 때에 과거에는 1차 및 2차의 프레스 성형과정, 스카이빙, 커팅 등의 복잡한 가공공정을 거치는 프레스 몰딩 성형법을 주로 사용하였지만 상기의 성형방법은 시간 및 원료의 손실이 크고 많은 인력을 필요로 하는 문제가 있어서 최근에는 사출 몰딩 성형법을 주로 사용한다. In general, when manufacturing a molded article, in the past, the press molding molding method, which mainly undergoes complicated processing processes such as primary and secondary press molding processes, skiving and cutting, is mainly used, but the molding method described above has a large loss of time and raw materials. Since there is a problem requiring manpower, the injection molding molding method is mainly used in recent years.
상기 사출 몰딩 성형법은 재성형이나 스카이빙, 커팅 등의 다른 복잡한 가공공정을 단순화시켜 금형에 직접 부품으로 제조할 혼합물을 사출시키는 방법이다. The injection molding method is a method of injecting a mixture to be manufactured as a part directly into a mold by simplifying other complicated processing processes such as remolding, skiving, and cutting.
그러나, 사출 몰딩 성형법으로 제조된 사출부품은 제조 특성상 사출부품의 외부에 두꺼운 피막층을 가지고 있으며, 이형제를 과량 사용해야 하기 때문에 표면에 불순물이 묻는 단점이 있다. However, an injection part manufactured by an injection molding molding method has a thick coating layer on the outside of the injection part due to its manufacturing characteristics, and since an excessive amount of a releasing agent is used, impurities are disadvantageous on the surface.
따라서 사출부품의 표면에 다양한 색상을 나타내기 위해 사출부품의 표면에 색을 입히는 코팅작업을 하는 데 사출부품과 착색코팅제의 결합력이 낮아 상호간의 부착력이 용이하지 않다. 또한, 착색코팅제의 조성 성분이 에테르계, 에스테르계, 카프로락톤계 등으로 나뉘는데, 이에 따라 부착력의 수치가 다양한 결과를 가지므로 착색코팅제의 종류와 관계없는 안정된 수치의 부착력이 요구된다.
Therefore, the coating work to color the surface of the injection part in order to show a variety of colors on the surface of the injection part is low adhesion force between the injection part and the coloring coating agent is not easy. In addition, the components of the coloring coating agent is divided into ether-based, ester-based, caprolactone-based, etc. As a result, the value of the adhesion has a variety of results, the adhesion of a stable value irrespective of the type of coloring coating agent is required.
상기와 같은 문제점으로 인해 최근에는 사출 파이론의 경우, 도 1에 도시된 바와 같이, 사출부품의 표면을 청결히 하는 세정 공정으로서 전처리 작업을 한 다음, 사출부품과 착색코팅제와의 부착력 증대를 위해 사출부품 표면에 UV형 프라이머 도포 과정을 거쳐 UV를 조사하고 최종으로 착색코팅제를 도포하는 방법을 사용하지만 상기와 같은 방법은 사출부품의 다양한 형태에 따라 UV를 조사하는 것이 용이하지 않고 공정이 번거로우며 세척제 및 UV 조사에 의한 유해한 작업장의 환경 개선이 요구된다. Due to the above problems, in the case of injection pylon, as shown in FIG. 1, the pre-treatment operation is performed as a cleaning process to clean the surface of the injection part, and then the injection part for increasing adhesion between the injection part and the coloring coating agent. UV coating is applied to the surface and UV coating is applied to the surface. Finally, the coloring coating agent is applied. However, the above method is not easy to irradiate UV according to various forms of injection parts, and the process is cumbersome. Improvement of the environment of harmful workplaces by UV irradiation is required.
그리고 사출 TPU 및 사출 플라스틱 부품을 착색코팅할 때는 도 1에 도시된 바와 같이, 상기의 사출 파이론과 마찬가지로 사출부품의 표면을 청결히 하는 세정 공정으로서 전처리 작업을 하고 다음 공정으로 사출부품과 착색코팅제와의 부착력 증대를 위해 선처리제를 처리하며 최종으로 착색코팅제를 도포하는 방법을 사용한다.And when coating the injection TPU and injection plastic parts as shown in Figure 1, as in the injection pylon as described above, as a cleaning process to clean the surface of the injection parts pre-treatment operation and the next step of the injection part and the coloring coating agent In order to increase adhesion, a pretreatment agent is treated and finally, a color coating agent is applied.
하지만 이러한 사출 TPU 및 사출 플라스틱 부품의 착색코팅 방법은 선처리제에 이소시아네이트계 경화제를 혼합 처리하여 보다 높은 부착성을 나타낼 수 있는 장점은 있으나, 이들 경화제 대부분은 부착성을 높이는 목적으로 방향족계 이소시아네이트로 이루어져 있어서 변색성이 나빠지는 문제가 있다.
However, the coloring coating method of the injection TPU and the injection plastic parts has an advantage of showing higher adhesion by mixing the isocyanate-based curing agent with the pretreatment agent, but most of these curing agents are composed of aromatic isocyanates for the purpose of increasing the adhesion. There is a problem that the color fading worse.
한편, 상기와 같은 실정에도 불구하고 현재 개발되고 있는 프라이머로서 대한민국 공개특허 제10-2006-0129505호의 변성 폴리올레핀 수지 조성물은 자일렌, 톨루엔 등과 같은 유독성 유기용제를 사용하므로 작업환경의 오염으로 인해 인체에 유해한 문제점이 있으며, 대한민국 공개특허 제 10-2006-0110398호에 폴리올레핀용 수성 수지 조성물은 사출 파이론과 사출 TPU같은 두꺼운 피막층과 유연성을 지닌 사출 소재에는 부착성이 약하여 단축공정 고착색 표면처리제 조성물의 용도로 사용하기에는 부적합한 문제점이 있었다.
On the other hand, despite the above circumstances, the modified polyolefin resin composition of the Republic of Korea Patent Publication No. 10-2006-0129505 as a primer that is currently being developed uses a toxic organic solvent such as xylene, toluene and the like due to contamination of the working environment There is a detrimental problem, the Republic of Korea Patent Publication No. 10-2006-0110398 polyolefin water-based resin composition has a weak adhesion to the injection film having a thick coating layer and flexibility such as injection pylon and injection TPU, the use of a short-fix process high-color surface treatment composition There was an unsuitable problem to use as.
따라서, 상기와 같은 문제점을 해결하기 위하여, 본 출원인은 대한민국 등록특허공보 제10-0983806호에 따른 "사출부품에 착색이 용이한 1액형 선처리제 조성물"을 개발하여 상기 문제점을 해결하였다.Therefore, in order to solve the above problems, the present applicant solved the above problems by developing a "one-component pretreatment composition that is easy to color the injection parts" according to Republic of Korea Patent Publication No. 10-0983806.
하지만, 본 출원인에 의해 선출원되어 등록된 "사출부품에 착색이 용이한 1액형 선처리제 조성물"은 착색코팅제 도포 부위 내변색성이 향상될 뿐만 아니라 사출부품과 착색코팅제 간의 부착성이 우수해져, 종래의 공정과는 달리 세척제 처리, UV형 선처리제 및 UV 조사 등의 복잡한 전처리공정을 생략할 수 있고, 이로 인해 경비절감 및 공정 간소화 그리고 작업장의 환경을 개선할 수는 있었지만, 사출부품의 표면에 코팅되는 착색 코팅제의 조성 성분별로 안정된 수치의 부착력을 나타내지 못하는 문제점이 있었다.
However, the "one-component pretreatment composition which is easy to color on injection parts" registered and filed by the applicant of the present invention not only improves discoloration resistance of the color coating agent application site, but also has excellent adhesion between the injection part and the color coating agent. Unlike the process, it is possible to omit complex pretreatment processes such as detergent treatment, UV pretreatment and UV irradiation, which can reduce costs, simplify the process, and improve the environment of the workplace. There was a problem in that it does not exhibit a stable value of adhesion for each component of the coloring coating.
따라서 상기와 같은 문제점을 해결하기 위하여, 본 출원인에 의해 선출원되어 등록된 '사출부품에 착색이 용이한 1액형 선처리제 조성물(등록번호 : 제10-0983806호)'을 개량하여, 아크릴변성 폴리올레핀 수지, 용제형 아크릴 화합물 그리고 염화폴리올레핀 그라프트 중합물을 주성분으로 사용하고 이에 접착 증진제, 충전제 및 광 및 산소에 의한 변색을 방지하기 위해 첨가되는 첨가제를 첨가하며 2종 이상의 저독성 유기용제를 사용함으로써, 착색코팅제 도포 부위 내변색성이 향상될 뿐만 아니라 사출부품과 착색코팅제 간의 부착성이 우수해져, 종래의 공정과는 달리 세척제 처리, UV형 선처리제 및 UV 조사 등의 복잡한 전처리공정을 생략할 수 있고, 또한 이로 인해 경비절감 및 공정 간소화 그리고 작업장의 환경을 개선할 수 있을 뿐만 아니라 이에 더하여 착색 코팅제의 조성 성분에 관계 없이 안정된 부착성을 나타내는 것을 특징으로 하는 단축공정 고착색 표면처리제 조성물을 제공함을 과제로 한다.
Therefore, in order to solve the above problems, the acrylic modified polyolefin resin was improved by improving the 'one-component pretreatment composition (registration number: No. 10-0983806) that is easy to color on the injection parts registered and filed by the applicant. Coloring agent by using solvent type acrylic compound and chlorinated polyolefin graft polymer as main ingredients, and adding adhesion enhancer, filler and additives to prevent discoloration by light and oxygen, and using two or more low-toxic organic solvents. Not only does the discoloration resistance of the coating part be improved, but also the adhesion between the injection part and the coloring coating agent is excellent, and thus, unlike the conventional process, complicated pretreatment processes such as cleaning agent treatment, UV type pretreatment agent and UV irradiation can be omitted. This not only reduces costs, streamlines processes, and improves the workplace environment. Speed-step, characterized in that indicating the stable adhesion regardless of the composition over the colored coating composition of the high and provide a colored surface treatment composition as a challenge.
상기의 과제를 달성하기 위한 본 발명은 아크릴변성 폴리올레핀 수지 25~45 중량부와, 용제형 아크릴 화합물 35~55 중량부 그리고 염화폴리올레핀 그라프트 중합물 20~40 중량부로 이루어진 혼합 고분자 기재 100 중량부에 대하여, 접착 증진제 5~20 중량부, 충진제 3~10 중량부, 광 및 산소에 의한 변색을 방지하기 위해 첨가되는 첨가제 2~5 중량부 및 용제 600~2600 중량부로 이루어지는 단축공정 고착색 표면처리제 조성물을 과제 해결 수단으로 한다.The present invention for achieving the above object with respect to 100 parts by weight of the mixed polymer substrate consisting of 25 to 45 parts by weight of the acrylic modified polyolefin resin, 35 to 55 parts by weight of the solvent-type acrylic compound and 20 to 40 parts by weight of chlorinated polyolefin graft polymer , 5 to 20 parts by weight of adhesion promoter, 3 to 10 parts by weight of filler, 2 to 5 parts by weight of additives added to prevent discoloration by light and oxygen and 600 to 2600 parts by weight of solvent It is a problem solving means.
한편, 상기 아크릴변성 폴리올레핀 수지는, 분자량이 40,000~80,000 이고 연화점이 60~140℃인 것 중에서 1종 또는 그 이상을 선택하여 사용할 수 있다.On the other hand, the said acrylic modified polyolefin resin can select and use 1 type or more from the thing whose molecular weight is 40,000-80,000, and a softening point of 60-140 degreeC.
또한, 상기 용제형 아크릴 화합물은, 단량체의 단일중합체가 -10℃이하의 유리전이온도를 가지는 소프트 단량체 60~90 중량부 및 단량체의 단일중합체가 50℃이상의 유리전이온도를 가지는 하드 단량체 10~30 중량부로 이루어진 기재 100 중량부에 대하여, 카르복실기를 갖는 단량체를 0.5~2 중량부를 유화중합 하여 제조할 수 있다.In addition, the solvent type acrylic compound is a hard monomer 10 ~ 30 to 60 parts by weight of a soft monomer having a glass transition temperature of less than -10 ℃ and a homo monomer of monomer and a hard monomer 10 to 30 having a glass transition temperature of 50 ℃ or more It can be prepared by emulsion polymerization of 0.5 to 2 parts by weight of the monomer having a carboxyl group with respect to 100 parts by weight of the base consisting of parts by weight.
또한, 상기 염화폴리올레핀 그라프트 중합물은 염화폴리프로필렌 또는 염화폴리에틸렌을 포함하는 염화폴리올레핀 수지 100 중량부에 대하여, 비관능성 아크릴계 모노머 에틸아크릴레이트, 부틸메타크릴레이트, 메틸메타크릴레이트 50~100 중량부를 그라프트 중합하여 제조할 수 있다.
In addition, the chlorinated polyolefin graft polymer is grafted 50 to 100 parts by weight of the non-functional acrylic monomer ethyl acrylate, butyl methacrylate, methyl methacrylate relative to 100 parts by weight of polychlorinated polyolefin resin or chloride containing polychlorinated polyethylene Can be prepared by polymerization.
본 발명에 따르면, 착색코팅제 도포 부위 내변색성이 향상될 뿐만 아니라 사출부품과 착색코팅제 간의 부착성이 우수해져, 종래 세척제 처리, UV형 선처리제 및 UV 조사 등의 복잡한 전처리공정을 생략할 수 있게 되고, 이로 인해 경비절감 및 공정 간소화 그리고 작업장의 환경을 개선할 수 있도록 하는 장점이 있다. According to the present invention, not only the discoloration resistance of the coated coating agent is improved, but also the adhesion between the injection part and the coloring coating agent is excellent, so that a complicated pretreatment process such as conventional cleaning agent treatment, UV type pretreatment agent and UV irradiation can be omitted. This has the advantage of reducing costs, simplifying processes and improving the workplace environment.
또한, 착색 코팅제의 조성 성분에 관계 없이 안정된 부착성을 나타내는 장점이 있다.
In addition, there is an advantage of showing a stable adhesion regardless of the composition components of the colored coating agent.
도 1은 종래의 사출 부품을 착색하는 공정과정을 나타낸 블록도
도 2는 본 발명에 따른 기술적 사상을 보여주는 사출 부품을 착색하는 공정과정을 나타낸 블록도1 is a block diagram showing a process of coloring a conventional injection part
Figure 2 is a block diagram showing the process of coloring the injection part showing the technical idea according to the invention
상기의 효과를 달성하기 위한 본 발명은 단축공정 고착색 표면처리제 조성물에 관한 것으로서, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.
The present invention for achieving the above effect relates to a short-term process high-colored surface treatment agent composition, only the parts necessary for understanding the technical configuration of the present invention will be described, the description of other parts will be omitted so as not to distract the gist of the present invention. It should be noted that
이하 본 발명에 따른 단축공정 고착색 표면처리제 조성물을 상세히 설명하면 다음과 같다.
Hereinafter, the shortening process high-colored surface treatment composition according to the present invention will be described in detail.
본 발명은 단축공정 고착색 표면처리제 조성물에 있어서, The present invention is a short-acting high color surface treatment agent composition,
아크릴변성 폴리올레핀 수지, 용제형 아크릴 화합물 그리고 염화폴리올레핀 그라프트 중합물로 이루어진 혼합 고분자 기재 100 중량부에 대하여, 접착 증진제 5~20 중량부, 충진제 3~10 중량부, 광 및 산소에 의한 변색을 방지하기 위해 첨가되는 첨가제 2~5 중량부 및 3~5종의 용제 600~2600 중량부로 이루어진 단축공정 고착색 표면처리제 조성물에 관한 것이다.
To 100 parts by weight of a mixed polymer substrate composed of an acrylic modified polyolefin resin, a solvent type acrylic compound and a chlorinated polyolefin graft polymer, 5 to 20 parts by weight of an adhesion promoter, 3 to 10 parts by weight of a filler, and prevention of discoloration by light and oxygen It is related with the shortening process high color surface treatment agent composition which consists of 2-5 weight part of additives added for the purpose, and 600-2600 weight part of 3-5 types of solvents.
그리고 상기 단축공정 고착색 표면처리제 조성물은 혼합용제들을 사용하여 선처리제의 고형분이 5~15 중량%가 되도록 조절한 것을 사용하는 것이 바람직하다.
And it is preferable to use the shortening process high color surface treatment agent composition adjusted so that solid content of the pretreatment agent may be 5-15 weight% using the mixed solvent.
본 발명에서 상기 혼합 고분자 기재로 사용되는 고분자는 아크릴변성 폴리올레핀 수지 25~45 중량부, 용제형 아크릴 화합물 35~55 중량부 그리고 염화폴리올레핀 그라프트 중합물 20~40 중량부로 이루어지고, 본 발명에서 상기 혼합 고분자 사용량은 100 중량부를 기준으로 한다.
The polymer used as the mixed polymer substrate in the present invention is composed of 25 to 45 parts by weight of an acrylic modified polyolefin resin, 35 to 55 parts by weight of a solvent type acrylic compound and 20 to 40 parts by weight of a chlorinated polyolefin graft polymer. The amount of the polymer used is based on 100 parts by weight.
상기 고분자 기재로 사용되는 본 발명에 사용된 아크릴변성 폴리올레핀 수지는 사출부품 기재와의 부착성과 착색코팅제와의 우수한 결합특성을 부여하기 위하여 사용하는 것으로서, 분자량이 40,000~80,000 이고 연화점이 60~140℃인 것을 단독 또는 병용하여 사용하는 것이 바람직하다.
The acrylic modified polyolefin resin used in the present invention, which is used as the polymer substrate, is used to impart adhesion to the injection part substrate and excellent bonding properties with the coloring coating agent, and has a molecular weight of 40,000 to 80,000 and a softening point of 60 to 140 ° C. It is preferable to use what is independent or uses together.
그리고 상기 아크릴변성 폴리올레핀 수지의 사용량은 25~45 중량부 범위 내에서 사용하는 것이 바람직하다. 25 중량부 미만일 경우 사출부품 기재에 대한 부착성, 내알칼리성 등의 화학적 성능이 저하되어 접착력이 감소하게 될 우려가 있고, 45 중량부를 초과할 경우에는 고가의 폴리올레핀의 사용량에 다른 가격이 상승하므로 이의 증가에 따른 효과의 상승 정도를 고려해 볼 때 타탕하지 않으며 또한, 수지 용액의 점도가 증가하여 작업성 및 용제에 대한 용해도가 저하될 우려가 있다.
And it is preferable to use the acryl-modified polyolefin resin within 25-45 weight part. If it is less than 25 parts by weight, the adhesion to the base material of the injection part, alkali resistance, etc. may decrease the adhesive strength, and if it exceeds 45 parts by weight, the use of expensive polyolefin increases the other price, so Considering the degree of increase of the effect of the increase is not detrimental, and there is a fear that the viscosity of the resin solution is increased to reduce workability and solubility in the solvent.
또한 본 발명에서 상기 혼합 고분자 기재로 사용되는 용제형 아크릴 화합물은 더욱 상세하게는 소프트 단량체 60~90 중량부 및 하드 단량체 10~30 중량부로 이루어진 기재 100 중량부에 대하여, 카르복실기를 갖는 단량체를 0.5~2 중량부를 유화중합하여 제조한다.In addition, in the present invention, the solvent type acrylic compound used as the mixed polymer substrate is more specifically 0.5 to 90 parts by weight of a monomer having a carboxyl group, based on 100 parts by weight of the substrate consisting of 60 to 90 parts by weight of the soft monomer and 10 to 30 parts by weight of the hard monomer. 2 parts by weight is prepared by emulsion polymerization.
상기 "소프트 단량체(soft monomer)"는 이 단량체의 단일중합체가 -10℃이하의 유리전이온도를 가짐을 의미하며, 용어 "하드 단량체(hard monomer)"는 이 단량체의 단일중합체가 최소 50℃의 유리전이온도를 가짐을 의미한다.
The term "soft monomer" means that the homopolymer of this monomer has a glass transition temperature of -10 ° C or less, and the term "hard monomer" means that the homopolymer of this monomer is at least 50 ° C. It has a glass transition temperature.
바람직한 실시예에 따르면, 상기 용제형 아크릴 화합물에 사용한 소프트 단량체는 60~90 중량부를 사용하는데, 60 중량부 미만일 경우 초기텍이 떨어져 접착제의 초기 고정성이 떨어지며, 90 중량부를 초과하면 접착제의 흐름성이 너무 커서 접착제의 기능을 발휘하지 못하게 된다. 본 발명에 사용할 수 있는 소프트 단량체는 부틸아크릴레이트, 이소부틸아크릴레이트, 에틸아크릴레이트, 2-에틸부틸아크릴레이트, 헥실아크릴레이트, 헵틸아크릴레이트, 옥틸아크릴레이트, n-펜틸아크릴레이트, 2-에틸헥실아크릴레이트 등이 있으며 단독 또는 2종 이상 병용하여 사용할 수 있다.According to a preferred embodiment, the soft monomer used in the solvent-type acrylic compound is used 60 to 90 parts by weight, if less than 60 parts by weight of the initial tec falls off the initial fixability of the adhesive, if more than 90 parts by weight flow of the adhesive This is so large that it can no longer function as an adhesive. Soft monomers that may be used in the present invention are butyl acrylate, isobutyl acrylate, ethyl acrylate, 2-ethylbutyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, n-pentyl acrylate, 2-ethyl Hexyl acrylate etc. can be used individually or in combination of 2 or more types.
또한 하드 단량체는 10~30 중량부로 사용하는데, 10 중량부 미만일 경우 접착제의 응집력이 떨어져 접착 물성이 떨어지며, 30 중량부를 초과하면 점도 제어가 어렵고 접착제의 유리전이온도가 높아져 접착제로서의 물성을 나타내지 못한다. 본 발명에 사용할 수 있는 하드 단량체로는 메틸아크릴레이트, 에틸메타크릴레이트, n-부틸메타크릴레이트, 이소부틸메타아크릴레이트, t-부틸아크릴레이트, 2-에틸헥실메타아크릴레이트, 라우릴아크릴레이트, 라우릴메타아크릴레이트 등이 있으며 단독 또는 2종 이상 병용하여 사용할 수 있다.
In addition, the hard monomer is used in 10 ~ 30 parts by weight, when less than 10 parts by weight, the cohesive strength of the adhesive is lowered, the adhesive properties are lowered, and if it exceeds 30 parts by weight, it is difficult to control the viscosity and the glass transition temperature of the adhesive is high and does not exhibit physical properties as the adhesive. Hard monomers that can be used in the present invention include methyl acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate , Lauryl methacrylate, and the like, and may be used alone or in combination of two or more thereof.
그리고 카르복실기를 갖는 단량체를 0.5~2 중량부 범위내에서 사용하고, 0.5중량부 미만일 경우에는 응집력이 낮아 접착력이 떨어지고, 2 중량부를 초과하였을 때는 합성 중 점도 제어가 용이하지 않고 시간이 경과함에 따라 접착제의 물성 변화를 초래한다. 본 발명에 사용한 단량체로는 아크릴산, 메타크릴산, 크로톤산, 말레인산, 푸말산, 이타콘산 등이 있으며 단독 또는 2종 이상 병용하여 사용할 수 있다.
When the monomer having a carboxyl group is used in the range of 0.5 to 2 parts by weight, and less than 0.5 parts by weight, the cohesive force is low to lower the adhesive strength. When the monomer is more than 2 parts by weight, the viscosity control during the synthesis is not easy and the adhesive is used as time passes. It causes a change in physical properties. The monomers used in the present invention include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, and can be used alone or in combination of two or more thereof.
이와 같은 조성물로 용액중합에 의해 제조된 용제형 아크릴 화합물의 점도는 3000~5000 cps의 일반적인 접착 물성이 양호하며 특히 내수성이 우수하다.
The viscosity of the solvent-type acrylic compound prepared by solution polymerization with such a composition is good general adhesive properties of 3000 ~ 5000 cps, in particular excellent water resistance.
그리고 상기 용제형 아크릴 화합물의 사용량은 35~55 중량부 범위 내에서 사용하는 것이 바람직하다. 35 중량부 미만일 경우 접착 보강의 효과가 떨어지며 55 중량부를 초과할 경우에는 취성으로 접착력 및 유연성이 떨어지는 단점이 있다.
And it is preferable to use the said solvent type acrylic compound within 35-55 weight part. If less than 35 parts by weight, the effect of the adhesive reinforcement is inferior, and if it exceeds 55 parts by weight, there is a disadvantage in that the adhesive strength and flexibility is poor due to brittleness.
또한 본 발명에서 상기 혼합 고분자 기재로 사용되는 염화폴리올레핀 그라프트 중합물은 착색 코팅제의 조성 성분에 관계 없이 사출부품과 착색 코팅제의 안정된 부착성을 부여하기 위해 사용하는 것으로서, 염화폴리올레핀 그라프트 중합물의 사용량은 20~40 중량부 범위 내에서 사용하는 것이 바람직하다. 20 중량부 미만일 경우 착색 코팅제의 부착성이 다소 떨어질 수 있으며, 40 중량부를 초과하면 사출부품의 젖음성을 향상시키는 저독성 용제에 대한 용해도가 저하될 우려가 있다.
In addition, in the present invention, the chlorinated polyolefin graft polymer used as the mixed polymer substrate is used to provide stable adhesion between the injection part and the coloring coating regardless of the composition of the coloring coating agent, and the amount of the chlorinated polyolefin graft polymer is It is preferable to use within the range of 20-40 weight part. If it is less than 20 parts by weight, the adhesion of the coloring coating agent may be somewhat deteriorated. If it exceeds 40 parts by weight, there is a fear that the solubility of the low-toxic solvent to improve the wettability of the injection part is lowered.
바람직한 실시예에 따르면, 상기 염화폴리올레핀 그라프트 중합물은 염화도가 10~50 중량%이고 연화점이 40~120℃인 염화폴리프로필렌이나 염화폴리에틸렌 등의 염화폴리올레핀 수지 100 중량부에 대하여 비관능성 아크릴계 모노머를 50~100 중량부를 사용하여 그라프트 중합하는데, 비관능성 아크릴계 모노머의 사용량이 50 중량부 미만일 경우, 착색 코팅제와의 부착력이 향상되지 않는 문제점이 있으며, 100 중량부를 초과될 경우, 택성이 높아져 오히려 피착재에 대한 계면 응집력이 낮아질 수 있다.According to a preferred embodiment, the chlorinated polyolefin graft polymer is a non-functional acrylic monomer with respect to 100 parts by weight of the chloride polyolefin resin such as polypropylene chloride or polyethylene chloride having a chloride degree of 10 to 50% by weight and a softening point of 40 to 120 ℃ When the graft polymerization is performed using 50 to 100 parts by weight, when the amount of the non-functional acrylic monomer is less than 50 parts by weight, there is a problem in that adhesion with the coloring coating agent is not improved. The interfacial cohesion for the ash may be lowered.
한편, 상기 비관능성 아크릴계 모노머로는 에틸아크릴레이트, 부틸메타크릴레이트, 메틸메타크릴레이트를 단독 또는 2종 이상 병용하여 사용할 수 있다.
In addition, as said nonfunctional acryl-type monomer, ethyl acrylate, butyl methacrylate, and methyl methacrylate can be used individually or in combination of 2 or more types.
또한 본 발명에서 사용하는 접착 증진제는 접착제 조성물의 접착력 향상을 목적으로 사용하는 화합물로서 변성에틸렌비닐아세테이트 수지를 사용하는데, 변성 에틸렌비닐아세테이트 수지는 에틸렌-아크릴 수지, 에틸렌비닐아세테이코폴리머, 아이노머 수지, 폴리프로필렌-아크릴산수지 및 열가소성 에틸렌메타아크릴산코폴리머 중에서 단독 또는 2종 이상 병용하여 사용하는 것이 바람직하다.
In addition, the adhesion promoter used in the present invention uses a modified ethylene vinyl acetate resin as a compound used for the purpose of improving the adhesive strength of the adhesive composition, the modified ethylene vinyl acetate resin is ethylene-acrylic resin, ethylene vinyl acetate copolymer, inomer It is preferable to use individually or in combination of 2 or more types of resin, polypropylene-acrylic-acid resin, and a thermoplastic ethylene methacrylate copolymer.
그리고 상기 접착 증진제의 사용량은 5~20 중량부를 사용하는 것이 바람직하며, 변성에틸렌비닐아세테이트 수지의 함량이 5 중량부 미만일 경우에는 수지의 용해도는 양호하나 접착력이 지나치게 저하될 우려가 있으며, 변성에틸렌비닐아세테이트수지의 함량이 20 중량부를 초과할 경우에는 용제에 잘 용해도지 않으며, 특히 고형분의 조절이 용이하지 않게 될 우려가 있다.
The amount of the adhesion promoter used is preferably 5 to 20 parts by weight. When the content of the modified ethylene vinyl acetate resin is less than 5 parts by weight, the solubility of the resin may be good but the adhesion may be excessively lowered. When the content of the acetate resin exceeds 20 parts by weight, it is difficult to dissolve in the solvent, in particular, there is a fear that the control of the solid content is not easy.
또한 본 발명에서 사용하는 충진제는 초기 응집력을 높이고 접착 보강 효과를 주기 위해 사용하는 것으로 무수규산, 함수규산, 규산 칼슘, 규산 알미튬 등의 규산계 및 금속산화물인 타이타늄다이세라믹사이드, 알루미늄세라믹사이드, 마그네슘세라믹사이드, 징크옥사이드, 산화철 중에서 단독 또는 그 이상 병용하여 사용할 수 있다.
In addition, the filler used in the present invention is used to increase the initial cohesion and to give an adhesion reinforcing effect, such as silicic acid based silicate and metal oxides such as silicic anhydride, hydrous silicic acid, calcium silicate, aluminum silicate, titanium dioxide, aluminum ceramic side, It can be used alone or in combination of magnesium ceramics, zinc oxide, iron oxide.
그리고 상기 충진제의 함량은 3~10 중량부를 사용하는 것이 바람직하며, 충진제의 사용량이 3 중량부 미만일 경우에는 가공성과 신도, 경도, 인장성질, 내열성등의 성질이 낮아질 우려가 있고, 충진제의 사용량이 10 중량부를 초과할 경우에는 용제에 잘 용해되지 않고 딱딱해질 수 있으며, 특히 점도 조절이 용이하지 않게 될 우려가 있다.
And the content of the filler is preferably used 3 to 10 parts by weight, when the amount of the filler used is less than 3 parts by weight, there is a fear that the properties such as workability and elongation, hardness, tensile properties, heat resistance, etc. are lowered, the amount of the filler used When it exceeds 10 parts by weight, it may be hard to dissolve in the solvent, and in particular, there is a fear that the viscosity is not easily adjusted.
또한 본 발명에서 사용하는 광 및 산소에 의한 변색을 방지하기 위해 첨가되는 첨가제는 선처리제가 광 및 산소에 의한 분해되어 변색되고 부스러지는 현상을 방지하기 위해 사용하는 것으로 HALS계, 벤조트리아졸계, 벤조페논계, 메톡시벤조페논계, 니켈유도체, 페놀계, 모노페놀계, 비스페놀계, 아민계, 유황계, 인계, Thio계가 있으며 2종 또는 그 이상을 선택하여 사용하는 것이 바람직하다.
In addition, additives added to prevent discoloration by light and oxygen used in the present invention are used to prevent discoloration and deterioration due to decomposition of the pretreatment agent by light and oxygen. HALS-based, benzotriazole-based and benzo-peptides Phenol type, methoxy benzophenone type, nickel derivative, phenol type, monophenol type, bisphenol type, amine type, sulfur type, phosphorus type and Thio type are preferable and it is preferable to use two or more types.
그리고 상기 광 및 산소에 의한 변색을 방지하기 위해 첨가되는 첨가제의 함량은 2~5 중량부 범위 내에서 사용하는 것이 바람직하며, 첨가제의 사용량이 2 중량부 미만일 경우 광 및 산소에 대한 안정성의 효과가 없으며, 첨가제의 사용량이 5 중량부를 초과할 경우에는 고분자 기재 수지와 상용성이 떨어지며 접착 물성에 방해인자가 될 우려가 있다.
The amount of the additive added to prevent discoloration by light and oxygen is preferably used in the range of 2 to 5 parts by weight, and when the amount of the additive is less than 2 parts by weight, the effect of stability on light and oxygen is improved. If the amount of the additive is more than 5 parts by weight, the compatibility with the polymer base resin is inferior and there is a fear that it may be an obstacle to adhesive properties.
또한 본 발명에서 사용가능한 용제는 구체적인 예를 들면, 메틸사이클로헥산, 메틸에틸케톤, 사이클로헥산, 아세톤, 초산에틸, 사이클로헥산올, 이소프로판올, n-프로판올, 에탄올 중에서 3종 또는 그 이상을 선택하여 사용하는 것이 바람직하다. 용제를 단독으로 사용할 경우에는 저장안정성 및 용해도가 떨어지게 된다. 본 발명에 사용된 용제는 총 고형분이 5~15 중량%가 되도록 조절하여 사용하는 것이 바람직하다.
In addition, solvents usable in the present invention are selected from three or more of specific examples, for example, methylcyclohexane, methyl ethyl ketone, cyclohexane, acetone, ethyl acetate, cyclohexanol, isopropanol, n-propanol, ethanol It is desirable to. If the solvent is used alone, the storage stability and solubility are inferior. The solvent used in the present invention is preferably used to adjust the total solid content is 5 to 15% by weight.
따라서, 본 발명은 착색코팅제 도포 부위 내변색성이 향상될 뿐만 아니라 사출부품과 착색코팅제 간의 부착성이 우수해지며, 도 2에 도시된 바와 같이, 본 발명에 따른 1액형의 선처리제(400)를 사용함에 따라, 도 1에 도시된 종래 UV형 선처리제(100), UV 조사(200) 및 세척제(300) 처리 등의 복잡한 전처리공정을 생략할 수 있게 되고, 이로 인해 경비절감 및 공정 간소화 그리고 작업장의 환경을 개선할 수 있게 된다.
Therefore, the present invention not only improves discoloration resistance of the color coating agent coating site, but also improves adhesion between the injection part and the coloring coating agent, and as shown in FIG. 2, the one-
이하, 본 발명의 구성을 아래 실시 예에 의해 상세히 설명하는바 본 발명의 구성은 아래의 실시예에 의해서만 반드시 한정되는 것은 아니다.
Hereinafter, the configuration of the present invention will be described in detail by the following examples, the configuration of the present invention is not necessarily limited only to the following examples.
1. 용제형 아크릴 화합물 제조예1. Preparation example of solvent type acrylic compound
혼합용기에 환류 냉각기와 교반기, 온도계 및 질소주입장치를 설치한 500ml 반응기에 부틸아크릴레이트 60 중량부, 에틸아크릴레이트 25 중량부, 메틸메타아크릴레이트 7 중량부 및 아크릴산 0,5 중량부로 구성되는 단량체 혼합물을 투입하였다. 그리고 용제로 메틸 에틸 케톤을 투입한 다음 질소를 30분간 퍼징하고 온도를 75℃로 승온하여 70 rpm의 교반 속도를 유지하였다. 다음으로 반응 개시제인 아조비스이소브티로니트릴 0.06 중량부를 50 중량% 농도로 메틸 에틸 케톤에 희석시켜 투입하고 10~12 시간 반응시켜 고형분 40 중량%인 용제형 아크릴 화합물을 제조한다.
Monomer consisting of 60 parts by weight of butyl acrylate, 25 parts by weight of ethyl acrylate, 7 parts by weight of methyl methacrylate and 0,5 parts by weight of acrylic acid in a 500 ml reactor equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen injection device in a mixing vessel. The mixture was added. Then, methyl ethyl ketone was added as a solvent, purged with nitrogen for 30 minutes, and the temperature was raised to 75 ° C. to maintain a stirring speed of 70 rpm. Next, 0.06 parts by weight of azobisisobutyronitrile, which is a reaction initiator, was diluted with 50% by weight of methyl ethyl ketone, and then reacted for 10 to 12 hours to prepare a solvent-type acrylic compound having a solid content of 40% by weight.
2. 염화폴리올레핀 그라프트 중합물 제조예2. Preparation example of chloride polyolefin graft polymer
혼합용기에 환류 냉각기와 교반기, 온도계 및 질소주입장치를 설치한 500ml 반응기에 염화폴리올레핀 수지(Superchlon 360, NIPPON PAPER CHEMICALS) 100 중량부, 메틸메타크릴레이트 50 중량부에 메틸 에틸 케톤 1000 중량부를 투입한 다음 70℃에서 1시간을 75 rpm 의 교반속도로 교반하였다. 다음으로 반응개시제인 벤조일퍼옥사이드 1 중량부를 메틸 에틸 케톤 100 중량부에 희석시킨 다음 4회에 걸쳐 1시간 단위로 투입하고 온도를 75℃로 승온하여 70 rpm의 교반 속도를 유지하여 그라프트 반응을 시켜 염화폴리올레핀 그라프트 중합물을 제조한다.
100 parts by weight of polyolefin resin (Superchlon 360, NIPPON PAPER CHEMICALS) and 1000 parts by weight of methyl ethyl ketone were added to a 500 ml reactor equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen injection device. Then, the mixture was stirred at 70 ° C. for 1 hour at a stirring speed of 75 rpm. Next, 1 part by weight of benzoyl peroxide, a reaction initiator, was diluted in 100 parts by weight of methyl ethyl ketone, and then charged in units of 1 hour over 4 times, and the temperature was raised to 75 ° C. to maintain a stirring speed of 70 rpm. To prepare a chlorinated polyolefin graft polymer.
3. 단축공정 고착색 표면처리제 조성물의 제조
3. Preparation of short colored high color surface treatment agent composition
아래 실시예 1 내지 4 및 비교에 1 내지 3의 단축공정 고착색 표면처리제를 아래 [표 1]의 구성성분비 내용에 따라 제조하였다.
In Example 1 to 4 below and 1 to 3 shortening process high-colored surface treatment agent in comparison was prepared according to the component ratio content of Table 1 below.
실시예 1Example 1
온도조절과 속도조절이 가능한 혼합용기에 아크릴변성 폴리올레핀 수지(100S, NIPPON PAPER CHEMICALS) 30 중량부와 용제형 아크릴 화합물 40 중량부에 염화폴리올레핀 그라프트 중합물 30 중량부, 접착 증진제(N-123, DUPONT) 15 중량부, 충진제(MOX 80, DEGUSSA) 4 중량부, 첨가제(S-1010, SONGWON) 1 중량부와 (S-2920, SONGWON) 2 중량부를 첨가한 후 사이클로 헥산, 메틸 에틸 케톤, 초산 에틸을 60 : 25 : 15의 비율로 병용하여 투입하여 상온에서 8시간 동안 교반하여 용해시킨 혼합액의 총고형분이 5중량%인 단축공정 고착색 표면처리제 조성물을 제조한다.
30 parts by weight of acrylic modified polyolefin resin (100S, NIPPON PAPER CHEMICALS) and 40 parts by weight of solvent type acrylic compound in a mixed container capable of temperature control and speed control, 30 parts by weight of polyolefin graft polymer, adhesion promoter (N-123, DUPONT) ) 15 parts by weight, 4 parts by weight of filler (MOX 80, DEGUSSA), 1 part by weight of additive (S-1010, SONGWON) and 2 parts by weight of (S-2920, SONGWON), followed by cyclohexane, methyl ethyl ketone, ethyl acetate Was used in combination at a ratio of 60:25:15 to prepare a short-acting solid-colored surface treating composition having a total solid content of 5% by weight of the mixed solution dissolved by stirring for 8 hours at room temperature.
실시예 2Example 2
온도조절과 속도조절이 가능한 혼합용기에 아크릴변성 폴리올레핀 수지(100S, NIPPON PAPER CHEMICALS) 35 중량부와 용제형 아크릴 화합물 35 중량부에 염화폴리올레핀 그라프트 중합물 30 중량부, 접착 증진제(N-123, DUPONT) 20 중량부, 충진제(MOX 80, DEGUSSA) 4 중량부, 첨가제(S-1010, SONGWON) 1 중량부와 (S-2920, SONGWON) 2 중량부를 첨가한 후 사이클로 헥산, 메틸 에틸 케톤, 초산 에틸을 60 : 25 : 15의 비율로 병용하여 투입하여 상온에서 8시간 동안 교반하여 용해시킨 혼합액의 총고형분이 5중량%인 단축공정 고착색 표면처리제 조성물을 제조한다.
35 parts by weight of acrylic modified polyolefin resin (100S, NIPPON PAPER CHEMICALS) and 35 parts by weight of solvent type acrylic compound in a mixed container capable of temperature control and speed control, 30 parts by weight of polyolefin graft polymer, adhesion promoter (N-123, DUPONT) ) 20 parts by weight, 4 parts by weight of filler (MOX 80, DEGUSSA), 1 part by weight of additive (S-1010, SONGWON) and 2 parts by weight of (S-2920, SONGWON), followed by cyclohexane, methyl ethyl ketone, ethyl acetate Was used in combination at a ratio of 60:25:15 to prepare a short-acting solid-colored surface treating composition having a total solid content of 5% by weight of the mixed solution dissolved by stirring for 8 hours at room temperature.
실시예 3Example 3
온도조절과 속도조절이 가능한 혼합용기에 아크릴변성 폴리올레핀 수지(100S, NIPPON PAPER CHEMICALS) 30 중량부와 용제형 아크릴 화합물 35 중량부에 염화폴리올레핀 그라프트 중합물 35 중량부, 접착 증진제(N-123, DUPONT) 15 중량부, 충진제(MOX 80, DEGUSSA) 4 중량부, 첨가제(S-1010, SONGWON) 1 중량부와 (S-2920, SONGWON) 2 중량부를 첨가한 후 사이클로 헥산, 메틸 에틸 케톤, 초산 에틸을 60 : 25 : 15의 비율로 병용하여 투입하여 상온에서 8시간 동안 교반하여 용해시킨 혼합액의 총고형분이 5중량%인 단축공정 고착색 표면처리제 조성물을 제조한다.
30 parts by weight of acrylic modified polyolefin resin (100S, NIPPON PAPER CHEMICALS) and 35 parts by weight of solvent type acrylic compound in a mixed container capable of temperature control and speed control 35 parts by weight of polyolefin graft polymer, adhesion promoter (N-123, DUPONT) ) 15 parts by weight, 4 parts by weight of filler (MOX 80, DEGUSSA), 1 part by weight of additive (S-1010, SONGWON) and 2 parts by weight of (S-2920, SONGWON), followed by cyclohexane, methyl ethyl ketone, ethyl acetate Was used in combination at a ratio of 60:25:15 to prepare a short-acting solid-colored surface treating composition having a total solid content of 5% by weight of the mixed solution dissolved by stirring for 8 hours at room temperature.
실시예 4Example 4
온도조절과 속도조절이 가능한 혼합용기에 아크릴변성 폴리올레핀 수지(100S, NIPPON PAPER CHEMICALS) 30 중량부와 용제형 아크릴 화합물 40 중량부에 염화폴리올레핀 그라프트 중합물 30 중량부, 접착 증진제(N-123, DUPONT) 10 중량부, 충진제(MOX 80, DEGUSSA) 5 중량부, 첨가제(S-1010, SONGWON) 1 중량부와 (S-2920, SONGWON) 2 중량부를 첨가한 후 사이클로 헥산, 메틸 에틸 케톤, 초산 에틸을 60 : 25 : 15의 비율로 병용하여 투입하여 상온에서 8시간 동안 교반하여 용해시킨 혼합액의 총고형분이 5중량%인 단축공정 고착색 표면처리제 조성물을 제조한다.
30 parts by weight of acrylic modified polyolefin resin (100S, NIPPON PAPER CHEMICALS) and 40 parts by weight of solvent type acrylic compound in a mixed container capable of temperature control and speed control, 30 parts by weight of polyolefin graft polymer, adhesion promoter (N-123, DUPONT) ) 10 parts by weight, 5 parts by weight of filler (MOX 80, DEGUSSA), 1 part by weight of additive (S-1010, SONGWON) and 2 parts by weight of (S-2920, SONGWON), followed by cyclohexane, methyl ethyl ketone, ethyl acetate Was used in combination at a ratio of 60:25:15 to prepare a short-acting solid-colored surface treating composition having a total solid content of 5% by weight of the mixed solution dissolved by stirring for 8 hours at room temperature.
비교예 1Comparative Example 1
온도조절과 속도조절이 가능한 혼합용기에 아크릴변성 폴리올레핀 수지(100S, NIPPON PAPER CHEMICALS) 30 중량부와 용제형 아크릴 화합물 40 중량부에 접착 증진제(N-123, DUPONT) 15 중량부, 충진제(MOX 80, DEGUSSA) 4 중량부, 첨가제(S-1010, SONGWON) 1 중량부와 (S-2920, SONGWON) 2 중량부를 첨가한 후 사이클로 헥산, 메틸 에틸 케톤, 초산 에틸을 60 : 25 : 15의 비율로 병용하여 투입하여 상온에서 8시간 동안 교반하여 용해시킨 혼합액의 총고형분이 5중량%인 단축공정 고착색 표면처리제 조성물을 제조한다.
30 parts by weight of acrylic modified polyolefin resin (100S, NIPPON PAPER CHEMICALS) and 40 parts by weight of a solvent type acrylic compound in a mixed container capable of temperature control and speed control 15 parts by weight of adhesion promoter (N-123, DUPONT), filler (MOX 80) , 4 parts by weight of DEGUSSA, 1 part by weight of additive (S-1010, SONGWON) and 2 parts by weight of (S-2920, SONGWON), and then added cyclohexane, methyl ethyl ketone and ethyl acetate in a ratio of 60:25:15. Combined and prepared in a short-term process high-colored surface treatment composition of 5% by weight of the total solid content of the mixed solution dissolved by stirring for 8 hours at room temperature.
비교예 2Comparative Example 2
온도조절과 속도조절이 가능한 혼합용기에 아크릴변성 폴리올레핀 수지(100S, NIPPON PAPER CHEMICALS) 35 중량부와 용제형 아크릴 화합물 35 중량부에 접착 증진제(N-123, DUPONT) 20 중량부, 충진제(MOX 80, DEGUSSA) 4 중량부, 첨가제(S-1010, SONGWON) 1 중량부와 (S-2920, SONGWON) 2 중량부를 첨가한 후 사이클로 헥산, 메틸 에틸 케톤, 초산 에틸을 60 : 25 : 15의 비율로 병용하여 투입하여 상온에서 8시간 동안 교반하여 용해시킨 혼합액의 총고형분이 5중량%인 단축공정 고착색 표면처리제 조성물을 제조한다.
Adhesion promoter (N-123, DUPONT) 20 parts by weight of acrylic modified polyolefin resin (100S, NIPPON PAPER CHEMICALS) and 35 parts by weight of solvent type acrylic compound in a mixing vessel capable of temperature control and speed control, filler (MOX 80) , 4 parts by weight of DEGUSSA, 1 part by weight of additive (S-1010, SONGWON) and 2 parts by weight of (S-2920, SONGWON), and then added cyclohexane, methyl ethyl ketone and ethyl acetate in a ratio of 60:25:15. Combined and prepared in a short-term process high-colored surface treatment composition of 5% by weight of the total solid content of the mixed solution dissolved by stirring for 8 hours at room temperature.
비교예 3Comparative Example 3
실시예 1과 같은 배합으로 제조한다. 단, 선처리제를 시험 평가할 때에는 방향족 이소시아네이트계 경화제를 5중량%를 첨하여 사용한다.
It is prepared by the same formulation as in Example 1. However, when trial-evaluating a pretreatment agent, 5 weight% of aromatic isocyanate type hardening | curing agents are added and used.
폴리올레핀 수지11) Acrylic modification
Polyolefin Resin1 1 )
화합물Solvent type acrylic
compound
그라프트 중합물Chlorinated Polyolefin
Graft polymer
2) N-123 : DUPONT
3) MOX 80 : DEGUSSA
4) S-1010 : SONGWON
5) S-2920 : SONGWONNote 1) 100S: NIPPON PAPER CHEMICALS
2) N-123: DUPONT
3) MOX 80: DEGUSSA
4) S-1010: SONGWON
5) S-2920: SONGWON
4. 단축공정 고착색 표면처리제 조성물의 평가
4. Evaluation of Shortening Process Coloring Agent Composition
상기 실시예 1 내지 4 및 비교예 1 내지 3에 따라 제조한 단축공정 고착색 표면처리제를 아래의 시험방법에 따라 평가하였으며, 그 결과를 아래 [표 2]에 나타내었다.
The shortened process high-colored surface treatment agent prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 was evaluated according to the following test method, and the results are shown in the following [Table 2].
가. 부착성 평가end. Adhesion evaluation
표면처리가 실시되지 않은 사출 파이론 표면에 선처리제를 도포하고 실온에서 5분 건조 한다. 다음에 착색 코팅제를 종류별로 건조 피막 두께가 45~50㎛로 되도록 도포하고 실온에서 15분 동안 건조한다. 시험편을 실온에서 1일 동안 방치한 후 도포면 위에 가로세로 1mm 간격으로 100개의 눈금을 형성한 후, 셀로판 테이프로 박리시켜 도포막의 잔존 정도로 판정하였다. 박리되는 개수가 전혀 없을 때에는 '우수'로 판정하고, 1개 이상이라도 떨어지는 경우에는 '불량'으로 판정하였다.
A pretreatment is applied to the surface of the injection pylon which is not subjected to the surface treatment and dried at room temperature for 5 minutes. Next, the coloring coating agent is applied so as to have a dry film thickness of 45 to 50 µm for each type, and dried at room temperature for 15 minutes. After leaving the test piece at room temperature for 1 day, 100 scales were formed at intervals of 1 mm on the coated surface, and then peeled off with cellophane tape to determine the degree of remaining of the coated film. When there was no number which peeled at all, it was determined as "good", and when it fell even more than one, it was determined as "bad."
나. 내변색성 평가I. Discoloration resistance evaluation
제조된 단축공정 고착색 표면처리제 조성물을 라벨지에 어플리케이터를 사용하여 10~15(wet)로 도포한 후 상온에서 30분간 방치하여 건조한 다음 50℃, 350nm, 300W의 UV lamp에 넣어 6시간 동안 유지하였고, 이 때 시편과 램프의 거리는 10inch이었다. 크로마미터(CR-300, Minolta, Japan)를 사용하여 조성물의 색상을 측정하였다.
After applying the prepared short-colored surface treatment agent composition to the label paper using an applicator 10 ~ 15 (wet) and left for 30 minutes at room temperature, dried and put in a UV lamp of 50 ℃, 350nm, 300W for 6 hours At this time, the distance between the specimen and the lamp was 10 inches. The color of the composition was measured using a chromameter (CR-300, Minolta, Japan).
(E)Full color difference
(E)
(6hr-0hr)(E)
(6hr-0hr)
2) NEUTRAL GRAY : GENERAL CHEMICAL
3) PRINTER GRAY : GENERAL CHEMICALNote 1) LT GRAPHITE: GENERAL CHEMICAL
2) NEUTRAL GRAY: GENERAL CHEMICAL
3) PRINTER GRAY: GENERAL CHEMICAL
상기 [표 2]에 나타난 바와 같이 단축공정 고착색 표면처리제를 사용함으로써 실시예 1 내지 4은 모두 비교예 1 내지 2에 비해 사출 파이론과 착색 코팅제간 그리고 착색 코팅제의 종류에 상관없이 부착성이 개선되었으며, 1액형으로 사용하므로 비교예 3에 비해 내변색성도 우수한 것으로 평가되었다.
As shown in [Table 2], by using the short-processing high-colored surface treatment agent, Examples 1 to 4 all improved the adhesion between the injection pyron and the coloring coating and irrespective of the type of the coloring coating compared to Comparative Examples 1 to 2. Since it is used as a one-component type, discoloration resistance was also evaluated as excellent compared to Comparative Example 3.
상술한 바와 같이, 본 발명에 따른 단축공정 고착색 표면처리제 조성물은 상기의 실시예를 통해 그 우수성이 확인되었으며, 그리고 본 발명은 해당 기술분야의 당업자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.
As described above, the short-term process high-colored surface treatment agent composition according to the present invention has been confirmed its superiority through the above examples, and the present invention is the spirit of the present invention described in the claims to those skilled in the art It will be understood that various modifications and variations can be made in the present invention without departing from the scope of the invention.
100 : UV형 선처리제 200 : UV 조사
300 : 세척제 400 : 단축공정 고착색 표면처리제100
300: cleaning agent 400: shortening process fixed color surface treatment agent
Claims (4)
아크릴변성 폴리올레핀 수지 25~45 중량부와, 용제형 아크릴 화합물 35~55 중량부 그리고 염화폴리올레핀 그라프트 중합물 20~40 중량부로 이루어진 혼합 고분자 기재 100 중량부에 대하여,
접착 증진제 5~20 중량부, 충진제 3~10 중량부, 광 및 산소에 의한 변색을 방지하기 위해 첨가되는 첨가제 2~5 중량부 및 용제 600~2600 중량부로 이루어지는 것을 특징으로 하는 단축공정 고착색 표면처리제 조성물
In the shortening process high color surface treatment composition,
To 100 parts by weight of the mixed polymer substrate consisting of 25 to 45 parts by weight of the acrylic modified polyolefin resin, 35 to 55 parts by weight of the solvent type acrylic compound and 20 to 40 parts by weight of the chlorinated polyolefin graft polymer,
Shortening process high-colored surface comprising 5 to 20 parts by weight of adhesion promoter, 3 to 10 parts by weight of filler, 2 to 5 parts by weight of additives added to prevent discoloration by light and oxygen, and 600 to 2600 parts by weight of solvent. Treatment Composition
상기 아크릴변성 폴리올레핀 수지는,
분자량이 40,000~80,000 이고 연화점이 60~140℃인 것 중에서 1종 또는 그 이상을 선택하여 사용하는 것을 특징으로 하는 단축공정 고착색 표면처리제 조성물.
The method of claim 1,
The acrylic modified polyolefin resin,
A shortened process high-colored surface treatment agent composition, characterized in that one or more selected from among those having a molecular weight of 40,000 to 80,000 and a softening point of 60 to 140 ° C.
상기 용제형 아크릴 화합물은,
단량체의 단일중합체가 -10℃이하의 유리전이온도를 가지는 소프트 단량체 60~90 중량부 및 단량체의 단일중합체가 50℃이상의 유리전이온도를 가지는 하드 단량체 10~30 중량부로 이루어진 기재 100 중량부에 대하여,
카르복실기를 갖는 단량체를 0.5~2 중량부를 유화중합 하여 제조한 것을 특징으로 하는 단축공정 고착색 표면처리제 조성물.
The method of claim 1,
The solvent type acrylic compound,
60 to 90 parts by weight of a soft monomer having a glass transition temperature of -10 ° C. or less, and 100 parts by weight of a substrate consisting of 10 to 30 parts by weight of a hard monomer having a glass transition temperature of 50 ° C. or more. ,
A shortening process high color surface treatment agent composition, which is prepared by emulsion polymerization of a monomer having a carboxyl group in an amount of 0.5 to 2 parts by weight.
상기 염화폴리올레핀 그라프트 중합물은,
염화도가 10~50 중량%이고 연화점이 40~120℃인 염화폴리프로필렌 또는 염화폴리에틸렌을 포함하는 염화폴리올레핀 수지 100 중량부에 대하여,
비관능성 아크릴계 모노머 에틸아크릴레이트, 부틸메타크릴레이트, 메틸메타크릴레이트를 단독 또는 2종 이상 병용하여 50~100 중량부를 그라프트 중합하여 제조하는 것을 특징으로 하는 단축공정 고착색 표면처리제 조성물.The method of claim 1,
The chlorinated polyolefin graft polymer,
With respect to 100 weight part of chlorinated polyolefin resins containing polypropylene chloride or chlorinated chloride whose chloride degree is 10-50 weight%, and a softening point is 40-120 degreeC,
A non-functional acryl-based monomer ethyl acrylate, butyl methacrylate, methyl methacrylate is used alone or in combination of two or more 50 to 100 parts by weight graft polymerization, characterized in that the short-term process high color surface treatment agent composition.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101357269B1 (en) | 2012-03-15 | 2014-02-04 | 대륭기업 주식회사 | Surface Treatment Composition |
| KR101440032B1 (en) | 2013-09-26 | 2014-09-24 | 주식회사 투에이취켐 | Powder coating material and method for manufacturing the same |
| KR20150121516A (en) | 2014-04-21 | 2015-10-29 | 한국신발피혁연구원 | Surface Treating Agent without halogen for Coloring and Shorter Process |
| WO2016209016A1 (en) * | 2015-06-26 | 2016-12-29 | 주식회사 케이씨씨 | Copolymer of acrylic-modified chlorinated polyolefin resin, and plastic primer coating composition comprising same |
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| CN115162019A (en) * | 2022-08-03 | 2022-10-11 | 常州雅美特窗饰股份有限公司 | Manufacturing method of high-sun-exposure curtain fabric |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101357269B1 (en) | 2012-03-15 | 2014-02-04 | 대륭기업 주식회사 | Surface Treatment Composition |
| KR101440032B1 (en) | 2013-09-26 | 2014-09-24 | 주식회사 투에이취켐 | Powder coating material and method for manufacturing the same |
| KR20150121516A (en) | 2014-04-21 | 2015-10-29 | 한국신발피혁연구원 | Surface Treating Agent without halogen for Coloring and Shorter Process |
| WO2016209016A1 (en) * | 2015-06-26 | 2016-12-29 | 주식회사 케이씨씨 | Copolymer of acrylic-modified chlorinated polyolefin resin, and plastic primer coating composition comprising same |
| CN107337971A (en) * | 2016-11-25 | 2017-11-10 | 广西点图包装有限公司 | Coating |
| CN115162019A (en) * | 2022-08-03 | 2022-10-11 | 常州雅美特窗饰股份有限公司 | Manufacturing method of high-sun-exposure curtain fabric |
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