KR100826754B1 - Poly ?-olefin resin for extrusion coating or extrusion laminating - Google Patents
Poly ?-olefin resin for extrusion coating or extrusion laminating Download PDFInfo
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- KR100826754B1 KR100826754B1 KR1020010082556A KR20010082556A KR100826754B1 KR 100826754 B1 KR100826754 B1 KR 100826754B1 KR 1020010082556 A KR1020010082556 A KR 1020010082556A KR 20010082556 A KR20010082556 A KR 20010082556A KR 100826754 B1 KR100826754 B1 KR 100826754B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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Abstract
본 발명은 접착성이 개선된 압출코팅 또는 압출라미네이트용 폴리알파올레핀 수지에 관한 것으로, 보다 상세하게는 에틸렌 70~99 중량%, 프로필렌 0.5~10 중량%, 및 헥센 0.5~20 중량%를 포함하며, 용융지수(190℃)가 0.5~100 g/10분이고 밀도가 0.900~0.940 g/㎤인 압출코팅 또는 압출라미네이트용 폴리알파올레핀 수지에 관한 것이며, 본 발명의 수지는 접착성이 매우 우수하여, 코팅기재로 일반적으로 사용되는 OPP(oriented polypropylene) 필름, 폴리에스터 필름, 실리콘 코팅지(silicon coating paper), 크래프트지(Kraft paper) 등에 널리 적용 가능하다.
The present invention relates to a polyalphaolefin resin for extrusion coating or extrusion laminate with improved adhesion, and more specifically comprises 70 to 99% by weight of ethylene, 0.5 to 10% by weight of propylene, and 0.5 to 20% by weight of hexene. And a melt index (190 ° C.) of 0.5 to 100 g / 10 minutes and a density of 0.900 to 0.940 g / cm 3, to a polyalphaolefin resin for extrusion coating or extrusion laminate, and the resin of the present invention is very excellent in adhesiveness, It is widely applicable to OPP (oriented polypropylene) film, polyester film, silicon coating paper, kraft paper and the like, which are generally used as coating materials.
폴리알파올레핀 수지, 압출코팅, 압출라미네이트, 접착성, 에틸렌, 프로필렌, 헥센Polyalphaolefin Resin, Extrusion Coating, Extrusion Laminate, Adhesive, Ethylene, Propylene, Hexene
Description
본 발명은 접착성이 개선된 압출코팅 또는 압출라미네이트용 폴리알파올레핀 수지에 관한 것으로, 보다 상세하게는 기본 단량체인 에틸렌에 접착성 개선용 공단량체로서 프로필렌과 헥센이 공중합된 고접착성 폴리알파올레핀 수지에 관한 것이다.The present invention relates to a polyalphaolefin resin for extrusion coating or extrusion laminate with improved adhesion, and more particularly, to a highly adhesive polyalphaolefin copolymerized with propylene and hexene as a co-monomer for improving adhesion to ethylene, which is a basic monomer. It is about resin.
압출코팅 및 압출라미네이트의 목적은 코팅수지와 기재(코팅대상 물질)를 일체화함으로써 각각의 특성을 상호보충하여 새로운 고기능성 복합 재료를 제공하는데 있다.The purpose of extrusion coating and extrusion laminate is to provide a new high-functional composite material by complementing each property by integrating the coating resin and the substrate (material to be coated).
그러나, 일반적인 코팅수지로 사용되는 폴리에틸렌은 무극성으로, 불활성이기 때문에 접착성이 열세하다. 이러한 단점을 극복하고자, 폴리에틸렌을 300℃ 이상의 고온에서 압출할 때, 코팅수지가 기재와의 접촉전 단시간 동안 공기중에 노출되게 함으로써 산화시켜 극성을 부여함과 동시에, 기재에 앵커코팅제(anchor coating agent)를 도포하여 접착성을 향상시키는 방법이 제안되었다. 여기서, 앵 커코팅제의 역할은 기재와 코팅수지간의 친화성을 개선하는 것으로, 주로 유기티탄계, 이소시아네이트계, 이민계 등의 유기 화합물이 사용된다. However, polyethylene, which is used as a general coating resin, is nonpolar and inert because of its inertness. To overcome this disadvantage, when extruded polyethylene at a high temperature of 300 ° C. or higher, the coating resin is exposed to air for a short time before contact with the substrate, thereby oxidizing to impart polarity and anchor coating agent to the substrate. A method of improving the adhesiveness by applying is proposed. Here, the role of the anchor coating agent is to improve the affinity between the substrate and the coating resin, mainly organic compounds such as organic titanium, isocyanate, imine-based.
유기티탄계 화합물로는 알킬티타네이트가 주로 사용되는데, 이 화합물은 초기 접착력이 좋고 기재에 코팅후 블로킹성이 없다는 장점이 있지만, 물이나 공기중의 수분과 반응하면 가수분해가 일어나 백색 분말이 형성되어 장기간 경과후 접착력이 떨어지는 단점이 있다. Alkyl titanate is mainly used as an organotitanium-based compound, which has the advantage of good initial adhesiveness and no blocking property after coating on the substrate, but when it reacts with water or water in the air, hydrolysis occurs and white powder is formed. There is a disadvantage that the adhesive strength after a long period of time is falling.
한편, 이소시아네이트계 화합물은 티탄계 화합물과는 달리 장기 접착력 저하 문제가 없고 내습성 및 내수성이 우수한 접착제로, 1액형과 2액형이 있다. 1액형은 말단에 NCO기를 가지고 있는 저분자량의 고분자이다. 따라서, 경화는 공기중의 수분 또는 기재상의 수분과 반응하여 진행된다. 2액형은 일정 비율의 폴리올(polyol) 성분과 이소시아네이트 성분으로 구성된다. 따라서, 경화는 OH기와 HCO기의 반응에 의해 우레탄 결합이 형성됨으로써 이루어진다. 2액형의 특징은 그 경화막이 유연하고, 앵커코팅제 층을 두껍게 할 수 있어 접착성능을 조절할 수 있다는 것이다. 그러나, 이들은 대부분 톨루엔 등과 같은 용제에 희석되어 사용 되기 때문에, 최종 제품에 톨루엔 등의 용제가 잔류하게 되어 식품포장재 등에의 적용에 많은 제약이 따르고, 특히 최근에는 이들 용제 자체의 사용을 규제하는 추세이다.On the other hand, the isocyanate compound, unlike the titanium compound, has no problem of lowering long-term adhesion and is excellent in moisture resistance and water resistance, and has a one-component type and a two-component type. One part type is a low molecular weight polymer which has NCO group at the terminal. Therefore, curing proceeds by reacting with moisture in the air or moisture on the substrate. The two-part form consists of a proportion of the polyol component and the isocyanate component. Therefore, hardening is achieved by forming a urethane bond by reaction of OH group and HCO group. The characteristic of the two-component type is that the cured film is flexible and the anchor coating agent layer can be thickened to adjust the adhesive performance. However, since most of them are diluted and used in solvents such as toluene, solvents such as toluene remain in the final product, which places a lot of restrictions on application to food packaging materials. .
반면에, 이민계 화합물은 3원환 구조의 이민기를 가진 매우 반응성이 우수한 수용성 수지로, 수용성이어서 사용하기에 편리하다는 장점이 있다. 하지만, 라미테이트 가공공정중 또는 라미네이트 후에도 화학적으로 거의 변화하지 않아서, 라 미네이트된 필름 사이에서도 수용성으로 존재하기 때문에, 내습성 및 내수성을 요하는 용도에는 적합하지 않다.
On the other hand, the imine compound is a very reactive water-soluble resin having an imine group having a three-membered ring structure, and has an advantage of being water-soluble and convenient to use. However, it is not suitable for applications requiring moisture resistance and water resistance because it hardly changes chemically during or after lamination processing, and thus exists water-soluble even between laminated films.
본 발명은 상기와 같은 종래기술의 문제점들을 해결하기 위한 것으로, 수지 자체의 접착성이 우수하여 별도의 앵커코팅제를 사용하지 않고도 기재와의 접착이 가능한 코팅수지를 제공함을 목적으로 한다. The present invention is to solve the problems of the prior art as described above, an object of the present invention is to provide a coating resin that can be adhered to the substrate without using an anchor coating agent is excellent in the adhesiveness of the resin itself.
즉, 본 발명은 에틸렌 70~99 중량%, 프로필렌 0.5~10 중량%, 및 헥센 0.5~20 중량%를 포함하며, 용융지수(190℃)가 0.5~100 g/10분이고 밀도가 0.900~0.940 g/㎤인 압출코팅 또는 압출라미네이트용 폴리알파올레핀 수지를 제공한다.
That is, the present invention includes 70 to 99% by weight of ethylene, 0.5 to 10% by weight of propylene, and 0.5 to 20% by weight of hexene, and has a melt index (190 ° C) of 0.5 to 100 g / 10 minutes and a density of 0.900 to 0.940 g. It provides a poly alpha olefin resin for extrusion coating or extrusion laminate of / cm 3.
이하, 본 발명을 보다 상세하게 설명한다. Hereinafter, the present invention will be described in more detail.
본 발명의 폴리알파올레핀 수지는 기본 수지인 에틸렌을 70~99 중량%의 함량으로 포함하며, 이외에 0.5~10 중량%의 프로필렌 및 이중결합이 탄소번호 1 내지 3 에 위치한 헥센 중에서 선택한 0.5~20 중량%의 헥센을 포함한다. 이러한 조성을 갖는 본 발명의 폴리알파올레핀 수지는 용융지수(190℃)가 0.5~100 g/10분이고, 밀도가 0.900~0.940 g/㎤이다.The polyalphaolefin resin of the present invention contains 70 to 99% by weight of ethylene, which is a basic resin, and 0.5 to 20% by weight of 0.5 to 10% by weight of propylene and double bonds selected from hexene located at carbon numbers 1 to 3 Contains% hexene. The polyalphaolefin resin of the present invention having such a composition has a melt index (190 ° C.) of 0.5 to 100 g / 10 min and a density of 0.900 to 0.940 g / cm 3.
본 발명에서 에틸렌과의 공단량체로서 사용된 프로필렌 및 헥센은 폴리머 주쇄에 삽입되어 결정구조 형성을 방해, 무정질화함으로써 본 발명의 수지의 접착성을 종래의 호모폴리에틸렌 코팅수지에 비해 현저히 개선하는 효과가 있다. 특히, 본 발명의 특징은 폴리알파올레핀 수지를 구성하는 각 단량체들, 즉 에틸렌, 프로필렌 및 헥센 간의 조성비에 있다. 본 발명의 폴리알파올레핀 수지 중의 프로필렌과 헥센의 함량이 상기 범위 내에 들 때, 폴리머 내의 결정 부위와 무정질 부위가 균형을 이루어, 상술한 접착성 개선 효과를 달성하면서도 범용 폴리올레핀 수지에 사용되는 것과 동일한 가공기기를 사용하여 동일 가공온도 영역에서 가공이 가능하게 된다.Propylene and hexene used as comonomers with ethylene in the present invention are inserted into the polymer backbone to prevent the formation of crystal structures and to amorphize, thereby significantly improving the adhesiveness of the resin of the present invention compared to conventional homopolyethylene coating resins. have. In particular, the feature of the present invention lies in the composition ratio between the respective monomers constituting the polyalphaolefin resin, that is, ethylene, propylene and hexene. When the content of propylene and hexene in the polyalphaolefin resin of the present invention falls within the above range, the crystalline site and the amorphous site in the polymer are balanced to achieve the above-described adhesion improving effect while achieving the same adhesion improving effect as those used in general-purpose polyolefin resins. It is possible to process in the same processing temperature range by using processing equipment.
본 발명의 폴리알파올레핀 수지의 제조에는 특별한 방법 또는 장치가 요구되지 않으며, 일반적인 설비와 제조 조건이 사용될 수 있다.
No particular method or apparatus is required for the production of the polyalphaolefin resin of the present invention, and general equipment and manufacturing conditions may be used.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로 본 발명을 제한하는 것으로 해석되어서는 안된다.
Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
실시예 및 비교예Examples and Comparative Examples
온도 80℃, 압력 10 KG/㎠로 유지되는 반응기에 에틸렌, 프로필렌 및 헥센을 하기 표 1의 조성비로 투입하고, 250rpm으로 교반하면서 공중합 반응을 진행하여 본 발명의 폴리알파올레핀 수지를 제조하였다. 기존의 코팅수지인, 용융지수(190℃)가 15 g/10분이고 밀도가 0.920 g/㎤인 저밀도 폴리에틸렌 수지를 비교예로 하여, 각 수지의 접착성을 ASTM D1876에 제시된 T Peel 테스트로 평가하였으며, 이 때 코팅기재로는 폴리에스터 필름을 사용하였고, 별도의 첨가제는 전혀 사용치 않 았다. 실시예 및 비교예에 사용된 각 수지의 기본물성 및 조성을 상기 접착성 평가결과와 함께 하기 표 1에 요약하여 나타내었다.Ethylene, propylene, and hexene were added to a reactor maintained at a temperature of 80 ° C. and a pressure of 10 KG / cm 2 at a composition ratio of Table 1 below, and a copolymerization reaction was performed while stirring at 250 rpm to prepare a polyalphaolefin resin of the present invention. As a comparative example, a low density polyethylene resin having a melt index (190 ° C.) of 15 g / 10 min and a density of 0.920 g / cm 3, which is a conventional coating resin, was evaluated by the T Peel test shown in ASTM D1876. At this time, a polyester film was used as the coating material, and no additional additive was used. The basic physical properties and compositions of each resin used in Examples and Comparative Examples are summarized in Table 1 together with the results of the adhesive evaluation.
이상에서 상세히 설명한 바와 같이, 본 발명의 폴리알파올레핀 수지는 접착성이 매우 우수하여, 코팅기재로 일반적으로 사용되는 OPP(oriented polypropylene) 필름, 폴리에스터 필름, 실리콘 코팅지(silicon coating paper), 크래프트지(Kraft paper) 등에 널리 적용 가능하다.As described in detail above, the polyalphaolefin resin of the present invention is very excellent in adhesion, OPP (oriented polypropylene) film, polyester film, silicon coating paper (kraft paper), kraft paper generally used as a coating material It is widely applicable to (Kraft paper) and the like.
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| KR100826754B1 true KR100826754B1 (en) | 2008-04-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920003034A (en) * | 1990-07-03 | 1992-02-29 | 김진희 | Gas General Monitor and Meter |
| KR950006124A (en) * | 1993-08-27 | 1995-03-20 | 이헌조 | Foam detection rinsing method of rotating drum type washing machine |
| JPH07258583A (en) * | 1994-03-28 | 1995-10-09 | Sekisui Jushi Co Ltd | Hot-melt traffic paint |
| KR20000031896A (en) * | 1998-11-11 | 2000-06-05 | 이영일 | Process for producing polyalphaolefin having high viscosity by using mixture of 1-octene and 1-hexene |
-
2001
- 2001-12-21 KR KR1020010082556A patent/KR100826754B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920003034A (en) * | 1990-07-03 | 1992-02-29 | 김진희 | Gas General Monitor and Meter |
| KR950006124A (en) * | 1993-08-27 | 1995-03-20 | 이헌조 | Foam detection rinsing method of rotating drum type washing machine |
| JPH07258583A (en) * | 1994-03-28 | 1995-10-09 | Sekisui Jushi Co Ltd | Hot-melt traffic paint |
| KR20000031896A (en) * | 1998-11-11 | 2000-06-05 | 이영일 | Process for producing polyalphaolefin having high viscosity by using mixture of 1-octene and 1-hexene |
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