KR100574682B1 - Polypropylene composition for extrusion coating - Google Patents
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- KR100574682B1 KR100574682B1 KR1020030098653A KR20030098653A KR100574682B1 KR 100574682 B1 KR100574682 B1 KR 100574682B1 KR 1020030098653 A KR1020030098653 A KR 1020030098653A KR 20030098653 A KR20030098653 A KR 20030098653A KR 100574682 B1 KR100574682 B1 KR 100574682B1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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Abstract
본 발명은 긴가지가 도입되고, 용융강도가 200mN 이상이며, 230℃, 2.16kg 조건에서 ASTM D1238 규격에 따른 용융지수가 10~30g/10분인, 압출코팅용 폴리프로필렌을 포함하는 수지조성물에 관한 것이다. 본 발명에 의하면, 용융장력이 기존 수지에 비해 우수하여 고속가공성, 열접착성, 네크인성 및 위빙 특성이 우수하여 압출코팅용으로 적합한 폴리프로필렌 수지조성물을 제공할 수 있다.The present invention relates to a resin composition comprising a polypropylene for extrusion coating, a long branch is introduced, the melt strength is 200mN or more, the melt index of 10 ~ 30g / 10 minutes according to ASTM D1238 standard at 230 ℃, 2.16kg conditions will be. According to the present invention, it is possible to provide a polypropylene resin composition suitable for extrusion coating because the melt tension is superior to that of the existing resin, so that the high-speed processability, heat adhesiveness, neck toughness, and weaving characteristics are excellent.
긴가지가 도입된 폴리프로필렌, 압출코팅, 위빙 특성 Polypropylene with long branches, extrusion coating, weaving characteristics
Description
본 발명은 압출코팅용 폴리프로필렌 수지조성물에 관한 것으로, 보다 상세하게는 긴가지가 도입된 폴리프로필렌 수지를 포함하는, 고속가공성 및 네크인(neck-in)성이 우수한 압출코팅용 폴리프로필렌 수지조성물에 관한 것이다.The present invention relates to a polypropylene resin composition for extrusion coating, and more particularly, to a polypropylene resin composition for extrusion coating having excellent high-speed processing and neck-in properties, including a polypropylene resin having a long branch introduced therein. It is about.
일반적으로 OPP 필름을 식품포장용으로 사용할 때, 필름의 강성을 향상시키기 위해 폴리올레핀계 수지를 압출코팅하여 사용한다. 이러한 압출코팅용 수지로서는 밀도 0.920g/cm3이하의 가지상 저밀도 폴리에틸렌이 많이 사용된다. 그러나 이러한 저밀도 폴리에틸렌은 강도가 약하여 높은 강도를 요구하는 경우에는 적용이 어렵다. 이러한 단점을 해결하기 위해서는 강성이 우수한 폴리프로필렌 수지를 사용할 수 있으나 폴리프로필렌 수지는 네크인성이 열세하다는 약점이 있다. In general, when the OPP film is used for food packaging, it is used by extrusion coating a polyolefin resin to improve the rigidity of the film. As the resin for extrusion coating, many branched low density polyethylenes having a density of 0.920 g / cm 3 or less are used. However, such low density polyethylene is difficult to apply when the strength is weak and requires high strength. In order to solve these disadvantages, a polypropylene resin having excellent rigidity may be used, but the polypropylene resin has a weak neck toughness.
본 발명은 상기한 바와 같은 문제점을 해결하기 위한 것으로, 내열성 및 용융장력이 우수하고, 고속가공성, 열접착성, 네크인성 및 위빙(weaving) 특성이 우수한 압출코팅용 폴리프로필렌 수지조성물을 제공함을 목적으로 한다. The present invention is to solve the problems as described above, to provide a polypropylene resin composition for extrusion coating excellent in heat resistance and melt tension, excellent in high-speed processing, heat adhesiveness, neck toughness and weaving (weaving) properties It is done.
본 발명의 수지조성물은 긴가지가 도입되고, 용융강도가 200mN 이상이며, 230℃, 2.16kg 조건에서 ASTM D1238 규격에 따른 용융지수가 10~30g/10분인 폴리프로필렌 100중량부 및 산화방지제 0.1~1.0중량부로 이루어진 것을 특징으로 한다.The resin composition of the present invention has a long branch is introduced, the melt strength is 200mN or more, 100 parts by weight of polypropylene and the antioxidant 0.1 ~ 10 ~ 30g / 10 minutes melt index according to ASTM D1238 standard at 230 ℃, 2.16kg conditions It is characterized by consisting of 1.0 parts by weight.
본 발명에서 사용되는 긴가지가 도입된 폴리프로필렌 중합체는 알파올레핀 중합용 촉매의 주위에 고분자량 단량체가 캡슐화한 형태의 전중합 촉매를 이용하여 통상의 방법으로 중합된 것으로서, 이의 제조에 사용되는 촉매성분은 본 출원인이 이미 출원한 대한민국 특허 출원 번호 제2001-0085640호에 기재되어 있다. 이 촉매 성분에 대해 간략히 요약해 보면, 올레핀 중합용 고체 티타늄 촉매를 두개 이상의 비닐기를 가지는 실란화합물로 표면처리한 다음, 이 표면 처리된 고체 티타늄촉매와 올레핀 단량체 및 디엔 화합물을 전중합시키므로써 촉매주위에 고분자량 단량체를 캡슐화시켜 제조된 것을 특징으로하는 알파올레핀 중합용 촉매이다. The polypropylene polymer having a long branch introduced in the present invention is polymerized by a conventional method using a prepolymerization catalyst in a form in which a high molecular weight monomer is encapsulated around the catalyst for alpha olefin polymerization, and a catalyst used for its preparation. The components are described in Korean Patent Application No. 2001-0085640, which the applicant has already filed. To summarize the catalyst components, the solid titanium catalyst for olefin polymerization is surface treated with a silane compound having two or more vinyl groups, and then the surface treatment is performed by prepolymerizing the surface treated solid titanium catalyst with an olefin monomer and a diene compound. A catalyst for alpha olefin polymerization, which is prepared by encapsulating a high molecular weight monomer in a mixture.
본 발명에서 사용되는 긴 가지가 도입된 폴리프로필렌 중합체는 그 용융지수가 10~30g/10분(230℃)인 것이 바람직하고, 15~25g/10분(230℃)인 것이 더욱 바람직하다. 상기 용융지수가 10g/10분 미만에서는 가공시 부하가 많이 걸리고, 급격한 압력 상승을 수반한다. 용융지수가 30g/10분 이상인 경우에는 용융강도 저하를 수반하여 네크인성이나 위빙특성이 열악하게 된다. It is preferable that the melt index of the polypropylene polymer into which the long branch is used in this invention is 10-30 g / 10min (230 degreeC), and it is more preferable that it is 15-25 g / 10min (230 degreeC). If the melt index is less than 10 g / 10 minutes, the processing takes a lot of load, accompanied by a rapid pressure rise. When the melt index is 30 g / 10 minutes or more, the neck toughness and the weaving characteristic are poor with the decrease in the melt strength.
본 발명의 폴리프로필렌계 수지 조성물은 연신점도의 측정시 변형율 속도가 어느 정도 이상의 값을 가지면, 점단후화(Extension Hardening) 현상이 발현되어 연신점도 값이 선형 곡선의 값보다 많이 커지는 것을 특징으로 하는 것이다.The polypropylene resin composition of the present invention is characterized in that when the strain rate has a value of a certain degree or more, the extension hardening phenomenon occurs and the stretch viscosity value becomes larger than that of the linear curve. .
본 발명의 폴리프로필렌 수지조성물에는 이러한 류의 조성물에 일반적으로 사용되는 것으로 알려진 공지의 산화방지제를 첨가하는데, 그 양은 긴가지가 도입된 폴리프로필렌 100중량부에 대하여 0.1~1.0중량부가 바람직하고, 0.3~0.7 중량부가 더욱 바람직하다. 0.1중량부 미만에서는, 산화방지효과가 불충분할 염려가 있고, 1.0중량부를 넘으면, 산화방지효과가 일정 수준에 달하여 더 이상 증가하지 않기 때문이다.To the polypropylene resin composition of the present invention, a known antioxidant known to be generally used in this kind of composition is added. The amount is preferably 0.1 to 1.0 parts by weight, and 0.3 to 100 parts by weight of polypropylene having long branches. 0.7 weight part is more preferable. If it is less than 0.1 part by weight, the antioxidant effect may be insufficient, and if it is more than 1.0 part by weight, the antioxidant effect reaches a certain level and does not increase any more.
본 발명의 수지조성물에는 내열안정제, 슬립제, 중화제등과 같이 통상적으로 압출코팅 수지조성물에 사용되는 각종의 첨가제를 본 발명의 특징에 어긋나지 않는 범위 내에서 첨가할 수 있다.To the resin composition of the present invention, various additives commonly used in extrusion-coated resin compositions, such as heat stabilizers, slip agents, neutralizers, and the like, can be added within a range not departing from the characteristics of the present invention.
본 발명의 수지조성물을 제조하는 방법에 있어서는 특별한 제한이 없고 보편적으로 알려진 폴리프로필렌 수지조성물 제조 방법을 이용할 수 있다. 즉 긴가지가 도입된 폴리프로필렌 수지 및 각 첨가제 성분들을 원하는 순서에 따라 자유롭게 선택하여 니더, 롤, 밤바리 믹서등의 혼련기와 1축 또는 2축 압출기 등을 사용하여 혼련함으로써 본 발명의 수지조성물을 제조 할 수 있다.The method for producing the resin composition of the present invention is not particularly limited, and a method for producing a polypropylene resin composition may be used. That is, the resin composition of the present invention is prepared by freely selecting the polypropylene resin and each additive component in which the long branch is introduced and kneading using a kneader such as a kneader, a roll, a chestnut mixer, or a single or twin screw extruder I can manufacture it.
본 발명의 수지조성물을 이용하는 압출코팅은 통상의 T-다이법에 의해 성형되며 고속가공성, 네크인성이 우수하고 강도가 뛰어나며, 가공성을 사용자에 맞게 용이하게 조절할 수 있어 BOPP 열접착용, BOPP/CPP 합지용 및 컨테이너 코팅용으로 응용될 수 있다. Extrusion coating using the resin composition of the present invention is molded by a conventional T-die method, excellent in high-speed processing, neck toughness and excellent strength, can easily adjust the workability to the user BOPP thermal bonding, BOPP / CPP It can be applied for lamination and container coating.
본 발명은 하기의 실시예에 의하여 보다 구체적으로 이해될 수 있으며, 하기의 실시예는 본 발명을 예시하기 위한 예에 지나지 않는 것으로 본 발명의 보호범위를 제한하는 것은 아니다. The present invention can be understood in more detail by the following examples, the following examples are merely examples for illustrating the present invention and do not limit the protection scope of the present invention.
[실시예 및 비교예][Examples and Comparative Examples]
각 실시예 및 비교예에 있어서의 제반 물성의 측정법은 다음과 같다.The measuring method of the physical property in each Example and a comparative example is as follows.
용융지수 측정Melt Index Measurement
ASTM D1238에 의거하여 230℃, 2.16kg에서 측정하였다.It measured at 230 degreeC and 2.16 kg based on ASTMD1238.
용융강도 및 연신점도 측정Melt strength and draw viscosity measurement
특허출원 제1999-8553호 및 제2001-30112호 등에 기재된SMER(Samsung Melt Tension Rheometer)을 이용하여 200℃에서 모세관유량계(capillary rheometer)의 판을 통해 나오는 스트랜드에 대하여 140℃ 쳄버온도에서 용융강도 및 연신점도를 측정하였다. 이때 판의 L/D는16이며, 가속비는 1mm/sec였다. Melt strength at 140 ° C. chamber temperature for strands exiting through a plate of capillary rheometer at 200 ° C. using SMER (Samsung Melt Tension Rheometer) described in Patent Application Nos. 1999-8553 and 2001-30112, etc. The draw viscosity was measured. At this time, the L / D of the plate was 16, and the acceleration ratio was 1 mm / sec.
고속가공성High Speed Machinability
압출기를 100rpm으로 일정하게 유지하고 코팅속도를 점차 증가시켜 파단이 일어나는 속도를 측정하였다. The extruder was kept constant at 100 rpm and the coating speed was gradually increased to measure the rate at which breakage occurred.
필름폭Film width
T-다이(Die)로부터 나오는 용융지수를 OPP필름에 코팅하여 코팅폭을 측정하여 T-다이 폭에 대한 %로 결정하였다. 이때 가공 온도는 290℃, T-Die 폭은 80mm이었다.The melt index from the T-die was coated on the OPP film to determine the coating width and determined as% of the T-die width. At this time, the processing temperature was 290 ° C and the T-Die width was 80 mm.
접착성Adhesive
코팅 기재로BOPP 필름을 사용하여, ASTM D1876에 제시된T Peel 테스트로 접착성을 평가하였다. Using a BOPP film as the coating substrate, adhesion was evaluated by the T Peel test presented in ASTM D1876.
위빙 발생 속도Weaving Speed
압출코팅시 일어나는 폭 변화 특성을 평가하기 위하여, 변화폭이 10% 이상인 가공 속도를 측정하였다In order to evaluate the characteristics of the width change occurring during extrusion coating, a processing speed of 10% or more was measured.
[실시예 1] Example 1
긴 가지가 도입되고, 용융강도가 200mN이며, 230℃, 2.16kg 조건에서 ASTM D1238 규격에 따른 용융지수가 15.0g/10분인, 폴리프로필렌 100중량부에 산화방지제 0.5중량부를 함께 혼합한 후 2축 압출기를 통해 용융 혼합하여 펠렛화하였다. 상기 수지조성물의 물성을 평가하고 이를 하기 표1에 나타내었다.Long axis is introduced, the melt strength is 200mN, and the mixture is mixed with 0.5 parts by weight of antioxidant to 100 parts by weight of polypropylene having a melt index of 15.0 g / 10 min according to ASTM D1238 standard at 230 ° C. and 2.16 kg. Pelletized by melt mixing through an extruder. The physical properties of the resin composition were evaluated and shown in Table 1 below.
[비교예 1] Comparative Example 1
실시예 1의 폴리프로필렌 대신에, 용융강도가 40mN이며, 230℃, 2.16kg 조건에서 ASTM D1238 규격에 따른 용융지수가 15.0g/10분인 폴리프로필렌 100중량부를 사용한 것 외에는 상기 실시예 1과 동일하게 펠렛화하고, 그 물성을 평가하여 이를 하기 표1에 나타내었다.Instead of the polypropylene of Example 1, the melt strength was 40mN, and the same as in Example 1 except that 100 parts by weight of polypropylene having a melt index of 15.0 g / 10 minutes in accordance with ASTM D1238 standard at 230 ℃, 2.16kg conditions Pelletizing and evaluation of the physical properties are shown in Table 1 below.
[비교예 2] Comparative Example 2
실시예 1의 폴리프로필렌 대신에, 용융강도가 20mN이며, 230℃, 2.16kg 조건에서 ASTM D1238 규격에 따른 용융지수가 30.0g/10분인 폴리프로필렌을 사용한 것 외에는 상기 실시예 1과 동일하게 펠렛화하고 그 물성을 평가하여 이를 하기 표1에 나타내었다. Instead of the polypropylene of Example 1, pelletized in the same manner as in Example 1 except that polypropylene having a melt strength of 20 mN and a melt index of 30.0 g / 10 min according to ASTM D1238 standard at 230 ° C. and 2.16 kg was used. And the physical properties were evaluated and shown in Table 1 below.
상기 비교예에 의한 수지조성물은 위빙현상이 발생하며, 접착력, 고속 가공성 및 네크인성이 열세한 것으로 드러난 것과 달리, 본 발명에 의하면 용융장력이 기존 수지에 비해 우수하여 고속가공성, 열접착성, 네크인성 및 위빙 특성이 우수한 압출코팅용 폴리프로필렌 수지조성물을 제공할 수 있다. 뿐만 아니라 열가소성수지의 성질을 그대로 유지할 수 있어 재활용이 가능하다는 장점이 있다.
In the resin composition according to the comparative example, the weaving phenomenon occurs, and the adhesion, high-speed workability and neck toughness are inferior, according to the present invention, the melt tension is superior to the conventional resin, high-speed processing, thermal adhesion, neck It is possible to provide a polypropylene resin composition for extrusion coating excellent in toughness and weaving properties. In addition, it is possible to maintain the properties of the thermoplastic resin as it is possible to recycle.
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