KR20140133745A - Cyclic olefin copolymer composition with HALS UV stabilizer and extrusion film comprising the same - Google Patents
Cyclic olefin copolymer composition with HALS UV stabilizer and extrusion film comprising the same Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 238000001125 extrusion Methods 0.000 title abstract description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title description 9
- 239000004713 Cyclic olefin copolymer Substances 0.000 title description 8
- 239000012963 UV stabilizer Substances 0.000 title description 2
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- -1 cyclic olefin Chemical class 0.000 claims abstract description 36
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 24
- 230000008859 change Effects 0.000 description 10
- 239000000654 additive Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
Abstract
Description
본 발명은 HALS계 자외선 안정제를 포함하는 고리형 올레핀계 공중합체 조성물 및 이를 포함하는 압출 필름에 관한 것이다.The present invention relates to a cyclic olefin-based copolymer composition comprising a HALS-based ultraviolet stabilizer and an extruded film containing the same.
고리형 올레핀계 공중합체(Cyclic Olefin Copolymer 또는 Cyclic Olefin Polymer)는 비정질의 폴리 올레핀 수지로 LCD용 투명 플라스틱 재료로서 액정패널 기판, 위상차 필름, 시야각 확대 필름 등에 사용되며, 기타 용도로서 CD-ROM, 광학렌즈, 광섬유 및 캐패시터 필름 등에 사용된다. 물질이 만들어진 처음 상태와 같은 조건이 되면 다시 원래의 모양으로 되돌아가려는 성질이 있는 노보넨(norbornene)계열의 고리형 모노머와 에틸렌을 공중합 성능을 가지는 메탈로센 촉매 또는 지글러-나타(Ziegler-Natta)촉매를 이용한 공중합 또는 ROMP(Ring Opening Metathesis Polymerization)방법으로 합성된다. 독성이 거의 없는 고리형 올레핀과 에틸렌을 사용하므로 환경문제를 근원적으로 차단할 수 있는 장점이 있으며, 열적, 기계적, 광학적 특성을 발현할 수 있다. 하지만 자외선 조사 시 중합체가 분해될 수 있으며, 황변 현상이나 투명도가 변화할 수 있다. 따라서 자외선 안정제 또는 자외선 흡수제를 첨가하여 이 같은 현상을 방지하여야 한다.A cyclic olefin copolymer (cyclic olefin copolymer or cyclic olefin polymer) is an amorphous polyolefin resin and is used as a liquid crystal panel substrate, a retardation film, a viewing angle enlargement film and the like as a transparent plastic material for an LCD. Lenses, optical fibers, and capacitor films. A metallocene catalyst or Ziegler-Natta copolymer having ethylene-co-polymerizable cyclic monomers of the norbornene series, which has the property of returning to its original shape when the conditions are the same as those of the original state in which the substance is made, Is synthesized by copolymerization using a catalyst or a ROMP (Ring Opening Metathesis Polymerization) method. The use of cyclic olefins and ethylene, which are virtually non-toxic, has the advantage of being able to fundamentally block environmental problems, and it can exhibit thermal, mechanical and optical properties. However, when irradiated with ultraviolet rays, the polymer may be decomposed, and yellowing phenomenon or transparency may be changed. Therefore, a UV stabilizer or an ultraviolet absorber should be added to prevent this phenomenon.
HALS(Hindered Amine light Stabilizer)는 광분해반응 중 생성된 자유라디칼을 제거하여 광산화 반응을 정지시키는 역할을 하며, 광안정성 및 고분자와의 상용성이 탁월하여 고분자 본래의 물성을 저하시키지 않고 내후성과 내광성을 향상시킬 수 있다. 또한 표면보호작용이 우수하여 얇은 단면을 갖는 제품에도 적용이 가능하며, 착색이 되지 않는다.HALS (Hindered Amine light Stabilizer) removes the free radicals generated during the photolysis reaction and stops the photooxidation reaction. It is excellent in light stability and compatibility with polymers, so it does not deteriorate the inherent properties of the polymer, Can be improved. In addition, it can be applied to products having a thin cross section because of excellent surface protecting action, and it is not colored.
그러나 HALS계 자외선 안정제는 자외선에 대해 보호 효과를 나타내지만, 첨가량이 증가될수록 블루밍 현상이 발생하므로 이에 대한 문제점을 개선해야 할 필요가 있다.However, the HALS-based ultraviolet stabilizer shows a protective effect against ultraviolet rays, but as the added amount increases, the blooming phenomenon occurs.
본 발명은 장시간 자외선 노출 시에도 안정한 HALS계 자외선 안정제를 포함하는 고리형 올레핀계 공중합체 조성물을 제공하는 것을 목적으로 한다. 또한, 상기 고리형 올레핀계 공중합체 조성물을 사용하여 제조된 압출 필름을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a cyclic olefin-based copolymer composition containing a HALS-based ultraviolet stabilizer that is stable even when exposed to ultraviolet rays for a long time. Another object of the present invention is to provide an extruded film produced by using the above-mentioned cyclic olefin-based copolymer composition.
상기의 목적을 달성하기 위하여 본 발명은,According to an aspect of the present invention,
고리형 올레핀계 공중합체 및 분자량이 500 이상 1000 미만인 HALS계 자외선 안정제를 포함하는 고리형 올레핀계 공중합체 조성물을 제공한다.A cyclic olefin-based copolymer and a HALS-based ultraviolet stabilizer having a molecular weight of 500 or more and less than 1,000.
또한, 본 발명은 상기 HALS계 자외선 안정제를 포함하는 고리형 올레핀계 공중합체 조성물로 제조된 압출 필름을 제공한다.The present invention also provides an extruded film produced from the cyclic olefin-based copolymer composition comprising the HALS-based ultraviolet stabilizer.
본 발명의 HALS계 자외선 안정제를 포함하는 고리형 올레핀계 공중합체조성물로 제조된 압출 필름은 장시간 자외선 노출 시에도 안정하며, 황색 변화가 적다. 또한, 높은 용융지수와 낮은 점도를 가지고 있어 우수한 가공성을 갖는다.The extruded film produced from the cyclic olefin-based copolymer composition containing the HALS-based ultraviolet stabilizer of the present invention is stable even when exposed to ultraviolet rays for a long time and has little change in yellow color. In addition, it has a high melt index and low viscosity, and has excellent processability.
도 1은 실시예 1, 실시예 3 및 실시예 4의 압출 필름을 촬영한 사진이다.
도 2는 실시예 1, 실시예 3 및 실시예 4의 압출 필름의 투명도와 황색도를 측정한 그래프이다.
도 3은 실시예 1, 실시예 3 및 실시예 4의 압출 필름의 Re와 Rth를 측정한 그래프이다.
도 4는 비교예 1, 실시예 2 및 실시예 5의 압출 필름의 용융지수와 용융지수 증감율을 측정한 그래프이다.
도 5는 260℃에서 비교예 1, 실시예 2 및 실시예 4의 압출 필름의 점도를 측정한 그래프이다.
도 6은 비교예 1 내지 3 및 실시예 1의 압출 필름의 시간에 따른 황색도를 측정한 그래프이다.
도 7은 비교예 1 내지 3 및 실시예 1의 압출 필름의 시간에 따른 b*를 측정한 그래프이다.Fig. 1 is a photograph of the extruded films of Examples 1, 3 and 4; Fig.
2 is a graph showing the transparency and yellowness of the extruded films of Examples 1, 3 and 4. Fig.
3 is a graph showing Re and Rth of the extruded films of Examples 1, 3, and 4.
4 is a graph showing the melt index and the melt index increase / decrease rate of the extruded films of Comparative Examples 1, 2, and 5.
5 is a graph showing the viscosity of extruded films of Comparative Examples 1, 2 and 4 at 260 캜.
Fig. 6 is a graph showing the yellowness of extruded films of Comparative Examples 1 to 3 and Example 1 over time. Fig.
7 is a graph showing b * values of extruded films of Comparative Examples 1 to 3 and Example 1 with time.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 고리형 올레핀계 공중합체 및 분자량이 500 이상 1000 미만인 HALS계 자외선 안정제를 포함하는 고리형 올레핀계 공중합체 조성물에 관한 것이다.The present invention relates to a cyclic olefin-based copolymer composition comprising a cyclic olefin-based copolymer and a HALS-based ultraviolet stabilizer having a molecular weight of 500 or more and less than 1,000.
상기 HALS계 자외선 안정제의 분자량은 500 이상 1000 미만이 바람직하며, 500 미만이면 고리형 올레핀계 공중합체와 유동성의 차이가 커지므로 바람직하지 않으며, 분자량이 1000 이상이면 고리형 올레핀계 공중합체와의 혼합이 용이하지 않다.The molecular weight of the HALS-based ultraviolet stabilizer is preferably in the range of 500 to less than 1000, and if it is less than 500, the difference in flowability from the cyclic olefin copolymer tends to increase, and if the molecular weight is 1000 or more, mixing with the cyclic olefin- This is not easy.
또한, HALS계 자외선 안정제의 녹는점은 고리형 올레핀계 공중합체의 유리전이온도보다 5 내지 25℃ 낮은 것이 바람직하며, 특히, 110 내지 130℃인 것이 바람직하다. 상기 녹는점 범위에서 코팅, 테이프 및 필름 등과 같은 성형품의 가공 시 HALS계 자외선 안정제와 고리형 올레핀계 공중합체의 혼합 및 가공이 용이하다.The melting point of the HALS-based ultraviolet stabilizer is preferably lower than the glass transition temperature of the cyclic olefin-based copolymer by 5 to 25 ° C, more preferably 110 to 130 ° C. It is easy to mix and process the HALS-based ultraviolet stabilizer and the cyclic olefin-based copolymer during the processing of the molded article such as coating, tape and film in the melting point range.
상기 HALS계 자외선 안정제는 하기 화학식 1의 구조를 가지는 것을 특징으로 한다. The HALS-based ultraviolet stabilizer has a structure represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 식에서 R1 내지 R10은 각각 독립적으로 탄소수 1 내지 5의 측쇄 또는 직쇄의 알킬기 일 수 있다.In the above formula, R 1 to R 10 may each independently be a branched or straight-chain alkyl group having 1 to 5 carbon atoms.
상기 HALS계 자외선 안정제는 HALS계 자외선 안정제를 포함하는 고리형 올레핀계 공중합체 100 중량부에 대하여 0.05 내지 5 중량부로 포함될 수 있으며, 바람직하게는 0.1 내지 2 중량부이다. 상기 범위에서 UV에 대한 안정적인 특성을 유지하며 가공성이 용이하다.The HALS-based ultraviolet stabilizer may be included in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the cyclic olefin-based copolymer containing a HALS-based ultraviolet stabilizer. In this range, stable properties against UV are maintained and workability is easy.
본 발명에서 고리형 올레핀계 공중합체의 종류는 특별히 한정되지 않으며, 예컨대, 하기와 같은 종류의 고리형 올레핀계 중합체가 사용될 수 있다.The kind of the cyclic olefin-based copolymer in the present invention is not particularly limited, and for example, the following cyclic olefin-based polymers may be used.
상기 고리형 올레핀계 공중합체는 중량평균 분자량이 10,000 내지 120,000인 것이 바람직하게 사용될 수 있다.The cyclic olefin-based copolymer preferably has a weight average molecular weight of 10,000 to 120,000.
상기 고리형 올레핀계 공중합체는 경우에 따라 HALS계 자외선 안정제 이외에 트리아진 광흡수제, 산화 방지제, 활제, 보충 광안정제, 가소제, 난연제, 대전 방지제, 증마제, 충전제, 염료 및 안료 등을 포함할 수 있다.The cyclic olefin-based copolymer may contain a triazine light absorber, an antioxidant, a lubricant, a light stabilizer, a plasticizer, a flame retardant, an antistatic agent, a diluent, a filler, a dye and a pigment in addition to a HALS- have.
또한, 본 발명은 상기 고리형 올레핀계 공중합체 조성물로 제조된 압출 필름에 관한 것이다. 상기 압출 필름은 이 분야에 공지된 통상의 방법에 의해 제조될 수 있다. 예컨대, 압출 필름은 압출기의 호퍼로 해당 고분자를 투입하고, 스크류를 거쳐서 용융된 수지는 매니폴드 방식의 티 다이를 통하여 필름으로 제조될 수 있다.The present invention also relates to an extruded film produced from the above-mentioned cyclic olefin-based copolymer composition. The extruded film may be produced by a conventional method known in the art. For example, the extruded film can be produced by putting the polymer into a hopper of an extruder, and the molten resin through a screw can be made into a film through a manifold type Ti-die.
상기 제조된 압출 필름은 자외선 노출시 황색도와 투명도의 변화가 적으며, 장시간 자외선에 노출되어도 부서지는 현상이 발생하지 않는다. 또한 용융지수가 높고, 점도가 낮아 압출 장비의 금속 표면에서 용융된 HALS계 자외선 안정제를 포함하는 고리형 올레핀계 공중합체의 유동성을 증가시키므로 가공성이 증대될 수 있다.
The extruded film has little change in yellow color and transparency when exposed to ultraviolet rays, and does not break even when exposed to ultraviolet rays for a long time. In addition, since the melt index is high and the viscosity is low, the flowability of the cyclic olefin-based copolymer containing the HALS-based ultraviolet stabilizer melted on the metal surface of the extrusion equipment is increased, so that the workability can be increased.
이하, 본 발명을 실시예에 의해 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to examples.
단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.
However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.
<첨가제를 포함한 고리형 올레핀계 공중합체 압출 필름 제조>≪ Preparation of extruded film of cyclic olefin-based copolymer containing additives >
실시예Example 1 내지 5 및 1 to 5 and 비교예Comparative Example 1 내지 3의 첨가제를 포함한 고리형 올레핀계 공중합체 압출 필름 제조 Production of a cyclic olefin-based copolymer extruded film containing 1 to 3 additives
하기 표 1에 기재된 성분과 함량으로 실시예 1 내지 5 및 비교예 1 내지 3의 고리형 올리핀계 공중합체 조성물을 제조하였다. 구체적으로 고리형 올레핀계 공중합체와 첨가제를 텀블러를 통하여 혼합하거나, 5 중량%의 마스터배치를 제조하여 0.1 중량%가 되도록 용융 블렌딩 시켜서 고리형 올레핀계 공중합체를 제조하고, 상기 고리형 올레핀계 공중합체 조성물을 사용하여 압출 필름을 제조하였다. 각각의 실시예 및 비교예에 따른 성분의 함량은 하기 표 1과 같다.The cyclic olefin-based copolymer compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were prepared by the ingredients and contents shown in Table 1 below. Specifically, the cyclic olefin-based copolymer and the additive are mixed through a tumbler, or a master batch of 5% by weight is prepared and melt-blended at 0.1% by weight to prepare a cyclic olefin-based copolymer, An extruded film was prepared using the coalescent composition. The contents of the components according to the respective Examples and Comparative Examples are shown in Table 1 below.
(%)COC content
(%)
(%)HALS content
(%)
함량 (%)Antioxidant
content (%)
(%)Lubricant content
(%)
상기 고리형 올레핀계 공중합체(상품명:COC, 제조사명:TOPAS) 의 분자량은 70,000이며 하기 화학식 2와 같다. HALS계 자외선 안정제(상품명:Hostavin, 제조사명:Clariant) 의 분자량은 529이다. 또한, 산화방지제(상품명:Hostanox, 제조사명:Clariant)와 활제(상품명:SZ-210, 제조사명:송원산업)를 첨가제로 사용하였다.The molecular weight of the cyclic olefin-based copolymer (trade name: COC, manufactured by TOPAS) is 70,000 and is shown in the following formula (2). The molecular weight of HALS-based ultraviolet stabilizer (trade name: Hostavin, manufacturer: Clariant) is 529. An antioxidant (trade name: Hostanox, manufactured by Clariant) and a lubricant (trade name: SZ-210, manufactured by Songwon Industrial Co., Ltd.) were used as additives.
[화학식 2](2)
실험예Experimental Example 1. One. HALSHALS 계 자외선 안정제를 포함한 고리형 올레핀계 공중합체 압출 필름의 광학 특성Optical properties of extruded films of cyclic olefinic copolymers containing ultraviolet stabilizer
실시예 1, 실시예 3 및 실시예 4의 고리형 올레핀계 공중합체로 제조된압출 필름의 두께, 투과도(TT), 투명도(Hz), 황색도(YI), 위상차값(Re 및 Rth)을 측정하였으며, 결과는 하기 표 2와 같다.Transparency (TT), transparency (Hz), yellowness (YI), and retardation values (Re and Rth) of the extruded films made from the cyclic olefin-based copolymers of Examples 1, The results are shown in Table 2 below.
황색도(YI)는 HALS계 자외선 안정제의 함량에 따라 거의 변화가 없었지만, 투명도(Hz)는 실시예 3의 압출 필름이 가장 높았으며, HALS계 자외선 안정제 함량이 적은 실시예 1과 HALS계 자외선 안정제 함량이 높은 실시예 4의 압출 필름에서는 실시예 3보다 낮은 값을 보였다. 또한, 방해분석에서 Re 및 Rth은 실시예 3의 압출 필름에서 가장 작은 값을 보였다. 상기의 결과를 도 2와 도 3에 도시하였다.
The yellowness index (YI) showed almost no change depending on the content of the HALS-based ultraviolet stabilizer. The transparency (Hz) of the extruded film of Example 3 was the highest and the ultraviolet stabilizer of Example 1 and HALS- The extruded film of Example 4 having a higher content showed a lower value than that of Example 3. In the disturbance analysis, Re and Rth showed the smallest value in the extruded film of Example 3. The above results are shown in FIG. 2 and FIG.
실험예Experimental Example 2. 2. HALSHALS 계 자외선 안정제를 포함한 고리형 올레핀계 공중합체 압출 필름의 용융지수 측정Measurement of melt index of extruded film of cyclic olefin copolymer containing ultraviolet stabilizer
비교예 1, 실시예 2 및 실시예 5의 압출 필름의 용융지수(MFI)를 측정하였으며, 결과는 하기 표 3과 같다.The melt index (MFI) of the extruded films of Comparative Example 1, Example 2 and Example 5 were measured, and the results are shown in Table 3 below.
HALS계 자외선 안정제를 포함하지 않은 비교예 1의 압출 필름과 비교하여 HALS계 자외선 안정제를 0.2 중량% 함유한 실시예 2의 압출 필름의 용융지수는 7.5% 향상된 결과를 보였고, HALS계 자외선 안정제를 5 중량% 포함한 실시예 5의 압출 필름은 43.6%의 높은 값을 보였다. 따라서, HALS계 자외선 안정제가 많이 포함될수록 압출 필름의 용융지수는 높은 증감율을 보이며, 상기 결과를 도 4에 도시하였다.The melt index of the extruded film of Example 2 containing 0.2% by weight of the HALS-based ultraviolet stabilizer was improved by 7.5% as compared with the extruded film of Comparative Example 1 which did not include the HALS-based ultraviolet stabilizer, and the HALS- The extruded film of Example 5 containing the% by weight showed a high value of 43.6%. Therefore, as the HALS-based ultraviolet stabilizer is more abundant, the melt index of the extruded film shows a high increase / decrease rate, and the results are shown in FIG.
또한, 상기 비교예 1, 실시예 2 및 4에 대하여 260℃에서의 점성을 측정한 결과 도 5에 나타낸 바와 같이 유동학 측면에서 점도가 감소하는 것을 확인할 수 있었다.As a result of measuring the viscosity at 260 ° C for Comparative Examples 1, 2 and 4, it was confirmed that the viscosity decreased in terms of rheology as shown in FIG.
따라서, HALS계 자외선 안정제를 포함하면 압출장비의 금속 표면에서 용융된 고분자의 유동성이 증가하여 가공성이 증대되는 것을 알 수 있었다.
Therefore, the inclusion of the HALS-based ultraviolet stabilizer increases the flowability of the molten polymer on the metal surface of the extrusion equipment, thereby increasing the workability.
실험예Experimental Example 3. 첨가제를 포함한 고리형 올레핀계 공중합체 압출 필름의 3. An extruded film of cyclic olefin copolymer containing additives QUVQUV 촉진 내후 실험 Accelerated weathering experiment
비교예 1, 산화방지제를 포함한 비교예 2, 활제를 포함한 비교예 3 및 HALS계 자외선 안정제 0.1중량%를 포함한 실시예 1의 압출 필름의 QUV 촉진 내후 실험을 통하여 200시간과 500시간에서 내후성을 관찰하였으며, 결과는 하기 표 4와 같으며, 도 6과 도 7에 결과를 도시하였다.Comparative Example 1 containing Comparative Example 1, Comparative Example 2 containing antioxidant, Comparative Example 3 containing a lubricant, and 0.1% by weight of a HALS-based ultraviolet stabilizer were subjected to the QUV accelerated weathering test for the extruded film of Example 1 to observe weatherability over 200 hours and 500 hours The results are shown in Table 4 below, and the results are shown in FIGS. 6 and 7.
(산화 방지제) (Antioxidant)
((
활제Lubricant
) )
((
HALSHALS
계 자외선 안정제)Based ultraviolet stabilizer)
(200시간-(200 hours -
초기값Initial value
))
(200시간-(200 hours -
초기값Initial value
))
(500시간-(500 hours -
초기값Initial value
))
(500시간-(500 hours -
초기값Initial value
))
비교예 1 내지 3의 압출 필름은 부러지기 쉬워 500시간까지 측정이 불가하였지만 실시예 1의 압출 필름은 500시간까지 측정할 수 있었다.The extruded films of Comparative Examples 1 to 3 were liable to be broken and thus the measurement was impossible up to 500 hours, but the extruded film of Example 1 was able to measure up to 500 hours.
비교예 1 내지 3의 압출 필름은 황색도의 변화값이 컸으나, 실시예 1의 황색도의 변화는 시간이 지날수록 증가하였으나 비교예에 비하여 작은 변화를 보였으며, CIE 색좌표값 중의 b* 역시 같은 경향을 나타내었다. 따라서, HALS계 자외선 안정제를 포함한 압출 필름은 장시간 자외선에 노출되었을지라도 자외선으로부터 안정하다고 할 수 있다.
The extruded films of Comparative Examples 1 to 3 exhibited a large change in yellowness value, but the change in yellowness of Example 1 increased with time, but showed a small change compared with the comparative example, and b * Respectively. Therefore, an extruded film including a HALS-based ultraviolet stabilizer can be said to be stable from ultraviolet rays even though it is exposed to ultraviolet rays for a long time.
Claims (6)
[화학식 1]
상기 식에서 R1 내지 R10은 각각 독립적으로, 탄소수 1 내지 5의 측쇄 또는 직쇄의 알킬기이다.The cyclic olefin-based copolymer composition according to claim 1, wherein the HALS-based ultraviolet stabilizer has a structure represented by the following formula (1):
[Chemical Formula 1]
In the above formula, R 1 to R 10 each independently represent a branched or straight-chain alkyl group having 1 to 5 carbon atoms.
An extruded film produced from a cyclic olefin-based copolymer composition comprising the HALS-based ultraviolet stabilizer of claim 1.
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