KR100252029B1 - Uv-curable composition and scratch resistant film - Google Patents
Uv-curable composition and scratch resistant film Download PDFInfo
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- KR100252029B1 KR100252029B1 KR1019980006141A KR19980006141A KR100252029B1 KR 100252029 B1 KR100252029 B1 KR 100252029B1 KR 1019980006141 A KR1019980006141 A KR 1019980006141A KR 19980006141 A KR19980006141 A KR 19980006141A KR 100252029 B1 KR100252029 B1 KR 100252029B1
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- ultraviolet
- curable composition
- acrylate
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- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000007513 acids Chemical class 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 7
- FHFVUEXQSQXWSP-UHFFFAOYSA-N 2-hydroxy-2,2-dimethoxy-1-phenylethanone Chemical compound COC(O)(OC)C(=O)C1=CC=CC=C1 FHFVUEXQSQXWSP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims abstract description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 7
- 239000002318 adhesion promoter Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 27
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000004383 yellowing Methods 0.000 abstract description 8
- SLVZOGVXUWUDJW-UHFFFAOYSA-L C(C=C)(=O)[O-].C(C=C)(=O)[O-].[Si+2] Chemical compound C(C=C)(=O)[O-].C(C=C)(=O)[O-].[Si+2] SLVZOGVXUWUDJW-UHFFFAOYSA-L 0.000 abstract 1
- 239000003505 polymerization initiator Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 13
- -1 polyethylene terephthalate Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001723 curing Methods 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 10
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- 230000004927 fusion Effects 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 6
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229920006267 polyester film Polymers 0.000 description 5
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YTLYLLTVENPWFT-UPHRSURJSA-N (Z)-3-aminoacrylic acid Chemical compound N\C=C/C(O)=O YTLYLLTVENPWFT-UPHRSURJSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- QDHUQRBYCVAWEN-UHFFFAOYSA-N amino prop-2-enoate Chemical class NOC(=O)C=C QDHUQRBYCVAWEN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
Abstract
Description
본 발명은 자외선 경화형 조성물 및 이를 이용한 내스크래치성 필름에 관한 것으로서, 보다 상세하게는 폴리에스테르 필름의 표면경도 향상을 위하여 필름 표면에 형성되는 하드 코팅층용으로 적합한 자외선 경화형 조성물 및 이를 이용한 내스크래치성 필름에 관한 것이다.The present invention relates to an ultraviolet curable composition and a scratch resistant film using the same, and more particularly, an ultraviolet curable composition and a scratch resistant film suitable for a hard coating layer formed on the surface of a film for improving the surface hardness of a polyester film. It is about.
폴리에틸렌테레프탈레이트 필름을 비롯한 폴리에스테르 소재는 타소재에는 없는 우수한 특징, 예를 들면 경량이지만 단단하고 가공하기 쉬운 여러 가지 장점을 가지고 있으므로 생산합리화, 에너지절약 등의 사회적 요구에 부응함으로써 그 용도가 폭넓게 확산되고 있다. 그러나, 이러한 폴리에스테르 제품은 표면경도가 낮아 상처받기 쉽고, 내스크래치성을 필요로 하는 분야에서의 사용은 곤란한 것으로 인식되고 있다. 따라서, 이러한 폴리에스테르 제품의 단점을 보완하기 위하여 제품의 표면을 하드 코팅 처리함으로써 표면경도를 향상시킨 내스크래치성 필름에 대한 요구가 증대되고 있다.Polyester materials, including polyethylene terephthalate films, have excellent features that are not found in other materials, such as light weight, but they have a number of advantages that are hard and easy to process, so they can be widely used by meeting social demands such as streamlining production and saving energy. It is becoming. However, it is recognized that such polyester products are susceptible to low surface hardness and are difficult to use in fields requiring scratch resistance. Accordingly, there is an increasing demand for a scratch resistant film having improved surface hardness by hard coating the surface of the product in order to compensate for the disadvantage of the polyester product.
종래부터 폴리에스테르 필름의 표면경도를 향상시켜 내스크래치성을 부여하기 위한 방법이 다수 제안되어 왔다. 그 예를 들면, 멜라민 수지, 우레탄 수지, 아크릴 수지 또는 알키드 수지 등을 도포하여 열경화시키는 방법, 폴리실록산 구조를 갖는 열경화형 실리콘 수지를 도포하여 열경화시키는 방법, 무기계 실리콘 옥사이드를 도포하는 방법, 다관능성 아크릴 수지를 주 바인더로 하여 자외선을 조사하여 경화시키는 방법 등이 알려져 있다.Conventionally, many methods for improving the surface hardness of a polyester film and providing scratch resistance have been proposed. Examples thereof include a method of applying a thermosetting silicone resin having a polysiloxane structure by applying a melamine resin, a urethane resin, an acrylic resin, an alkyd resin, or the like, and a thermosetting silicone resin, a method of applying an inorganic silicon oxide, or a polyfunctional acrylic resin. The method of hardening by irradiating an ultraviolet-ray using resin as a main binder is known.
그러나, 상기 방법중 열경화 방법은 다음과 같은 단점을 지니고 있다.However, the thermal curing method of the above method has the following disadvantages.
즉, 주로 고온에서 경화가 진행되기 때문에 열에 약한 소재에는 사용할 수 없고, 용제를 사용하기 때문에 공기오염 등의 환경문제가 발생하고, 경화시키기 위하여 에너지가 많이 소비되고, 경화장치를 설치하기 위하여 넓은 면적이 소요되며 경화를 위하여 장시간이 소요되므로 생산성이 저하된다는 등의 문제가 있다.That is, it is hardly used at high temperatures, so it cannot be used for materials that are weak to heat, and because of the use of solvents, environmental problems such as air pollution occur, energy is consumed to cure, and a large area for installing curing devices. This takes a long time for curing, there is a problem such as productivity is lowered.
이에 반해, 자외선 경화방식은 상기 열경화 방식의 단점을 극복할 수 있고 열경화 방식에 비해 저장안정성이 우수하며 상온에서 수초 내에 경화가 가능하기 때문에 생산성이 높을 뿐 아니라, 경화막의 변화가 적고 이 방식을 통해 제조된 필름의 경우 내마모성, 내수성, 내용제성, 내열성, 내후성등이 우수하다는 장점을 지닌다. 그러나, 상기 장점에도 불구하고 자외선 경화방식을 이용하면 하드 코팅층용 조성물과 폴리에스테르 필름과의 부착력을 바람직한 수준으로 유지할 수 없다는 단점을 피할 수 없다. 통상적으로 이러한 문제는 필름 표면에 프라이머 처리를 함으로써 해결하여 왔다. 그러나, 프라이머층 형성공정의 추가는 생산성의 저하 및 생산비용의 증대를 불가피하게 초래하게 된다.On the contrary, the ultraviolet curing method can overcome the disadvantages of the above-mentioned thermosetting method, and has excellent storage stability and can be cured in a few seconds at room temperature compared to the thermosetting method, so that the productivity is high and the change of the cured film is small. In the case of the film produced through the wear resistance, water resistance, solvent resistance, heat resistance, weather resistance and the like has an advantage. However, in spite of the above advantages, the UV curing method cannot avoid the disadvantage that the adhesion between the composition for the hard coating layer and the polyester film cannot be maintained at a desirable level. Typically this problem has been solved by subjecting the film surface to a primer. However, the addition of the primer layer forming process inevitably leads to a decrease in productivity and an increase in production cost.
또한, 상기 자외선 경화방식을 적용하여 제조된 필름의 경우 표면경도가 그다지 높지 못하여 표면보호용 필름으로 사용되기에는 불충분하기 때문에 이에 대한 해결이 요망되고 있는 실정이다.In addition, the film produced by applying the UV curing method is not so high surface hardness is insufficient to be used as a surface protection film is a situation that needs to be solved.
본 발명이 이루고자하는 기술적 과제는 프라이머층 없이도 폴리에스테르 기재 필름에의 접착성이 우수함은 물론, 폴리에스테르 필름의 표면경도 향상을 위하여 필름 표면에 형성되는 하드 코팅층용으로 적합한 자외선 경화형 조성물 및 이를 이용한 내스크래치성 필름을 제공하는 것이다.The technical problem to be achieved by the present invention is not only excellent adhesion to the polyester base film without a primer layer, but also suitable for the hard-curing layer formed on the surface of the film to improve the surface hardness of the polyester film and a UV-resistant composition using the same It is to provide a scratchable film.
상기 기술적 과제를 달성하기 위하여, 본 발명에서는 올리고머, 자외선 반응성 희석제, 부착력 증진제, 광중합 개시제 및 첨가제를 포함하는 자외선 경화형 조성물에 있어서, 상기 올리고머는 함량이 전체 조성물 기준으로 40 내지 70중량%이고, 관능기가 6개인 지방족 우레탄 아크릴레이트이고, 상기 자외선 반응성 희석제는 함량이 전체 조성물 기준으로 1 내지 30중량%이고, 단/다관능성 아크릴레이트계 모노머의 2종 이상 혼합물이고, 상기 부착력 증진제는 함량이 전체 조성물 기준으로 1 내지 30중량%이고, 하이드록시 에틸 아크릴레이트 및 메타크릴레이트화 산성 화합물(Methacrylated Acidic Compound)로 이루어진 군으로부터 선택된 적어도 어느 하나이고, 상기 광중합 개시제는 함량이 전체 조성물 기준으로 0.1 내지 10중량%이고, 1-하이드록시-사이클로헥실-페닐 케톤(1-Hydroxy-cyclohexyl-phenyl Ketone) 및 α,α-디메톡시-α-하이드록시아세토페논(α,α-Dimethoxy-α-hydroxyacetophenone)으로 이루어진 군으로부터 선택된 적어도 어느 하나이며 상기 첨가제는 실리콘 디아크릴레이트인 것을 특징으로 하는 자외선 경화형 조성물이 제공된다.In order to achieve the above technical problem, in the present invention, in the UV curable composition comprising an oligomer, UV reactive diluent, adhesion promoter, photopolymerization initiator and additives, the oligomer is 40 to 70% by weight based on the total composition, the functional group Is an aliphatic urethane acrylate having 6, the ultraviolet reactive diluent is 1 to 30% by weight based on the total composition, a mixture of two or more kinds of mono / polyfunctional acrylate monomers, and the adhesion promoter is the total composition It is 1 to 30% by weight, at least one selected from the group consisting of hydroxy ethyl acrylate and Methacrylated Acidic Compound, the photopolymerization initiator is 0.1 to 10% by weight of the total composition %, 1-hydroxy-cyclohexyl- At least one selected from the group consisting of 1-Hydroxy-cyclohexyl-phenyl Ketone and α, α-dimethoxy-α-hydroxyacetophenone (α, α-Dimethoxy-α-hydroxyacetophenone) and the additive is silicone There is provided an ultraviolet curable composition, which is a diacrylate.
상기 다른 기술적 과제를 달성하기 위하여, 본 발명에서는 상기 조성물을 이용한 내스크래치성 필름이 제공된다. 본 발명의 내스크래치성 필름에 있어서, 자외선 경화형 조성물로 형성되는 하드 코팅층은 1 내지 10㎛의 두께를 갖는 것이 바람직하다.In order to achieve the above another technical problem, the present invention provides a scratch resistant film using the composition. In the scratch resistant film of the present invention, the hard coat layer formed of the ultraviolet curable composition preferably has a thickness of 1 to 10 µm.
이하, 본 발명을 보다 상세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
일반적으로 올리고머는 분자량이 500 내지 5000인 화합물로서 점도 및 물성에 따라 각각의 모노머로 희석되어 사용되기도 하는데, 최종 제품의 주요 특성을 좌우하는 성분이기도 하다. 본 발명에 의한 자외선 경화형 조성물에 포함되는 올리고머는 그 말단이 아크릴레이트 또는 메타크릴레이트로 이루어지며, 주쇄의 구조에 따라 우레탄 아크릴레이트, 에폭시 아크릴레이트, 폴리에스테르 아크릴레이트, 아크릴릭 아크릴레이트, 실리콘 아크릴레이트 또는 아미노 아크릴레이트 등으로 나누어진다. 구체적으로 상기 각각의 올리고머의 특성을 살펴보면 다음과 같다.In general, the oligomer is a compound having a molecular weight of 500 to 5000 may be diluted with each monomer according to the viscosity and physical properties, it is also a component that determines the main characteristics of the final product. The oligomers contained in the ultraviolet curable composition according to the present invention are composed of acrylates or methacrylates at the ends thereof, and urethane acrylate, epoxy acrylate, polyester acrylate, acrylic acrylate, and silicone acrylate depending on the structure of the main chain. Or amino acrylates and the like. Specifically, the characteristics of each oligomer are as follows.
우레탄 아크릴레이트는 우레탄 결합을 반복단위로 포함하며 통상적으로 유연한 물성을 지닌다. 종류가 아주 다양하며, 이소시아네이트의 종류에 따라 지방족 우레탄 아크릴레이트와 방향족 우레탄 아크릴레이트로 나누어진다. 지방족 우레탄 아크릴레이트는 무황변 타입이며 2 내지 6개의 관능기를 갖는다. 방향족 우레탄 아크릴레이트는 황변 타입이며, 반응성이 빠른 특성을 지닌다. 에폭시 아크릴레이트는 주쇄에 에폭시 결합을 함유하며 황변을 일으키는 단점은 있으나, 경도, 내용제성 및 경화성이 우수하다. 폴리에스테르 아크릴레이트는 점도가 낮고 내후성이 우수하다. 아크릴릭 아크릴레이트는 내후성 및 내수성이 좋으며 특히 모든 소재에 대한 접착성이 우수하다. 아미노 아크릴레이트는 경화촉진제로 사용되어 표면경화를 향상시키며 황변을 일으키는 단점이 있다. 실리콘 아크릴레이트는 습윤제, 슬립제 또는 이형제로 사용된다.Urethane acrylates include urethane bonds as repeating units and typically have flexible physical properties. There are many different types, and depending on the type of isocyanate, it is divided into aliphatic urethane acrylate and aromatic urethane acrylate. Aliphatic urethane acrylates are of the yellowing type and have 2 to 6 functional groups. Aromatic urethane acrylates are yellowing type and have fast reactivity. Epoxy acrylate contains an epoxy bond in the main chain and causes yellowing, but has excellent hardness, solvent resistance and curability. Polyester acrylate is low in viscosity and excellent in weather resistance. Acrylic acrylate has good weather resistance and water resistance, in particular good adhesion to all materials. Amino acrylate is used as a curing accelerator to improve the surface hardening and has the disadvantage of causing yellowing. Silicone acrylates are used as wetting agents, slip agents or release agents.
본 발명의 바람직한 일실시예에 의하면, 상기 언급된 여러 가지 올리고머중 황변이 없고 유연성에 악영향을 미치지 않는 범위내에서 가교밀도를 향상시켜 표면경도를 극대화하기 위하여 6관능성의 지방족 우레탄 아크릴레이트가 선택된다. 그 함량은 전체 조성물 기준으로 40 내지 70중량%가 바람직하다. 함량이 40중량% 미만이면 표면경도가 충분하지 못하고 70중량%를 초과하게 되면 점도문제 및 코팅 부착력 감소현상이 발생하므로 바람직하지 못하다.According to a preferred embodiment of the present invention, a six-functional aliphatic urethane acrylate is selected in order to maximize the surface hardness by improving the crosslinking density within the range of no yellowing of the above-mentioned oligomers and does not adversely affect the flexibility . The content is preferably 40 to 70% by weight based on the total composition. If the content is less than 40% by weight it is not preferable because the surface hardness is not sufficient and exceeds 70% by weight because viscosity problems and coating adhesion decreases occur.
본 발명에 있어서, 상기 자외선 반응성 희석제는 분자량이 500 이하인 모노머로서, 주로 자외선 경화형 조성물의 점도를 낮추는 목적으로 사용되는 것이다. 이러한 모노머는 관능기의 수에 따라 다음과 같은 특성의 차이를 보인다.In the present invention, the ultraviolet reactive diluent is a monomer having a molecular weight of 500 or less, and is mainly used for the purpose of lowering the viscosity of the ultraviolet curable composition. These monomers exhibit the following characteristics depending on the number of functional groups.
우선, 1관능성(단관능성) 모노머는 기재에 대한 부착성 및 유연성이 우수한 반면, 반응성이 낮고 과량 사용시 끈적임성을 나타내는 단점이 있다. 또한, 2관능성 모노머는 점도, 반응성 및 유연성이 적당하여 일반적으로 가장 많이 사용되고 있으며, 3관능성 모노머는 경도 및 반응성이 높은 장점을 지니고 있다. 그리고, 4 내지 6관능성 모노머는 반응성이 뛰어나고 가교밀도가 높아 경도가 우수한 반면, 유연성이 떨어지는 단점을 지니고 있다.First, while monofunctional (monofunctional) monomers have excellent adhesion and flexibility to the substrate, they have disadvantages of low reactivity and stickiness when used in excess. In addition, bifunctional monomers are most commonly used because of their proper viscosity, reactivity and flexibility, and trifunctional monomers have advantages of high hardness and reactivity. In addition, the 4 to 6 functional monomers have excellent reactivity and high crosslinking density, and thus have excellent hardness, but have disadvantages of low flexibility.
본 발명에 의하면, 유연성을 해치지 않는 범위내에서 가교밀도 및 경화속도를 향상시키기 위하여 상기 여러 가지 모노머중에서 2종 이상의 아크릴레이트계 모노머를 혼합하여 사용하는 것이 바람직하다. 예를 들어, 3관능성의 펜타에리트리톨 트리아크릴레이트와 4관능성의 펜타에리트리톨 테트라아크릴레이트를 혼용하거나, 상기 혼합물에 3관능성의 트리메틸올 프로판 트리아크릴레이트를 첨가, 사용한다. 이러한 단/다관능성 아크릴레이트계 모노머 혼합물을 사용함으로 인해 하드 코팅에 있어서 가교밀도 및 경화속도를 바람직하게 유지할 수 있다.According to the present invention, it is preferable to mix and use two or more acrylate monomers among the various monomers in order to improve the crosslinking density and the curing rate within a range that does not impair flexibility. For example, trifunctional pentaerythritol triacrylate and tetrafunctional pentaerythritol tetraacrylate are mixed, or trifunctional trimethylol propane triacrylate is added to the mixture and used. By using such a mono / polyfunctional acrylate monomer mixture, the crosslinking density and curing rate can be preferably maintained in hard coating.
이 때, 상기 단/다관능성 아크릴레이트계 모노머 혼합물의 함량은 전체 조성물 기준으로 1 내지 30중량%인 것이 바람직하다. 함량이 1중량% 미만이면 희석효과가 거의 없어 고점도의 문제가 야기되며, 함량이 30중량%를 초과하면 유연성이 저하되고 경화층의 수축이 발생하며 기재에 대한 부착력이 감소한다.At this time, the content of the mono / polyfunctional acrylate monomer mixture is preferably 1 to 30% by weight based on the total composition. If the content is less than 1% by weight, there is almost no dilution effect, resulting in a problem of high viscosity. When the content is more than 30% by weight, flexibility decreases, shrinkage of the cured layer occurs, and adhesion to the substrate decreases.
또한, 본 발명에 의하면, 기재 필름에 대한 하드 코팅층용 조성물의 부착력을 증진시키기 위한, 일명 부착력 증진제를 사용한다. 부착력 증진제의 투입으로 인해서 본 발명에 의한 조성물은 프라이머층 형성없이도 기재 필름에 대한 우수한 부착력을 나타내게 된다. 부착력 증진제로서는 단관능성 모노머중 경화성이 특히 뛰어난 하이드록시 에틸 아크릴레이트 또는 270 내지 330mgKOH/g의 산가를 갖는 메타크릴레이트화 산성 화합물(Methacrylated Acidic Compound)중에서 선택된 어느 하나 또는 양자 모두가 바람직하다.In addition, according to the present invention, a so-called adhesion enhancer is used to enhance the adhesion of the composition for a hard coat layer to the base film. Due to the addition of the adhesion promoter, the composition according to the present invention exhibits excellent adhesion to the base film without forming a primer layer. As the adhesion promoter, one or both of hydroxy ethyl acrylate having excellent curability in the monofunctional monomer or Methacrylated Acidic Compound having an acid value of 270 to 330 mgKOH / g is preferable.
상기 두 물질의 함량은 모두 1 내지 30중량%가 바람직한데, 하이드록시 에틸 아크릴레이트의 경우 함량이 30중량%를 초과하게 되면 휘발도가 상대적으로 높아 자외선 경화형 조성물의 독성이 심해지게 되고, 메타크릴레이트화 산성 화합물이 30중량%보다 과량 투입되면 표면의 끈적임을 유발할 우려가 있다.The content of both materials is preferably 1 to 30% by weight. In the case of hydroxyethyl acrylate, when the content exceeds 30% by weight, the volatilization is relatively high, and the toxicity of the UV-curable composition is increased. If the acidified acidic compound is added in excess of 30% by weight, the surface may be sticky.
광중합 개시제는 자외선을 흡수하여 자유 라디칼을 생성함으로써 반응을 개시시키는 작용을 한다. 개시제의 종류에 따라 흡수하는 파장영역을 달리 하며, 대부분이 반응에는 참가하지 않는다. 황변 타입과 저황변 타입이 있다. 일반적으로 300 내지 360nm의 파장을 흡수하는데, 다양한 파장을 흡수하여 반응성을 촉진시키기 위해서는 2종 이상의 개시제를 함께 사용한다. 또한, 도포 두께가 얇은 경우 함량이 높을수록 반응성이 좋아지며, 도포두께가 두꺼운 경우에는 함량이 감소할수록 전체 경화속도가 증가하게 된다.The photopolymerization initiator acts to initiate the reaction by absorbing ultraviolet light to generate free radicals. The wavelength range of absorption varies depending on the type of initiator, and most of them do not participate in the reaction. There are yellow type and low yellow type. Generally, a wavelength of 300 to 360 nm is absorbed, and two or more kinds of initiators are used together to absorb various wavelengths and promote reactivity. In addition, when the coating thickness is thin, the higher the content, the better the reactivity, and when the coating thickness is thick, the total curing rate increases as the content decreases.
본 발명에 있어서는, 통상적으로 사용되는 저황변 타입의 개시제중에서 반응성 향상을 위해 α-하이드록시알킬페논계 물질을 선택한다. 구체적으로는 1-하이드록시-사이클로헥실-페닐 케톤(1-Hydroxy-cyclohexyl-phenyl Ketone) 또는 α,α-디메톡시-α-하이드록시아세토페논(α,α-Dimethoxy-α-hydroxyacetophenone)중 어느 하나 또는 두 물질의 혼합물이 바람직하다. 광중합 개시제의 함량은 전체 조성물 기준으로 0.1 내지 10중량%가 바람직한데, 함량이 0.1중량% 미만인 경우에는 반응성이 느리다는 결점이 있고, 반면 10중량%를 초과하면 반응성은 증가하지만 표면경도가 저하된다는 문제가 있다.In the present invention, an α-hydroxyalkylphenone-based material is selected for improving reactivity among the commonly used low-yellowing type initiators. Specifically, 1-Hydroxy-cyclohexyl-phenyl Ketone or α, α-dimethoxy-α-hydroxyacetophenone (α, α-Dimethoxy-α-hydroxyacetophenone) Preference is given to mixtures of one or two substances. The content of the photopolymerization initiator is preferably 0.1 to 10% by weight based on the total composition, but when the content is less than 0.1% by weight, the reactivity is slow. On the other hand, when the content is more than 10% by weight, the reactivity is increased but the surface hardness is decreased. there is a problem.
한편, 자외선 경화형 조성물은 경우에 따라 첨가제 성분을 포함할 수 있다. 예를 들어 도료의 평활성을 증대시키기 위한 레벨링제(leveling agent), 도료의 표면장력을 감소시켜 기재 필름에 대한 습윤성을 향상시키는 습윤제(wettting agent), 자외선 안정제 또는 기타 물질이 포함될 수 있다.On the other hand, the ultraviolet curable composition may optionally include an additive component. For example, it may include a leveling agent to increase the smoothness of the paint, a wettting agent to reduce the surface tension of the paint to improve the wettability to the base film, UV stabilizers or other materials.
본 발명의 자외선 경화형 조성물에 있어서는 첨가제로서 실리콘 디아크릴레이트를 포함한다. 이 물질은 올리고머 주쇄와 직접 경화반응을 일으키는 특성으로 인해 필름표면으로의 이행(migration)이 일어나지 않고, 필름에 우수한 습윤성 및 레벨링성을 부여하는 역할을 수행한다. 실리콘 디아크릴레이트의 함량은 0.1 내지 5중량%가 바람직하며, 과량 사용할 때에는 표면이 흐려지는 부작용이 발생한다.In the ultraviolet curable composition of this invention, silicone diacrylate is contained as an additive. This material does not migrate to the film surface due to the property of causing a direct curing reaction with the oligomer backbone, and serves to give the film excellent wettability and leveling property. The content of the silicone diacrylate is preferably 0.1 to 5% by weight, and the side effect of clouding of the surface occurs when used in excess.
이하, 본 발명에 의한 자외선 경화형 조성물을 이용한 내스크래치성 필름의 제조방법에 관하여 설명하기로 한다.Hereinafter, the manufacturing method of the scratch resistant film using the ultraviolet curable composition by this invention is demonstrated.
제조된 조성물을 기재 필름에 도포하는 방법은 당해 기술분야에서 통상적으로 알려져 있는 방법이라면 특별히 제한되지 않고 채택될 수 있다. 예를 들어, 에어 나이프(air knife) 방식, 그라비아 방식(gravure), 리버스 롤(reverse roll) 방식, 키스 롤(kiss roll) 방식, 스프레이(spray) 방식 또는 블레이드(blade) 방식 중에서 기재 필름의 형상 및 재질에 따라 임의로 선택하여 사용할 수 있다. 도포 두께는 1 내지 10㎛ 정도가 적당하다. 도포 두께가 1㎛ 미만이면 충분한 경화 도막을 얻기 어렵고, 10㎛를 넘으면 도막의 유연성이 떨어져 부서지기 쉽다는 단점으로 인해 사용이 곤란하다.The method for applying the prepared composition to the base film is not particularly limited as long as it is a method commonly known in the art and may be adopted. For example, the shape of the base film in an air knife method, gravure method, reverse roll method, kiss roll method, spray method or blade method And can be used arbitrarily selected according to the material. As for application thickness, about 1-10 micrometers is suitable. If the coating thickness is less than 1 µm, it is difficult to obtain a sufficient cured coating film. If the coating thickness is more than 10 µm, the coating film is difficult to be used due to the disadvantage that the coating film has a low flexibility.
이상과 같은 방법을 이용하여 자외선 경화형 조성물을 기재 필름에 도포한 다음, 열풍, 적외선, 원적외선 등을 조사하여 가열, 건조후 자외선을 조사하거나, 이러한 건조 공정 없이 바로 자외선을 조사함으로써 경화 도막을 형성시킨다. 자외선 조사에 사용되는 자외선 램프의 종류 역시 통상적으로 사용되는 것이라면 특별히 제한되지 않는다. 예를 들어, 고압수은등, 초고압수은등, 무전극 램프, 메타할라이드 램프 등이 사용가능하다. 통상적으로 출력이 60 내지 240W/cm인 램프를 벨트 컨베이어 식으로 이동시키면서 자외선을 조사함으로써 경화도막을 형성시킨다. 본 발명에 의한 자외선 경화형 조성물은 산소의 영향을 거의 받지 않으므로 질소와 같은 불활성 환경이 필요없이 공기중에서 경화가 가능하다. 자외선 램프와 기재 필름간의 거리는 30 내지 300mm 정도로 유지한다.After applying the ultraviolet curable composition to the base film using the method described above, the cured coating film is formed by irradiating ultraviolet rays after heating and drying by irradiating hot air, infrared rays, far infrared rays, or the like, or irradiating ultraviolet rays immediately without such a drying process. . The type of ultraviolet lamp used for ultraviolet irradiation is also not particularly limited as long as it is commonly used. For example, a high pressure mercury lamp, an ultra high pressure mercury lamp, an electrodeless lamp, a metahalide lamp and the like can be used. Usually, the cured coating film is formed by irradiating an ultraviolet-ray, moving the lamp of 60-240W / cm in a belt conveyor type. The ultraviolet curable composition according to the present invention is hardly affected by oxygen, and thus can be cured in air without the need for an inert environment such as nitrogen. The distance between the ultraviolet lamp and the base film is maintained at about 30 to 300 mm.
이하, 실시예 및 비교예를 통하여 본 발명을 보다 상세히 설명하기로 한다. 단, 하기 실시예는 본 발명의 효과를 나타내기 위하여 제시된 일례에 불과한 것으로서, 본 발명의 범위가 하기 실시예에 의해 제한되지 않음은 물론이다. 하기 실시예 및 비교예에 있어서, 제조된 내스크래치성 필름의 물성 평가는 다음과 같은 방법으로 실시하였다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are merely examples given to show the effects of the present invention, and the scope of the present invention is not limited by the following examples. In the following Examples and Comparative Examples, the physical properties of the prepared scratch-resistant film was evaluated by the following method.
(1) 부착력(1) adhesion
1mm 간격으로 도막을 크로스 해치한 후, 셀로판 테이프를 부착, 박리하였을 때 박리되지 않고 남아 있는 개수를 나타낸다.After cross hatching the coating film at 1 mm intervals, the number remaining without peeling when the cellophane tape is attached and peeled is shown.
(2) 연필 경도(2) pencil hardness
일본 공업 규격(JIS) JIS-K5400의 조건하에서, 쉰(Sheen)사의 연필경도계로 스테들러(Steadler)사의 연필을 사용하여 평가한다. 사용된 연필의 규격은 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H이다.Under the conditions of Japanese Industrial Standards (JIS) JIS-K5400, evaluation was made using a pencil made by Steadler with a pencil hardness meter of Sheen. The pencils used were 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H.
(3) 내스크래치성(3) scratch resistance
직경 10㎛인 강철 솜으로 도막을 문질러 스크래치 발생여부를 육안으로 관찰하여 평가한다.The coating film was rubbed with a steel batter having a diameter of 10 µm and the scratch was visually observed for evaluation.
(4) 내약품성(4) chemical resistance
실온에서 5% 수산화나트륨 수용액 및 5% 염산 수용액에 각각 4시간 동안 침적시킨 후, 도막의 물성변화 여부에 따라 불량, 양호로 평가한다.After immersion in a 5% aqueous sodium hydroxide solution and a 5% aqueous hydrochloric acid solution at room temperature for 4 hours, respectively, it is evaluated as poor or good depending on whether or not the physical properties of the coating film change.
(5) 내용제성(5) solvent resistance
실온에서 톨루엔, 아세톤, 메틸에틸케톤, 메탄올, 이소프로필알코올, 부틸아세테이트 등에 48시간 동안 침적시킨 후, 도막의 물성변화 여부에 따라 불량, 양호로 평가한다.After immersion for 48 hours in toluene, acetone, methyl ethyl ketone, methanol, isopropyl alcohol, butyl acetate and the like at room temperature, it is evaluated as poor or good according to the change of physical properties of the coating film.
(6) 황색도(6) yellowness
ASTM D1925의 조건하에서 헌터랩(HunterLab)사의 측색계(ColorQUEST Ⅱ)를 사용하여 평가한다.Evaluation is carried out using HunterLab's colorimeter (ColorQUEST II) under the conditions of ASTM D1925.
<실시예 1><Example 1>
아래와 같은 조성을 갖는 자외선 경화형 조성물을 0.05mm의 메이어 바를 이용하여 100㎛ 두께의 미처리 폴리에틸렌테레프탈레이트 필름상에 도포하고 50℃에서 20초간 건조한 후 자외선 조사장치(미국 Fusion사 제품, F450)와 자외선 램프(미국 Fusion사 제품, 무전극형의 H-bulb)를 이용하여 도포된 필름표면에 자외선을 조사하였다. 자외선 조사거리는 50mm로 하고, 적산광량이 200mJ/sq.cm가 되도록 벨트 스피드를 조절하였다. 이렇게 하여 형성된 자외선 경화형 수지층의 도막 두께는 3㎛이었다. 상기와 같이 하여 제조된 필름의 물성을 측정하여 표 1에 나타내었다.The UV curable composition having the composition described below was applied onto an untreated polyethylene terephthalate film having a thickness of 100 μm using a Mayer bar of 0.05 mm, dried at 50 ° C. for 20 seconds, and then irradiated with an ultraviolet irradiation device (F450, manufactured by Fusion, USA) and an ultraviolet lamp ( Ultraviolet rays were irradiated on the surface of the coated film by using an electrodeless type H-bulb) manufactured by Fusion, USA. The ultraviolet irradiation distance was 50 mm, and the belt speed was adjusted so that accumulated light amount might be 200 mJ / sq.cm. The coating film thickness of the ultraviolet curable resin layer formed in this way was 3 micrometers. The physical properties of the film produced as described above are measured and shown in Table 1.
6관능성 지방족 우레탄 아크릴레이트 올리고머 70 중량부70 parts by weight of a 6 functional aliphatic urethane acrylate oligomer
(Ebecryl 1290, UCB Chemicals사 제품)(Ebecryl 1290, manufactured by UCB Chemicals)
트리메틸올프로판 트리아크릴레이트 5.0 중량부5.0 parts by weight of trimethylolpropane triacrylate
(SR 350, Sartomer사 제품)(SR 350, product of Sartomer)
펜타에리트리톨 트리/테트라 아크릴레이트 혼합물 10.0 중량부10.0 parts by weight of pentaerythritol tri / tetra acrylate mixture
(PETA, UCB Chemicals사 제품)(PETA, manufactured by UCB Chemicals)
메타크릴레이트화 산성 화합물 3.0 중량부3.0 parts by weight of methacrylated acidic compound
(Ebecryl 169, UCB Chemicals사 제품)(Ebecryl 169, manufactured by UCB Chemicals)
하이드록시 에틸 아크릴레이트 5.0 중량부5.0 parts by weight of hydroxyethyl acrylate
(HEA, UCB Chemicals사 제품)(HEA, manufactured by UCB Chemicals)
α-하이드록시-케톤 6.0 중량부6.0 parts by weight of α-hydroxy ketone
(Irgacure 184, Ciba-geigy사 제품)(Irgacure 184, manufactured by Ciba-geigy)
레벨링제 1.0 중량부1.0 part by weight of leveling agent
(Silwet L7602, Union Carbide사 제품)(Silwet L7602, manufactured by Union Carbide)
이소프로필 알코올 50.0 중량부50.0 parts by weight of isopropyl alcohol
<실시예 2><Example 2>
아래와 같은 조성을 갖는 자외선 경화형 조성물을 200메쉬(Mesh)의 그라비아 롤을 이용하여 25㎛ 두께의 미처리 폴리에틸렌테레프탈레이트 필름상에 도포하고 50℃에서 20초간 건조한 후 자외선 조사장치(미국 Fusion사 제품, F450)와 출력 80W/cm의 고압수은등 4개로 구성되어 있는 자외선 램프를 이용하여 도포된 필름표면에 자외선을 조사하였다. 자외선 조사거리는 150mm로 하고, 적산광량이 200mJ/sq.cm가 되도록 벨트 스피드를 조절하였다. 이렇게 하여 형성된 자외선 경화형 수지층의 도막 두께는 2㎛이었다. 상기와 같이 하여 제조된 필름의 물성을 측정하여 표 1에 나타내었다.An ultraviolet curable composition having the composition described below was applied on an untreated polyethylene terephthalate film having a thickness of 25 μm using a 200-mesh gravure roll, dried at 50 ° C. for 20 seconds, and then irradiated with an ultraviolet ray (F450, manufactured by Fusion, USA). Ultraviolet rays were irradiated on the surface of the coated film using an ultraviolet lamp composed of four high-pressure mercury lamps with a power output of 80 W / cm. The ultraviolet irradiation distance was 150 mm, and the belt speed was adjusted so that accumulated light amount might be 200 mJ / sq.cm. The coating film thickness of the ultraviolet curable resin layer formed in this way was 2 micrometers. The physical properties of the film produced as described above are measured and shown in Table 1.
6관능성 지방족 우레탄 아크릴레이트 올리고머 70 중량부70 parts by weight of a 6 functional aliphatic urethane acrylate oligomer
(Ebecryl 1290, UCB Chemicals사 제품)(Ebecryl 1290, manufactured by UCB Chemicals)
트리메틸올프로판 트리아크릴레이트 5.0 중량부5.0 parts by weight of trimethylolpropane triacrylate
(TMPTA, UCB Chemicals사 제품)(TMPTA, manufactured by UCB Chemicals)
펜타에리트리톨 트리/테트라 아크릴레이트 혼합물 10.0 중량부10.0 parts by weight of pentaerythritol tri / tetra acrylate mixture
(PETA, UCB Chemicals사 제품)(PETA, manufactured by UCB Chemicals)
메타크릴레이트화 산성 화합물 3.0 중량부3.0 parts by weight of methacrylated acidic compound
(Ebecryl 169, UCB Chemicals사 제품)(Ebecryl 169, manufactured by UCB Chemicals)
하이드록시 에틸 아크릴레이트 5.0 중량부5.0 parts by weight of hydroxyethyl acrylate
(HEA, UCB Chemicals사 제품)(HEA, manufactured by UCB Chemicals)
α-하이드록시-알킬 페논 6.0 중량부6.0 parts by weight of α-hydroxyalkyl phenone
(Darocure 1173, Ciba-geigy사 제품)(Darocure 1173, manufactured by Ciba-geigy)
레벨링제 1.0 중량부1.0 part by weight of leveling agent
(Fluorad FC430, 3M사 제품)(Fluorad FC430, product of 3M company)
이소프로필 알코올 50.0 중량부50.0 parts by weight of isopropyl alcohol
<실시예 3><Example 3>
아래와 같은 조성을 갖는 자외선 경화형 조성물을 3본 리버스 롤을 이용하여 100㎛ 두께의 미처리 폴리에틸렌테레프탈레이트 필름상에 도포하고 50℃에서 20초간 건조한 후 자외선 조사장치(미국 Fusion사 제품, F450)와 출력 120W/cm의 고압수은등 4개로 구성되어 있는 자외선 램프를 이용하여 도포된 필름표면에 자외선을 조사하였다. 자외선 조사거리는 150mm로 하고, 적산광량이 200mJ/sq.cm가 되도록 벨트 스피드를 조절하였다. 이렇게 하여 형성된 자외선 경화형 수지층의 도막 두께는 3㎛이었다. 상기와 같이 하여 제조된 필름의 물성을 측정하여 표 1에 나타내었다.The UV curable composition having the composition shown below was applied onto an untreated polyethylene terephthalate film having a thickness of 100 μm using three reverse rolls and dried at 50 ° C. for 20 seconds, followed by an ultraviolet irradiation device (F450, manufactured by Fusion, USA), and output 120 W / Ultraviolet rays were irradiated onto the surface of the coated film using an ultraviolet lamp composed of 4 cm high-pressure mercury lamps. The ultraviolet irradiation distance was 150 mm, and the belt speed was adjusted so that accumulated light amount might be 200 mJ / sq.cm. The coating film thickness of the ultraviolet curable resin layer formed in this way was 3 micrometers. The physical properties of the film produced as described above are measured and shown in Table 1.
6관능성 지방족 우레탄 아크릴레이트 올리고머 70 중량부70 parts by weight of a 6 functional aliphatic urethane acrylate oligomer
(Ebecryl 1290, UCB Chemicals사 제품)(Ebecryl 1290, manufactured by UCB Chemicals)
트리메틸올프로판 트리아크릴레이트 5.0 중량부5.0 parts by weight of trimethylolpropane triacrylate
(TMPTA, UCB Chemicals사 제품)(TMPTA, manufactured by UCB Chemicals)
펜타에리트리톨 트리/테트라 아크릴레이트 혼합물 10.0 중량부10.0 parts by weight of pentaerythritol tri / tetra acrylate mixture
(PETA, UCB Chemicals사 제품)(PETA, manufactured by UCB Chemicals)
메타크릴레이트화 산성 화합물 3.0 중량부3.0 parts by weight of methacrylated acidic compound
(Ebecryl 169, UCB Chemicals사 제품)(Ebecryl 169, manufactured by UCB Chemicals)
하이드록시 에틸 아크릴레이트 5.0 중량부5.0 parts by weight of hydroxyethyl acrylate
(HEA, UCB Chemicals사 제품)(HEA, manufactured by UCB Chemicals)
α-하이드록시-케톤 3.0 중량부α-hydroxy-ketone 3.0 parts by weight
(Irgacure 184, Ciba-geigy사 제품)(Irgacure 184, manufactured by Ciba-geigy)
α-하이드록시-알킬 페논 3.0 중량부α-hydroxy-alkyl phenone 3.0 parts by weight
(Darocure 1173, Ciba-geigy사 제품)(Darocure 1173, manufactured by Ciba-geigy)
레벨링제 1.0 중량부1.0 part by weight of leveling agent
(HS-300, UCB Chemicals사 제품)(HS-300, manufactured by UCB Chemicals)
이소프로필 알코올 50.0 중량부50.0 parts by weight of isopropyl alcohol
<실시예 4><Example 4>
아래와 같은 조성을 갖는 자외선 경화형 조성물을 0.05mm의 메이어 바를 이용하여 100㎛ 두께의 미처리 폴리에틸렌테레프탈레이트 필름상에 도포하고 50℃에서 20초간 건조한 후 자외선 조사장치(미국 Fusion사 제품, F450)와 출력 120W/cm의 고압수은등 4개로 구성되어 있는 자외선 램프를 이용하여 도포된 필름표면에 자외선을 조사하였다. 자외선 조사거리는 150mm로 하고, 적산광량이 200mJ/sq.cm가 되도록 벨트 스피드를 조절하였다. 이렇게 하여 형성된 자외선 경화형 수지층의 도막 두께는 5㎛이었다. 상기와 같이 하여 제조된 필름의 물성을 측정하여 표 1에 나타내었다.The UV curable composition having the composition shown below was applied onto an untreated polyethylene terephthalate film having a thickness of 100 μm using a Mayer bar of 0.05 mm and dried at 50 ° C. for 20 seconds, followed by an ultraviolet irradiation device (F450, manufactured by Fusion, USA) and output 120 W / Ultraviolet rays were irradiated onto the surface of the coated film using an ultraviolet lamp composed of 4 cm high-pressure mercury lamps. The ultraviolet irradiation distance was 150 mm, and the belt speed was adjusted so that accumulated light amount might be 200 mJ / sq.cm. The coating film thickness of the ultraviolet curable resin layer formed in this way was 5 micrometers. The physical properties of the film produced as described above are measured and shown in Table 1.
6관능성 지방족 우레탄 아크릴레이트 올리고머 50 중량부50 parts by weight of a 6-functional aliphatic urethane acrylate oligomer
(Ebecryl 1290, UCB Chemicals사 제품)(Ebecryl 1290, manufactured by UCB Chemicals)
트리메틸올프로판 트리아크릴레이트 10.0 중량부10.0 parts by weight of trimethylolpropane triacrylate
(TMPTA, UCB Chemicals사 제품)(TMPTA, manufactured by UCB Chemicals)
펜타에리트리톨 트리/테트라 아크릴레이트 혼합물 10.0 중량부10.0 parts by weight of pentaerythritol tri / tetra acrylate mixture
(PETA, UCB Chemicals사 제품)(PETA, manufactured by UCB Chemicals)
메타크릴레이트화 산성 화합물 10.0 중량부10.0 parts by weight of methacrylated acidic compound
(Ebecryl 169, UCB Chemicals사 제품)(Ebecryl 169, manufactured by UCB Chemicals)
하이드록시 에틸 아크릴레이트 10.0 중량부10.0 parts by weight of hydroxyethyl acrylate
(HEA, UCB Chemicals사 제품)(HEA, manufactured by UCB Chemicals)
α-하이드록시-케톤 3.0 중량부α-hydroxy-ketone 3.0 parts by weight
(Irgacure 184, Ciba-geigy사 제품)(Irgacure 184, manufactured by Ciba-geigy)
α-하이드록시-알킬 페논 3.0 중량부α-hydroxy-alkyl phenone 3.0 parts by weight
(Darocure 1173, Ciba-geigy사 제품)(Darocure 1173, manufactured by Ciba-geigy)
레벨링제 1.0 중량부1.0 part by weight of leveling agent
(HS-300, UCB Chemicals사 제품)(HS-300, manufactured by UCB Chemicals)
이소프로필 알코올 50.0 중량부50.0 parts by weight of isopropyl alcohol
<비교예 1>Comparative Example 1
아래와 같은 조성을 갖는 자외선 경화형 조성물을 0.05mm의 메이어 바를 이용하여 100㎛ 두께의 미처리 폴리에틸렌테레프탈레이트 필름(Skyrol, SKC사 제품)상에 도포하고 160℃에서 1분간 경화시켜 3㎛ 두께의 도막을 형성하였다. 제조된 필름의 물성을 측정하여 표 1에 나타내었다.An ultraviolet curable composition having the composition described below was applied onto an untreated polyethylene terephthalate film (Skyrol, SKC, Inc.) having a thickness of 100 μm using a Mayer bar of 0.05 mm, and cured at 160 ° C. for 1 minute to form a 3 μm thick coating film. . The physical properties of the prepared film were measured and shown in Table 1.
용제 79.7중량%Solvent 79.7 wt%
열경화형 아크릴 수지 15 중량%Thermosetting Acrylic Resin 15% by weight
멜라민계 경화제 5 중량%5% by weight of melamine curing agent
산촉매 0.3 중량%0.3% by weight of acid catalyst
<비교예 2>Comparative Example 2
열경화형 아크릴 수지를 첨가하지 않는 대신, 열경화형 우레탄 수지 15중량%를 첨가하는 것을 제외하고는 비교예 1과 동일한 방법으로 제조한 필름에 대하여 물성을 측정하여 표 1에 나타내었다.The physical properties of the film prepared in the same manner as in Comparative Example 1 were measured and shown in Table 1 except that 15 wt% of the thermosetting urethane resin was added instead of the thermosetting acrylic resin.
<비교예 3>Comparative Example 3
아래와 같은 조성을 갖는 자외선 경화형 조성물을 0.05mm의 메이어 바를 이용하여 100㎛ 두께의 미처리 폴리에틸렌테레프탈레이트 필름(Skyrol, SKC사 제품)상에 도포하고 50℃에서 20초간 건조한 후 자외선 조사장치(미국 Fusion사 제품, F450)와 출력 120W/cm의 고압수은등 4개로 구성되어 있는 자외선 램프를 이용하여 도포된 필름표면에 자외선을 조사하였다. 자외선 조사거리는 50mm로 하고, 적산광량이 200mJ/sq.cm가 되도록 벨트 스피드를 조절하였다. 이렇게 하여 형성된 자외선 경화형 수지층의 도막 두께는 5㎛이었다. 상기와 같이 하여 제조된 필름의 물성을 측정하여 표 1에 나타내었다.The UV curable composition having the composition shown below was coated on a 100 μm thick untreated polyethylene terephthalate film (Skyrol, SKC Co., Ltd.) using a 0.05 mm Meyer Bar, dried at 50 ° C. for 20 seconds, and then irradiated with an ultraviolet ray irradiation device (manufactured by Fusion, USA). , F450) and an ultraviolet lamp composed of four high-pressure mercury lamps having an output power of 120 W / cm were irradiated with ultraviolet rays. The ultraviolet irradiation distance was 50 mm, and the belt speed was adjusted so that accumulated light amount might be 200 mJ / sq.cm. The coating film thickness of the ultraviolet curable resin layer formed in this way was 5 micrometers. The physical properties of the film produced as described above are measured and shown in Table 1.
2관능성 지방족 우레탄 아크릴레이트 올리고머 60 중량부60 parts by weight of bifunctional aliphatic urethane acrylate oligomer
(Ebecryl 254, UCB Chemicals사 제품)(Ebecryl 254, manufactured by UCB Chemicals)
트리메틸올프로판 트리아크릴레이트 20 중량부20 parts by weight of trimethylolpropane triacrylate
(SR 350, Sartomer사 제품)(SR 350, product of Sartomer)
n-비닐피롤리돈 15 중량부15 parts by weight of n-vinylpyrrolidone
(NVP, ISP사 제품)(NVP, ISP company product)
α-하이드록시-케톤 5.0 중량부α-hydroxy-ketone 5.0 parts by weight
(Irgacure 184, Ciba-geigy사 제품)(Irgacure 184, manufactured by Ciba-geigy)
이소프로필 알코올 30.0 중량부Isopropyl alcohol 30.0 parts by weight
<비교예 4><Comparative Example 4>
하드 코팅처리를 하지 않은 폴리에틸렌테레프탈레이트 필름(Skyrol, SKC사 제품)에 대하여 물성을 측정하여 그 결과를 표 1에 나타내었다.The physical properties of the polyethylene terephthalate film (Skyrol, SKC Co., Ltd.) not subjected to the hard coating was measured, and the results are shown in Table 1.
이상에서 알 수 있는 바와 같이, 본 발명에 의한 자외선 경화형 조성물을 통상적인 도포방법을 이용하여 폴리에스테르 필름에 도포한 후, 자외선을 조사하여 경화시킴으로써 제조되는 필름은 내용제성, 내약품성 등이 우수하고 황변 현상이 나타나지 않음은 물론, 프라이머층이 없음에도 불구하고 부착력이 우수할 뿐만 아니라, 표면경도가 2H 수준으로 높아서 내스크래치성이 요구되는 다양한 분야의 필름으로 사용적합하다.As can be seen from the above, the film produced by applying the ultraviolet curable composition according to the present invention to a polyester film using a conventional coating method and then irradiating with ultraviolet rays to cure is excellent in solvent resistance, chemical resistance and the like. Not only does not appear yellowing, it is not only excellent adhesion even in the absence of a primer layer, the surface hardness is high to 2H level is suitable for use in various fields of film that requires scratch resistance.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019980006141A KR100252029B1 (en) | 1998-02-26 | 1998-02-26 | Uv-curable composition and scratch resistant film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019980006141A KR100252029B1 (en) | 1998-02-26 | 1998-02-26 | Uv-curable composition and scratch resistant film |
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|---|---|
| KR19990070963A KR19990070963A (en) | 1999-09-15 |
| KR100252029B1 true KR100252029B1 (en) | 2000-04-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100731209B1 (en) | 2006-04-14 | 2007-06-22 | 주식회사 유니테크 | Coating composition for ultraviolet curing and accessory ornaments using the same |
| CN110997733A (en) * | 2017-04-11 | 2020-04-10 | 分子公司 | Preparation of solid materials or films from polymerizable liquids |
-
1998
- 1998-02-26 KR KR1019980006141A patent/KR100252029B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100731209B1 (en) | 2006-04-14 | 2007-06-22 | 주식회사 유니테크 | Coating composition for ultraviolet curing and accessory ornaments using the same |
| CN110997733A (en) * | 2017-04-11 | 2020-04-10 | 分子公司 | Preparation of solid materials or films from polymerizable liquids |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990070963A (en) | 1999-09-15 |
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