KR20160080656A - Hard coat composition, hard coat film and method the same - Google Patents
Hard coat composition, hard coat film and method the same Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims description 11
- 238000000034 method Methods 0.000 title description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 30
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 11
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 7
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical group O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000077 silane Inorganic materials 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000012788 optical film Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- -1 acryl Chemical group 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- PCVUMABZZZSILN-UHFFFAOYSA-N (5-methyl-4-oxo-1-trimethoxysilylhex-5-en-3-yl) 2-methylprop-2-enoate Chemical compound CO[Si](CCC(OC(=O)C(C)=C)C(=O)C(C)=C)(OC)OC PCVUMABZZZSILN-UHFFFAOYSA-N 0.000 description 1
- PCGYKFJWPSAGHE-UHFFFAOYSA-N 3-[diethoxy(methoxy)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OC)CCCOC(=O)C(C)=C PCGYKFJWPSAGHE-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
표면경도가 우수하고 저투습성을 갖는 하드코트용 코팅액이 소개된다. 그 코팅액은 실란과 실란 커플링제의 졸겔 반응에 의해 생성된 실록산 올리고머를 포함하며, 이 코팅액을 이용하여 얻어진 하드코트는 코팅액의 경화를 통해 얻어진 실록산 네트워크를 갖는다.A coating liquid for hard coating having excellent surface hardness and low moisture permeability is introduced. The coating solution includes a siloxane oligomer produced by a sol-gel reaction of silane and a silane coupling agent, and the hard coat obtained by using the coating solution has a siloxane network obtained through curing of the coating solution.
Description
본 발명은 하드코트, 특히 플라스틱의 보호를 위해 그 표면에 코팅되는 하드코트와 관련된 것이다.The present invention relates to a hard coat, especially a hard coat coated on its surface for the protection of plastics.
플라스틱은 유리와 달리 연질의 표면을 가지고 있어 긁히기 쉬우며 용제 등에 대한 내성이 좋지 않다. 특히 디스플레이용 필름은 투명도 등 광학특성이 매우 중요하기에, 통상 이러한 광학필름은 하드코팅된다.Unlike glass, plastic has a soft surface and is easy to scratch and is not resistant to solvents. In particular, optical films such as transparency are very important for display films, and generally these optical films are hard coated.
하드코팅은 유기 코팅제와 무기 코팅제로 나뉜다. 유기 코팅제로는 멜라민, 아크릴, 우레탄 등이 사용되며, 무기 코팅제로는 실리콘계가 주종을 이룬다. 졸겔 반응에 의해 실리콘계 무기물에 유기 실란커플링제를 반응시키는 하이브리드 코팅제도 최근 관심이 높다.Hard coatings are divided into organic coatings and inorganic coatings. As the organic coating agent, melamine, acryl, urethane and the like are used, and as the inorganic coating agent, silicone system is main. A hybrid coating agent for reacting an organosilane coupling agent with a silicon-based inorganic material by a sol-gel reaction is also of great interest in recent years.
한편 디스플레이 장치에 사용되는 편광판은 폴리비닐알콜(PVA), 트리아세틸 셀룰로오스(TAC)와 같은 광학용 필름의 적층체이다. 편광판 제조용 등으로 이들 광학필름을 해외로 수출하는 경우, 적도 부근을 지나면서 외부환경, 특히 습기에 노출되어 물성이 변하는 문제가 발생한다.On the other hand, the polarizing plate used in the display device is a laminate of optical films such as polyvinyl alcohol (PVA) and triacetyl cellulose (TAC). When these optical films are exported to overseas for the production of a polarizing plate, there is a problem that physical properties are changed due to exposure to external environment, especially moisture, as they pass near the equator.
본 발명은 위와 같은 종래의 문제점에 대한 인식에 기초한 것으로, 표면 경도 및 광학특성이 우수하며 투습성이 낮은 플라스틱용 하드코트 제조기술을 제공하고자 한다.The present invention is based on the recognition of the above-described conventional problems, and aims to provide a technique for manufacturing a hard coat for plastic having excellent surface hardness and optical characteristics and low moisture permeability.
위 목적을 달성하기 위하여 본 발명자들은 유리와 같은 강한 표면경도를 가지며 공기와 수분에 대해 낮은 투습력을 갖는 하드코트를 개발하고자 하였고 그 결과를 기초로 본 발명을 출원하게 되었다.In order to achieve the above object, the present inventors have developed a hard coat having a strong surface hardness such as glass and a low moisture permeability against air and moisture, and the present invention has been filed based on the result.
본 발명은 하드코트에 실란 네트워크(Siloxane Network)를 형성함으로써 기존 하드코트의 물성은 그대로 유지하면서 하드코트가 추가적으로 저투습력을 갖도록 한 것에 특징이 있다.The present invention is characterized in that the hard coat further has a low moisture permeability while maintaining the physical properties of the existing hard coat by forming a siloxane network on the hard coat.
종래기술로서 일본공개특허 제1996-169968호에서와 같이 불소계 실란 커플링제를 이용한 코팅막 제조기술이 공지되어 있었다. 그러나 이러한 불소계 실란 커플링제를 이용한 코팅막은 경도가 좋지 못하다.As a conventional technique, a coating film production technique using a fluorine-based silane coupling agent as disclosed in Japanese Patent Laid-Open No. 1996-169968 has been known. However, the coating film using such a fluorine-based silane coupling agent has poor hardness.
본 발명에서는 하드코트의 제조를 위해 아래에서 상세하게 서술되는 바와 같은 실록산 올리고머가 이용된다. 일반 실록산 올리고머를 사용할 경우에 비해 본 발명에 따른 하드코트는 광특성, 표면경도는 물론 투습 특성이 우수하다.In the present invention, siloxane oligomers as described in detail below are used for the production of hard coats. The hard coat according to the present invention is excellent in optical characteristics, surface hardness and moisture permeability as compared with the case of using a general siloxane oligomer.
일 측면에 따르면 본 발명에 따라 하드코트 조성물로 사용되는 실록산 올리고머는 중량평균분자량이 1,000~5,000g/mol인 것이 바람직하다. 또한 기재와의 충분한 탈수축합 반응을 위해 말단에 수산기(OH)를 80% 이상 포함하는 것이 바람직하다.According to one aspect, the siloxane oligomer used in the hard coat composition according to the present invention preferably has a weight average molecular weight of 1,000 to 5,000 g / mol. In addition, it is preferable that at least 80% of hydroxyl groups (OH) are contained at the terminals for a sufficient dehydration condensation reaction with the substrate.
일 측면에 따르면 본 발명에 따른 실록산 올리고머는 알콕시 실란과 에폭시계 실란 커플링제의 졸겔 반응에 의해 제조될 수 있다.According to one aspect, the siloxane oligomer according to the present invention can be prepared by a sol-gel reaction of an alkoxysilane and an epoxy silane coupling agent.
한편 본 발명에 따른 하드코트 필름은 상기된 실록산 올리고머를 포함하는 하드코트 조성물을 기재에 코팅 후 건조한 다음, 자외선 경화 및 열경화시킴에 의해 제조될 수 있다. 경화된 하드코트는 저투습력을 갖는 실록산 네트워크를 갖는다.Meanwhile, the hard coat film according to the present invention can be prepared by coating a substrate with a hard coat composition containing the siloxane oligomer described above, followed by drying, followed by ultraviolet curing and thermal curing. The cured hard coat has a siloxane network with low moisture permeability.
상술한 바와 같은 본 발명에 따라 제조된 하드코팅은 표면경도 및 광학특성이 우수할 뿐만 아니라 투습성이 낮아, 광학용 필름이나 각종의 플라스틱의 표면 보호 코팅으로 활용될 수 있다.The hard coating prepared according to the present invention as described above is excellent in surface hardness and optical characteristics and low in moisture permeability and can be utilized as a surface protective coating for optical films and various plastics.
이하에서는 실시예를 참조하여 본 발명에 대하여 상세하게 살펴본다.Hereinafter, the present invention will be described in detail with reference to examples.
하드코트 조성물Hard coat composition
실시예에 따른 하드코트 조성물은 하기 화학식 1로 표시되는 반복 단위를 갖는 실록산 올리고머룰 포함한다.The hard coat composition according to an embodiment includes a siloxane oligomer having a repeating unit represented by the following formula (1).
위 화학식 1에서 n은 정수이며, R1, R2에는 UV에 의한 중합반응을 위한 불포화기 성분으로 에폭시 또는 불포화 결합을 갖는 작용기가 위치하며, R3, R4에는 기재 표면에서의 수소 결합 또는 탈수축합 반응을 위한 에톡시기, 메톡시기 또는 수산기가 위치한다.In the formula 1, n is an integer, and R1 and R2 each represent a functional group having an epoxy or unsaturated bond as an unsaturated group component for the polymerization reaction by UV, and R3 and R4 are hydrogen bonding or dehydration condensation reaction Methoxy group, or hydroxyl group is located.
구체적으로 R1, R2는 각각 독립적으로 하기 화학식 2 내지 화학식 4으로 표시되는 화합물들 중의 어느 하나일 수 있으며, R3, R4는 각각 독립적으로 메톡시기(OCH3), 에톡시기(OC2H5) 또는 수산기(OH)일 수 있다.Specifically, R 1 and R 2 can each independently be any one of the compounds represented by the following Chemical Formulas 2 to 4, and each of R 3 and R 4 independently represents a methoxy group (OCH 3 ), an ethoxy group (OC 2 H 5 ) And may be a hydroxyl group (OH).
위와 같은 실록산 올리고머는 분자량과 작용기의 함량이 중요하다. 실록산 올리고머의 중량평균분자량은 1,000~5,000g/mol인 것이 바람직하며, R3 및 R4에 위치하는 총 관능기 중 수산기의 비율은 80% 이상인 것이 바람직하다.The molecular weight and the content of the functional groups are important for the above siloxane oligomer. The weight average molecular weight of the siloxane oligomer is preferably 1,000 to 5,000 g / mol, and the ratio of the hydroxyl group among the total functional groups located at R3 and R4 is preferably 80% or more.
실록산 올리고머의 1,000g/mol 이하일 경우 코팅 층 내 SiO2 함량 부족으로 저투습력 특성을 얻기 어렵고, 5,000g/mol이상일 경우 과도한 SiO2 결합으로 인해 코팅층 내 크랙을 유발할 수 있다. 유연특성을 갖는 광학필름 상에 저투습력 기능을 부여하기 위해서는 분자량이 1,000~5,000g/mol로 한정되는 것이 바람직하다.When the siloxane oligomer content is less than 1,000 g / mol, low moisture permeability is difficult to obtain due to insufficient SiO 2 content in the coating layer. If the siloxane oligomer content is more than 5,000 g / mol, excessive SiO 2 bonding may cause cracks in the coating layer. In order to impart a low moisture permeability function to an optical film having flexibility properties, it is preferable that the molecular weight is limited to 1,000 to 5,000 g / mol.
또한 기재와의 안정한 부착특성을 갖기 위해서는 수산기의 비율이 80% 이상이 되어야 한다.In addition, in order to have a stable adhesion property with a substrate, the ratio of hydroxyl groups should be 80% or more.
하드코트 코팅액(조성물) 제조방법Hard Coat Coating Solution (Composition) Manufacturing Method
실시예에 따르면 하드코트 코팅액은 알콕시 실란과 실란 커플링제의 졸겔 반응에 의해 실록산 올리고머를 제조한 후 여기에 용매를 혼합하여 제조된다.According to the embodiment, the hard coat coating solution is prepared by preparing a siloxane oligomer by a sol-gel reaction of an alkoxysilane and a silane coupling agent, and then mixing the solvent with the siloxane oligomer.
실란으로는 테트라메톡시실란, 메틸트리메톡시실란, 메틸트리메톡시실란 등이 사용 가능하며, 실란 커플링제는 2-(3,4 에폭시사이클로헥실)-에틸트리메톡시실란, 3-메타크릴록시프로필트리에톡시실란, 3-메타아크리록시프로필트리메톡시실란, 3-메타크릴록시프로필메톡시디메톡시실란, 3-메타크릴록시프로필메톡시디에톡시실란 등이 사용 가능하다.As the silane, tetramethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane and the like can be used. As the silane coupling agent, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 3-methacryl 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethoxydimethoxysilane, 3-methacryloxypropylmethoxydiethoxysilane, and the like can be used.
졸겔 반응 시 위의 실란, 실란커플링제와 더불어 물, 알코올계 용매 및 촉매가 사용된다. 실란 및 실란커플링제의 메톡시/에톡시기 부분과 물이 반응하며 결합이 형성되며, 알코올계 용매는 실란 계통과 물의 상호간의 상용성을 높여주기 위해 사용된다. 산 촉매는 졸겔 반응의 속도를 조절하기 위해 사용된다.In the sol-gel reaction, water, an alcohol-based solvent and a catalyst are used in addition to the above silane and silane coupling agent. The methoxy / ethoxy moiety of the silane and silane coupling agent reacts with water to form a bond, and the alcoholic solvent is used to enhance mutual compatibility between the silane system and water. The acid catalyst is used to control the rate of the sol-gel reaction.
졸겔 반응 시 실란/실란커플링제, 물, 알코올계 용매는 중량비로 각각 50~60 : 10~15 : 20~30으로 사용되는 것이 바람직하며, 실란과 실란커플링제는 30~50 : 50~70의 비율로 혼합하는 것이 바람직하다.In the sol-gel reaction, the silane / silane coupling agent, the water and the alcohol solvent are preferably used in a weight ratio of 50 to 60:10 to 15:20 to 30, and the silane and silane coupling agent are used in a ratio of 30 to 50:50 to 70 By weight.
코팅액은 졸겔 반응을 통해 제조된 실록산 올리고머와 용매, 광개시제를 혼합하여 제조되며, 적용되는 코팅방식에 따라 고형분 조절을 위해 혼합비가 조절이 될 수 있다.The coating solution is prepared by mixing a siloxane oligomer prepared through a sol-gel reaction with a solvent and a photoinitiator, and the mixing ratio can be adjusted for controlling the solid content according to the coating method applied.
하드코트 필름 제조방법Hard Coat Film Manufacturing Method
실시예에 따르면 하드코트 필름은 위에서 설명된 코팅액을 기재에 코팅한 다음 건조 및 용제 제거 후, 자외선 경화 및 열경화시킴에 의해 제조될 수 있다.According to the embodiment, the hard coat film can be prepared by coating the above described coating liquid onto a substrate, followed by drying and solvent removal, followed by ultraviolet curing and thermosetting.
코팅액의 기재 코팅은 스핀(spin) 코팅, 딥(dip) 코팅, 바(bar) 코팅 등 다양한 공지기술이 이용될 수 있다. 용액상태이기에 나노미터에서 마이크로 단위의 두께까지 박막으로 형성할 수 있다. 물론 캐스팅도 가능할 것이다.Various known techniques such as spin coating, dip coating, bar coating and the like can be used as the substrate coating of the coating liquid. Since it is in a solution state, it can be formed into a thin film from nanometer to micro-unit thickness. Of course casting is also possible.
코팅액이 도포된 기재는 건조된다. 80~100℃의 온도 하에서 건조가 이루어지며, 열에 의해 도포된 코팅액 내의 용매가 증발되어 제거된다. The substrate to which the coating liquid is applied is dried. Drying is carried out at a temperature of 80 to 100 DEG C, and the solvent in the coating liquid applied by heat is evaporated and removed.
코팅액 건조 후 자외선을 조사하여 경화한 다음, 열경화시킨다. 자외선으로부터 받은 활성화 에너지가 실록산 올리고머내의 R1, R2의 불포화기에 작용하여 실록산 네트워크를 더욱 강하게 형성하는 반응이 이루어진다. 코팅층 내의 광개시제도 개시제 반응을 통해 실록산 네트워크의 형성을 돕는 역할을 한다.After drying the coating liquid, it is cured by irradiating ultraviolet rays, and then thermally cured. Activation energy from ultraviolet light acts on the unsaturated groups of R1 and R2 in the siloxane oligomer to form a stronger siloxane network. Photoinitiators in the coating layer also serve to assist in the formation of siloxane networks through initiator reactions.
열경화는 80~100℃ 온도 하에서 20~30시간 동안 이루어지며, 이 과정에서 잔류 수분이 제거 되면서 실록산 네트워크가 견고하게 형성된다. 이러한 과정들을 거치면서 코팅 층 내 SiO2 함량이 상승하게 된다. Thermal curing is carried out at a temperature of 80 to 100 ° C for 20 to 30 hours, in which the residual moisture is removed and the siloxane network is firmly formed. Through these processes, the SiO 2 content in the coating layer is increased.
기재는 특별하게 제한하지 않으나 광학용 필름의 보호에 사용될 경우라면 트리아세틸 셀룰로오스(TAC)인 것이 바람직하다. 이외에 폴리카보네이트, 아크릴계 폴리머, 폴리에틸렌테레프탈레이트 등도 가능할 것이다.The substrate is not particularly limited, but it is preferably triacetyl cellulose (TAC) if it is used for protecting an optical film. In addition, polycarbonate, acrylic polymer, polyethylene terephthalate and the like may be used.
하드코트 필름Hard coat film
위 실시예에 따른 하드코트 필름 제조방법에 의해 제조된 하드코트는 하기 화학식 5와 같은 형태의 실록산 네트워크가 분산된 구조를 갖는다.The hard coat prepared by the hard coat film manufacturing method according to the present embodiment has a structure in which a siloxane network of the following formula (5) is dispersed.
본 발명에 따른 하드코트의 물성에 대한 비교 평가를 위해 아래와 같은 실험예를 준비하였다.For comparative evaluation of physical properties of the hard coat according to the present invention, the following experimental examples were prepared.
(실시예)(Example)
물, 에탄올, 산촉매 존재하에 테트라에톡시실란(TEOS) 26.3중량%, 2-(3,4 에폭시사이클로헥실)-에틸트리메톡시실란 커플링제 36.0중량%를 졸겔 반응시켜 얻어진 실록산 올리고머를 제조하였다.A siloxane oligomer was obtained by subjecting 26.3% by weight of tetraethoxysilane (TEOS) and 36.0% by weight of 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane coupling agent to sol-gel reaction in the presence of water, ethanol and an acid catalyst.
제조된 실록산 올리고머를 용매에 43.2중량 : 56.1중량% 혼합하고 여기에 개시제 0.8중량%를 혼합하여 코팅액을 제조한 후, 트리아세틸 셀룰로오스 기재 상에 두께 8㎛로 바(Meyer bar) 코팅하였다. The prepared siloxane oligomer was mixed with 43.2 wt%: 56.1 wt% of the solvent and 0.8 wt% of initiator was mixed therewith to prepare a coating solution. Then, the coating solution was coated with a Meyer bar to a thickness of 8 탆 on a triacetylcellulose substrate.
코팅 후에는 80℃에서 1분 건조시킨 다음, 광량 200~300mJ/㎠의 UV 경화 후 100℃에서 24시간 열경화하여 하드코트필름을 제조하였다.After the coating, the coated film was dried at 80 ° C for 1 minute, then UV-cured at a light quantity of 200 to 300 mJ / cm 2, and thermally cured at 100 ° C for 24 hours to produce a hard coat film.
(비교예 1)(Comparative Example 1)
발수, 발유성을 부여하는 목적으로 주로 불소를 포함한 코팅제가 많이 사용이 되고 있다. 이 중에 UV 경화 타입의 불소계 코팅제(KD3500UV, 칸토덴카)를 사용하여 실시예와 동일한 방법으로 하드코트 필름을 제조하였다.Fluorine-containing coating agents are mainly used for the purpose of imparting water repellency and oil repellency. A hard coat film was prepared in the same manner as in Example using a UV curing type fluorine-based coating agent (KD3500UV, Canton Denka).
(비교예 2)(Comparative Example 2)
유기물 하드코팅(EKOCOT HZ3007, 엔씨켐)을 이용하여 실시예와 동일한 방법으로 하드코트 필름을 제조하였다.A hard coat film was prepared in the same manner as in Example by using an organic hard coat (EKOCOT HZ3007, NC Chem).
제조된 실시예 및 비교예 1,2에 대하여 연필경도 및 기타 물성을 평가하였다. 그 결과는 아래 표 1, 2에 기재되어 있다.Pencil hardness and other physical properties were evaluated for the prepared examples and Comparative Examples 1 and 2. The results are shown in Tables 1 and 2 below.
실시예는 비교예 1과 비교하여 동일 이상의 투습도 특성을 가지면서도 2H 이상의 우수한 경도 특성을 얻을 수 있었고(표 1 참조), 비교예 2에 비하여 투습도가 23% 이상 향상되며 비교예 2와 유사하거나 우수한 광학적 특성 및 경도 특성을 얻을 수 있었다(표 2 참조).The Example exhibited the same moisture permeability characteristics as those of Comparative Example 1, and superior hardness characteristics of 2H or higher were obtained (see Table 1), and the moisture permeability was improved by 23% or more as compared with Comparative Example 2, Optical properties and hardness characteristics were obtained (see Table 2).
이상 본 발명의 특정 실시예를 들어 설명하였지만, 하기의 특허청구범위에 기재된 발명의 기술적 사상으로부터 벗어나지 않는 범위 내에서 본 발명은 다양하게 수정 또는 변형될 수 있고 또 이것이 본 발명의 기술분야에서 통상의 지식을 가진 자에게 자명하다는 것이 이해될 필요가 있다.While this invention has been described in connection with what is presently considered to be practical exemplary embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art. It is necessary to understand that it is self-evident to those with knowledge.
Claims (6)
[화학식 1]
화학식 1식에서 R1, R2는 각각 독립적으로 하기 화학식 2 내지 화학식 4로 표시되는 화합물들 중의 어느 하나이며, R3, R4는 각각 독립적으로 메톡시기, 에톡시기 또는 수산기임.
[화학식 2]
[화학식 3]
[화학식 4]
[Chemical Formula 1]
Wherein R1 and R2 are each independently any one of the compounds represented by the following Chemical Formulas 2 to 4 and R3 and R4 are each independently a methoxy group, an ethoxy group or a hydroxyl group.
(2)
(3)
[Chemical Formula 4]
상기 코팅액을 건조한 다음, 자외선 경화 및 열경화시키는 과정;을 포함하는 것을 특징으로 하는 하드코트 필름 제조방법.Coating the substrate with the hard coat composition according to claim 3; And
Drying the coating liquid, and then curing and thermally curing the coating liquid.
상기 기재 상에 형성되며, 청구항 3에 따른 하드코팅 조성물을 경화시켜 얻은 실록산 네트워크를 갖는 하드코팅층;을 포함하는 하드코트 필름.materials; And
A hard coat layer formed on the substrate and having a siloxane network obtained by curing the hard coat composition according to claim 3.
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| JPH08169968A (en) | 1994-12-20 | 1996-07-02 | Toyota Autom Loom Works Ltd | Method of forming water-repellent abrasion-resistant thin film |
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| JPH08169968A (en) | 1994-12-20 | 1996-07-02 | Toyota Autom Loom Works Ltd | Method of forming water-repellent abrasion-resistant thin film |
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| KR20240062504A (en) * | 2022-11-02 | 2024-05-09 | 한국생산기술연구원 | Resin composition for manufacturing flexible hard coating film and flexible hard coating film manufactured using the same |
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