KR20120002366A - A composition for making hard coating layer and hard coating film made by using the same - Google Patents
A composition for making hard coating layer and hard coating film made by using the same Download PDFInfo
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- KR20120002366A KR20120002366A KR1020100063202A KR20100063202A KR20120002366A KR 20120002366 A KR20120002366 A KR 20120002366A KR 1020100063202 A KR1020100063202 A KR 1020100063202A KR 20100063202 A KR20100063202 A KR 20100063202A KR 20120002366 A KR20120002366 A KR 20120002366A
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- urethane acrylate
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- acrylate oligomer
- chain extender
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
Description
본 발명은 디스플레이 보호용 하드코팅 필름의 하드코팅층 형성용 조성물 및 이를 이용하여 제조된 디스플레이 보호용 하드코팅 필름에 관한 것이다.
The present invention relates to a composition for forming a hard coat layer of a hard coat film for display protection and a hard coat film for display protection manufactured using the same.
텔레비전, 컴퓨터, 플라즈마디스플레이(PDP), 액정디스플레이(LCD) 등과 같은 각종 디스플레이에 사용되던 유리 기판은 내충격성이 취약하여 파손되기 쉬웠다. 이러한 단점을 보완하고 디스플레이를 보호하기 위해서 플라스틱 필름이 도입되어 사용되고 있다.Glass substrates used in various displays such as televisions, computers, plasma displays (PDPs), liquid crystal displays (LCDs), and the like are easily damaged due to their poor impact resistance. Plastic films have been introduced and used to supplement these shortcomings and to protect displays.
디스플레이 보호용 플라스틱 필름으로서는 활성에너지 자외선 경화성 수지를 코팅한 하드코팅층을 가지는 동시에 반사방지처리 또는 대전방지처리 등의 표면처리를 한 플라스틱 필름이 사용되고 있다. As the plastic film for display protection, a plastic film having a hard coating layer coated with an active energy ultraviolet curable resin and subjected to a surface treatment such as an antireflection treatment or an antistatic treatment is used.
그러나, 상기 디스플레이 보호용 플라스틱 필름은 표면처리에 수반되는 가열처리에 의한 컬, 가공시 굴곡에 의한 하드코팅층의 갈라짐, 벗겨짐 등과 같은 현상이 나타나는 문제점이 있었다.
However, the display protective plastic film has a problem such as cracking, peeling, etc. of the hard coating layer due to curling by heat treatment and bending during processing accompanying surface treatment.
본 발명은 각종 디스플레이 보호를 위한 하드코팅 필름의 하드코팅층 형성용 조성물로서, 하드코팅층의 경도, 밀착성, 내굴곡성 및 내마모성을 향상시키는 하드코팅층 형성용 조성물을 제공하고자 한다.The present invention as a composition for forming a hard coating layer of the hard coating film for various display protection, to provide a composition for forming a hard coating layer to improve the hardness, adhesion, bending resistance and wear resistance of the hard coating layer.
또한 본 발명은 경도, 밀착성, 내굴곡성 및 내마모성이 향상된 하드코팅층 형성용 조성물을 포함하는 하드코팅 필름을 제공하고자 한다.In another aspect, the present invention is to provide a hard coating film comprising a composition for forming a hard coating layer with improved hardness, adhesion, bending resistance and wear resistance.
이에 본 발명은 바람직한 제1 구현예로서, 우레탄 아크릴레이트 올리고머, 우레탄 아크릴레이트 올리고머 이외의 광경화성 물질 및 광중합개시제를 포함하는 하드코팅층 형성용 조성물로서, 상기 우레탄 아크릴레이트 올리고머는 사슬연장제를 포함하는 것을 특징으로 하는 하드코팅층 형성용 조성물을 제공한다.Accordingly, the present invention provides a hard coating layer-forming composition comprising a urethane acrylate oligomer, a photocurable material other than the urethane acrylate oligomer, and a photopolymerization initiator, wherein the urethane acrylate oligomer comprises a chain extender. It provides a composition for forming a hard coat layer, characterized in that.
상기 구현예에 의한 사슬연장제는 글리세린, 트리메틸롤에탄(trimethylol ethane), 트리메틸롤프로판(trimethylol propane) 및 1,2,6-헥산 트리올(1,2,6-hexane triol)로 구성된 군에서 선택되는 것일 수 있다.Chain extender according to the embodiment in the group consisting of glycerin, trimethylol ethane (trimethylol ethane), trimethylol propane and 1,2,6-hexane triol (1,2,6-hexane triol) It may be selected.
상기 구현예에 의한 상기 우레탄 아크릴레이트 올리고머는 분자량이 6,000~10,000인 것일 수 있다.The urethane acrylate oligomer according to the embodiment may have a molecular weight of 6,000 ~ 10,000.
상기 구현예에 의한 사슬연장제의 함량은 2~6중량%인 것일 수 있다.The content of the chain extender according to the embodiment may be 2 to 6% by weight.
본 발명은 바람직한 제2 구현예로서, 우레탄 아크릴레이트 올리고머, 우레탄 아크릴레이트 올리고머 이외의 광경화성 물질 및 광중합개시제로 제조된 하드코팅층 형성용 조성물을 포함하는 하드코팅 필름으로서, 상기 우레탄 아크릴레이트 올리고머는 사슬연장제를 포함하는 것을 특징으로 하는 하드코팅 필름을 제공한다.
As a second preferred embodiment of the present invention, there is provided a hard coating film comprising a composition for forming a hard coating layer made of a photocurable material and a photopolymerization initiator other than a urethane acrylate oligomer, a urethane acrylate oligomer, wherein the urethane acrylate oligomer is a chain It provides a hard coating film comprising an extender.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 바람직한 일구현예로서, 우레탄 아크릴레이트 올리고머, 우레탄 아크릴레이트 올리고머 이외의 광경화성 물질 및 광중합개시제를 포함하는 하드코팅층 형성용 조성물을 제공하며, 상기 우레탄 아크릴레이트 올리고머는 사슬연장제를 포함하는 것을 특징으로 한다.
As a preferred embodiment, the present invention provides a composition for forming a hard coating layer comprising a urethane acrylate oligomer, a photocurable material other than the urethane acrylate oligomer, and a photopolymerization initiator, wherein the urethane acrylate oligomer comprises a chain extender. It is characterized by.
일반적으로, 우레탄 아크릴레이트 올리고머는 접착제 조성물로 사용되는 UV 경화형 수지로서, 벤젠고리를 포함하고 있지 않는 구조이며 황변 현상이 나타나지 않아 디스플레이 코팅 용도로 많이 사용된다.In general, the urethane acrylate oligomer is a UV curable resin used as an adhesive composition, does not contain a benzene ring and does not appear yellowing phenomenon is used for display coatings.
본 발명에 따른 하드코팅층 형성용 조성물에 있어서, 각 성분의 함량은 하드코팅층 형성을 고려하여 우레탄 아크릴레이트 올리고머 100 중량부에 대하여, 우레탄 아크릴레이트 올리고머 이외의 광경화성 물질 20~60 중량부 및 광중합개시제 3~10 중량부인 것이 바람직하다. 이때, 광경화성 물질의 함량이 20중량부 미만이면 하드코팅층에 적합한 경도를 얻을 수 없고, 60중량부를 초과하면 경도는 높아지지만 원료물질의 혼합성이 떨어지는 문제가 있다. 또한, 광중합개시제가 3중량부 미만이면 광경화가 이루어지지 않아 블로킹 현상이 발생하는 문제가 있고, 10중량부를 초과하면 경화에는 문제가 없으나 잔존 개시제에 의해 장시간 방치시 표면에 개시제가 석출되는 문제가 있다.In the composition for forming a hard coating layer according to the present invention, the content of each component is 20 to 60 parts by weight of a photocurable material other than the urethane acrylate oligomer and photopolymerization initiator with respect to 100 parts by weight of the urethane acrylate oligomer in consideration of forming the hard coating layer. It is preferable that it is 3-10 weight part. In this case, when the content of the photocurable material is less than 20 parts by weight, a hardness suitable for the hard coating layer may not be obtained. When the content of the photocurable material is greater than 60 parts by weight, the hardness is high, but there is a problem in that the raw materials are incompatible. In addition, when the photopolymerization initiator is less than 3 parts by weight, there is a problem in that a blocking phenomenon occurs because photocuring is not performed. When the photopolymerization initiator is more than 10 parts by weight, there is no problem in curing. .
한편, 우레탄 아크릴레이트 올리고머 이외의 광경화성 물질은 디펜타에리스리톨펜타아크릴레이트, 트리히드록시에틸이소시아누레이트 트리아크릴레이트, 이소시아누레이트디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 디펜타에리트리톨트리(메타)아크릴레이트, 프로피온산 변성 디펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 프로필렌옥시드 변성 트리메틸올프로판트리(메타)아크릴레이트, 트리스(아크릴록시에틸)이소시아누레이트, 프로피온산 변성 디펜타에리트리톨펜타(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트 및 카프로락톤 변성 디펜타에리트리톨헥사(메타)아크릴레이트로 구성된 군에서 선택되는 다관능성 아크릴레이트로서 1종을 이용하거나 또는 2종 이상을 조합해서 이용하는 것도 가능하다. On the other hand, photocurable substances other than a urethane acrylate oligomer are dipentaerythritol pentaacrylate, trihydroxyethyl isocyanurate triacrylate, isocyanurate di (meth) acrylate, and trimethylolpropane tri (meth) acryl. Latent, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, Consist of tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and caprolactone modified dipentaerythritol hexa (meth) acrylate 1 type or 2 or more types of polyfunctional acrylate selected from the group It may be used in combination.
또한, 광중합개시제는 라디칼 중합형의 광중합성 프레폴리머 또는 광중합성 모노머에 대한 광중합개시제와 양이온 중합형의 광중합성 프레폴리머에 대한 광중합개시제로 나눌 수 있다. 상기 라디칼 중합형의 광중합성 프레폴리머 또는 광중합성 모노머에 대한 광중합개시제는 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르, 벤조인-n―부틸에테르, 벤조인이소부틸에테르, 아세토페논, 디메틸아미노아세토페논, 2,2―디메톡시-2―페닐아세토페논, 2,2-디에톡시-2―페닐아세토페논, 2-히드록시-2-메틸-1-페닐프로판-1-온, 1-히드록시시클로헥실페닐케톤, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노-프로판-1-온, 4-(2-히드록시에톡시)페닐-2(히드록시-2-프로필)케톤, 벤조페논, p-페닐벤조페논, 4,4'-디에틸아미노벤조페논, 디클로로벤조페논, 2―메틸안트라퀴논, 2-에틸안트라퀴논, 2-터샤리-부틸안트라퀴논, 2-아미노안트라퀴논, 2-메틸티오크산톤, 2-에틸티오크산톤, 2-클로로티오크산톤, 2,4-디메틸티오크산톤, 2,4-디에틸티오크산톤, 벤질디메틸케탈, 아세토페논디메틸케탈 및 p-디메틸아민안식향산에스테르로 구성된 군에서 선택되는 1종 또는 2종 이상의 혼합물이고, 상기 양이온 중합형의 광중합성 프레폴리머에 대한 광중합개시제는 방향족 옥소설포늄이온, 방향족요도늄이온 등의 오늄과, 테트라플루오로볼레트, 헥사플루오로포스페이트, 헥사플루오로안티모네이트, 헥사플루오로아르세네이트 등의 음이온 중 1종 또는 2종 이상을 조합한 화합물일 수 있다.
In addition, the photopolymerization initiator may be classified into a photopolymerization initiator for a radically polymerized photopolymerizable prepolymer or a photopolymerizable monomer and a photopolymerization initiator for a cationic polymerizable photopolymerizable prepolymer. The photopolymerization initiator for the radically polymerized photopolymerizable prepolymer or photopolymerizable monomer is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether. , Acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 4- (2-hydroxyethoxy) Phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 Tertary-butyl anthraquinone, 2-aminoanthraquinone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl Tioke It is 1 type, or 2 or more types of mixtures chosen from the group which consists of a Santon, benzyl dimethyl ketal, acetophenone dimethyl ketal, and p-dimethylamine benzoic acid ester, The photoinitiator for the said cationic polymerization type photopolymerizable prepolymer is aromatic oxosulfonium A compound in which one or two or more of onium such as ions and aromatic iodonium ions, and anions such as tetrafluorobolet, hexafluorophosphate, hexafluoroantimonate and hexafluoroarsenate are combined Can be.
본 발명에 따른 하드코팅층 형성용 조성물에 함유된 우레탄 아크릴레이트 올리고머는 사슬연장제를 함유하여 하드코팅층의 경도를 향상시키는 것을 특징으로 한다. 즉, 사슬연장제에 의하여 하드코팅층 형성용 조성물의 가교도 및 분자량이 증가하여 하드코팅층의 경도를 향상시킬 수 있다. The urethane acrylate oligomer contained in the composition for forming a hard coat layer according to the present invention is characterized by containing a chain extender to improve the hardness of the hard coat layer. That is, the crosslinking degree and molecular weight of the composition for forming the hard coat layer may be increased by the chain extender to improve the hardness of the hard coat layer.
여기서, 사슬연장제의 함량은 우레탄 아크릴레이트 올리고머 100중량%에서 2~6중량%인 것이 바람직하며, 사슬연장제의 함량이 2중량% 미만이면 경도향상을 위한 가교도 증가가 낮아 경도향상 효과가 미미하며, 6중량% 초과이면 겔링 현상이 발생하여 하드코팅 필름 제조시 제어하기 어려운 문제점이 있다.Herein, the content of the chain extender is preferably 2 to 6% by weight based on 100% by weight of the urethane acrylate oligomer. When the content of the chain extender is less than 2% by weight, the increase in the degree of crosslinking for the improvement of hardness is low, thereby improving the hardness. It is insignificant, and if it is more than 6% by weight, a gelling phenomenon occurs, which makes it difficult to control the manufacturing of the hard coat film.
상기 사슬연장제는 글리세린, 트리메틸롤에탄(trimethylol ethane), 트리메틸롤프로판(trimethylol propane) 및 1,2,6-헥산 트리올(1,2,6-hexane triol)로 구성된 군에서 선택되는 알코올로서, 특히, 3가 알코올, 4가 알코올일 수 있으며, 이 중에서 3가 알코올이 더욱 바람직한 것이다. 1종 단독으로 사용해도 되고, 2종 이상을 혼합하여 사용하는 것도 가능하다.The chain extender is an alcohol selected from the group consisting of glycerin, trimethylol ethane, trimethylol propane and 1,2,6-hexane triol. In particular, trihydric alcohol and tetrahydric alcohol may be used, and trihydric alcohol is more preferable. You may use individually by 1 type, and can also mix and use 2 or more types.
전술한 바와 같은 사슬연장제를 포함한 우레탄 아크릴레이트 올리고머는 하드코팅 필름의 경도를 고려하여 그 분자량이 6,000~10,000인 것이 바람직하며, 6,000미만일 경우 하드코팅층이 부드러워져 하드코팅 기능이 저하되고 내찰상성, 막강도 등이 우수하지 못하는 문제점이 있고, 10,000를 초과할 경우 내찰상성 등은 우수하나 경화 수축이 커지기 때문에 하드 코팅층의 컬 현상을 억제할 수 없는 문제점과 점도가 상당히 높아 가공성 저하 등의 문제점이 있다.
The urethane acrylate oligomer including the chain extender as described above preferably has a molecular weight of 6,000 to 10,000 in consideration of the hardness of the hard coating film, and if it is less than 6,000, the hard coating layer is softened so that the hard coating function is deteriorated and scratch resistance, There is a problem that the film strength is not excellent, and if it exceeds 10,000, the scratch resistance is excellent, but since the shrinkage of the hardening increases, the curling phenomenon of the hard coating layer cannot be suppressed, and the viscosity is considerably high, resulting in deterioration of workability. .
본 발명에 따른 사슬연장제를 포함하는 우레탄 아크릴레이트 올리고머는 다가 알코올, 사슬연장제, 반응 촉매 및 지방족 이소시아네이트류 등을 이용하여 말단이 이소시아네이트로 되어 있는 우레탄 프레폴리머를 제조한 후, 아크릴레이트 화합물을 첨가하여 말단의 이소시아네이트가 완전히 소모될 때까지 반응시킨 후, 제조할 수 있다.The urethane acrylate oligomer comprising a chain extender according to the present invention is prepared by using a polyhydric alcohol, a chain extender, a reaction catalyst, and aliphatic isocyanates, and then preparing a urethane prepolymer having an isocyanate terminal. It can be prepared after addition and reaction until the terminal isocyanate is completely consumed.
하드코팅층 형성용 조성물을 제조하는 방법은 상기와 같이 제조된 사슬연장제를 포함하는 우레탄 아크릴레이트 올리고머, 우레탄 아크릴레이트 올리고머 이외의 광경화성 물질 및 광중합 개시제를 용매와 혼합하여 제조할 수 있다.The method for preparing a composition for forming a hard coat layer may be prepared by mixing a urethane acrylate oligomer, a photocurable material other than a urethane acrylate oligomer, and a photopolymerization initiator including a chain extender prepared as described above with a solvent.
여기서, 상기 용매는 메탄올, 에탄올, 프로판올, 이소프로판올 등의 알코올, 메틸에틸케톤, 메틸이소부틸케톤 등의 케톤류, 메틸아세테이트, 에틸아세테이트 등의 에스테르류, 톨루엔, 벤젠, 크실렌 등의 방향족 화합물, 에테르류 등의 용매 중 1종 또는 2종 이상의 혼합물일 수 있다. Here, the solvent is alcohol such as methanol, ethanol, propanol, isopropanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate, aromatic compounds such as toluene, benzene, xylene, ethers It may be one kind or a mixture of two or more kinds of solvents.
하드코팅 필름은 상기와 같이 제조된 하드코팅층 형성용 조성물을 기재층의 일면에 도포하고, 자외선 조사 후 제조할 수 있다.
The hard coat film may be prepared by applying the hard coat layer-forming composition prepared as described above to one surface of the base layer and irradiating ultraviolet rays.
이상 설명한 바와 같은 우레탄 아크릴레이트 올리고머, 광경화성 물질 및 광중합개시제를 포함하되, 상기 우레탄 아크릴레이트가 사슬연장제를 포함하는 하드코팅층 형성용 조성물을 하드코팅 필름에 적용함으로써, 경도, 밀착성, 내굴곡성 및 내마모성이 우수하며, 표면처리에 의한 컬을 저감할 수 있는 하드코팅 필름을 제공할 수 있다.Urethane acrylate oligomers, photocurable materials and photopolymerization initiators as described above, wherein the urethane acrylate is a hard coating film forming composition comprising a chain extender, by applying a hard coating film, hardness, adhesion, flex resistance and It is excellent in wear resistance and can provide a hard coat film which can reduce curl by surface treatment.
특히, 하드코팅 필름의 경도는 연필경도에 의해 평가하며, 바람직하게는 3H이상인 것이 좋다. 그 이유는 외부의 접촉이나 충격에 내스크래치성을 주기 위해서는 3H 이상의 연필경도를 필요로 하기 때문이다. 이러한 이유로 본 발명의 하드코팅 필름의 경도는 3H 이상의 기계적 강도를 갖는 것이 바람직하다.
In particular, the hardness of the hard coat film is evaluated by the pencil hardness, preferably 3H or more. The reason is that pencil hardness of 3H or more is required in order to provide scratch resistance to external contact or impact. For this reason, the hardness of the hard coat film of the present invention preferably has a mechanical strength of 3H or more.
이하, 본 발명을 실시예를 통하여 보다 상세히 설명하나, 본 발명의 범위가 하기 실시예로 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.
우레탄 urethane 아크릴레이트Acrylate 올리고머Oligomer
<합성예 1>Synthesis Example 1
오일배스, 온도계, 환류냉각기, 적가펀넬이 설치된 1000㎕ 4구 플라스크에 펜타에리스리톨(Aldrich)사 0.436 mol, 사슬연장제인 트리메틸롤프로판 0.08mol, 반응 촉매인 디부틸틴디라우레이트 0.03g을 투입하여 70℃에서 30분 교반하여 혼합시킨 후, 헥사메틸렌디이소시아네이트 2.014 mol을 1시간 간격으로 3단계로 나누어 첨가하여 3시간 동안 반응을 진행하여, 말단이 이소시아네이트로 되어 있는 우레탄 프레폴리머를 제조하였다. 이때, 상기 말단이 이소시아네이트로 되어 있는 우레탄 프레폴리머의 R(N=C=O/OH, 이소시아네이트기와 히드록시기와의 비율)값은 1.91이다.Into a 1000 µl four-necked flask equipped with an oil bath, thermometer, reflux cooler, and dropping funnel, 0.436 mol of pentaerythritol (Aldrich), 0.08 mol of chain extender and 0.03 g of dibutyltin dilaurate, a reaction catalyst, were added. After stirring at 30 ° C. for 30 minutes, 2.014 mol of hexamethylene diisocyanate was added in three steps at 1 hour intervals to carry out the reaction for 3 hours, thereby preparing a urethane prepolymer having an isocyanate terminal. At this time, the value of R (N = C = O / OH, ratio of isocyanate group and hydroxyl group) of the urethane prepolymer whose terminal is isocyanate is 1.91.
그후, 비닐그룹의 열중합을 막기 위해 반응기의 온도를 50℃로 떨어뜨린 후, 히드록시 에틸 아크릴레이드 1.744몰을 첨가하여 이소시아네이트기가 완전히 소모될 때까지 5시간 동안 교반하였다. FT-IR 스펙트럼을 이용하여 2270㎝-1 부근의 N=C=O의 특성피크로 잔여 이소시아네이트가 없는 것을 확인하고, 반응을 종결하여, 약 560g의 우레탄 아크릴레이트 올리고머를 제조하였다.
Thereafter, the temperature of the reactor was lowered to 50 ° C. to prevent thermal polymerization of the vinyl group, and then 1.744 moles of hydroxy ethyl acrylate was added and stirred for 5 hours until the isocyanate group was completely consumed. Using the FT-IR spectrum, it was confirmed that there was no residual isocyanate by the characteristic peak of N = C = O near 2270 cm -1 , and the reaction was terminated to prepare about 560 g of urethane acrylate oligomer.
<합성예 2>Synthesis Example 2
상기 합성예 1에서 사슬연장제인 트리메틸롤프로판 0.18mol을 사용한 것을 제외하고는 동일한 방법으로 우레탄 아크릴레이트 올리고머를 제조하였다.
A urethane acrylate oligomer was prepared in the same manner, except that 0.18 mol of trimethylolpropane, a chain extender, was used in Synthesis Example 1.
<합성예 3>≪ Synthesis Example 3 &
상기 합성예 1에서 사슬연장제인 트리메틸롤프로판 0.25mol을 사용한 것을 제외하고는 동일한 방법으로 우레탄 아크릴레이트 올리고머를 제조하였다.
A urethane acrylate oligomer was prepared in the same manner, except that 0.25 mol of trimethylolpropane, which is a chain extender, was used in Synthesis Example 1.
<합성예 4>≪ Synthesis Example 4 &
상기 합성예 1에서 사슬연장제인 트리메틸롤프로판 0.04mol을 사용한 것을 제외하고는 동일한 방법으로 우레탄 아크릴레이트 올리고머를 제조하였다.
A urethane acrylate oligomer was prepared in the same manner except that 0.04 mol of trimethylolpropane, a chain extender, was used in Synthesis Example 1.
<합성예 5>≪ Synthesis Example 5 &
상기 합성예 1에서 사슬연장제인 트리메틸롤프로판 0.33mol을 사용한 것을 제외하고는 동일한 방법으로 우레탄 아크릴레이트 올리고머를 제조하였다.
A urethane acrylate oligomer was prepared in the same manner except that 0.33 mol of trimethylolpropane, which is a chain extender, was used in Synthesis Example 1.
<합성예 6>≪ Synthesis Example 6 &
상기 합성예 1에서 사슬연장제를 사용하지 않은 것을 제외하고는 동일한 방법으로 우레탄 아크릴레이트 올리고머를 제조하였다.
A urethane acrylate oligomer was prepared in the same manner except that a chain extender was not used in Synthesis Example 1.
<합성예 7>Synthesis Example 7
상기 합성예 1에서 펜타에리스리톨 대신 디펜타에리스리톨을 사용하고, 사슬연장제를 사용하지 않은 것을 제외하고는 동일한 방법으로 우레탄 아크릴레이트 올리고머를 제조하였다.
A urethane acrylate oligomer was prepared in the same manner, except that dipentaerythritol was used instead of pentaerythritol in Synthesis Example 1, and a chain extender was not used.
<합성예 8>Synthesis Example 8
상기 합성예 1에서 펜타에리스리톨 대신 트리펜타에리스리톨을 사용하고, 사슬연장제를 사용하지 않은 것을 제외하고는 동일한 방법으로 우레탄 아크릴레이트 올리고머를 제조하였다.
A urethane acrylate oligomer was prepared in the same manner except for using tripentaerythritol instead of pentaerythritol in Synthesis Example 1 and not using a chain extender.
하드코팅층Hard coating layer 형성용 조성물 Formation composition
<실시예 1>≪ Example 1 >
합성예 1에서 합성된 우레탄 아크릴레이트 올리고머 100중량부에 대하여, 디펜타에리스리톨펜타아크릴레이트(동아합성, M-402) 33.3 중량부, 트리히드록시에틸 이소시아누레이트 트리아크릴레이트(동아합성, M-315) 16.6 중량부, 광중합개시제로서 1-히드록시 시클로헥실 페닐 케톤 5 중량부 및 용매로서 메틸에틸케톤 234 중량부를 60℃에서 1시간 동안 혼합하여 하드코팅층 형성용 조성물을 제조하였다.
33.3 parts by weight of dipentaerythritol pentaacrylate (synthetic synthetic, M-402) with respect to 100 parts by weight of the urethane acrylate oligomer synthesized in Synthesis Example 1, trihydroxyethyl isocyanurate triacrylate (dong-a synthetic, M 1315 parts by weight, 1 part of hydroxy cyclohexyl phenyl ketone as a photopolymerization initiator and 234 parts by weight of methyl ethyl ketone as a solvent were mixed at 60 ° C. for 1 hour to prepare a composition for forming a hard coat layer.
<실시예 2><Example 2>
상기 실시예 1에서, 합성예 2에서 수득한 우레탄 아크릴레이트 올리고머를 사용한 것을 제외하고 동일한 방법으로 하드코팅층 형성용 조성물을 제조하였다.
In Example 1, a hard coating layer-forming composition was prepared in the same manner except that the urethane acrylate oligomer obtained in Synthesis Example 2 was used.
<실시예 3><Example 3>
상기 실시예 1에서, 합성예 3에서 수득한 우레탄 아크릴레이트 올리고머를 사용한 것을 제외하고 동일한 방법으로 하드코팅층 형성용 조성물을 제조하였다.
In Example 1, a composition for forming a hard coat layer was prepared in the same manner except that the urethane acrylate oligomer obtained in Synthesis Example 3 was used.
<비교예 1>Comparative Example 1
상기 실시예 1에서, 합성예 4에서 수득한 우레탄 아크릴레이트 올리고머를 사용한 것을 제외하고 동일한 방법으로 하드코팅층 형성용 조성물을 제조하였다.
In Example 1, a hard coating layer-forming composition was prepared in the same manner except that the urethane acrylate oligomer obtained in Synthesis Example 4 was used.
<비교예 2>Comparative Example 2
상기 실시예 1에서, 합성예 5에서 수득한 우레탄 아크릴레이트 올리고머를 사용한 것을 제외하고 동일한 방법으로 하드코팅층 형성용 조성물을 제조하였다.
In Example 1, a composition for forming a hard coat layer was prepared in the same manner except that the urethane acrylate oligomer obtained in Synthesis Example 5 was used.
<비교예 3>Comparative Example 3
상기 실시예 1에서, 합성예 6에서 수득한 우레탄 아크릴레이트 올리고머를 사용한 것을 제외하고 동일한 방법으로 하드코팅층 형성용 조성물을 제조하였다.
In Example 1, a composition for forming a hard coat layer was prepared in the same manner except that the urethane acrylate oligomer obtained in Synthesis Example 6 was used.
<비교예 4><Comparative Example 4>
상기 실시예 1에서, 합성예 7에서 수득한 우레탄 아크릴레이트 올리고머를 사용한 것을 제외하고 동일한 방법으로 하드코팅층 형성용 조성물을 제조하였다.
In Example 1, a hard coating layer-forming composition was prepared in the same manner except that the urethane acrylate oligomer obtained in Synthesis Example 7 was used.
<비교예 5>Comparative Example 5
상기 실시예 1에서, 합성예 8에서 수득한 우레탄 아크릴레이트 올리고머를 사용한 것을 제외하고 동일한 방법으로 하드코팅층 형성용 조성물을 제조하였다.
In Example 1, a composition for forming a hard coat layer was prepared in the same manner except that the urethane acrylate oligomer obtained in Synthesis Example 8 was used.
하드코팅Hard coating 필름 film
<실시예 4><Example 4>
실시예 1에서 제조된 하드코팅층 형성용 조성물을 기재층인 폴리에틸렌테레프탈레이트(KOLON社, 두께 188㎛) 일면에 도포한 후, 80℃ 오븐에서 3분 동안 건조하고, 자외선조사장치(Fusion社, 600mJ/㎠)에 type-D bulb를 장착하여 하드코팅층 형성용 조성물을 도포한 방향에서 500mJ/㎠의 조사하여 하드코팅 필름(두께 200㎛)을 제조하였다.
The composition for forming a hard coat layer prepared in Example 1 was applied to one surface of a polyethylene terephthalate (KOLON, 188 μm) as a base layer, dried in an oven at 80 ° C. for 3 minutes, and then irradiated with an ultraviolet irradiation device (Fusion, 600 mJ). / Cm2) by mounting a type-D bulb was irradiated with 500mJ / ㎠ in the direction of applying the composition for forming a hard coat layer to prepare a hard coating film (thickness 200㎛).
<실시예 5>Example 5
상기 실시예 4에서, 실시예 2에서 제조된 하드코팅층 형성용 조성물을 사용한 것을 제외하고 동일한 방법으로 하드코팅 필름을 제조하였다.
In Example 4, a hard coat film was prepared in the same manner except for using the composition for forming a hard coat layer prepared in Example 2.
<실시예 6><Example 6>
상기 실시예 4에서, 실시예 3에서 제조된 하드코팅층 형성용 조성물을 사용한 것을 제외하고 동일한 방법으로 하드코팅 필름을 제조하였다.
In Example 4, a hard coat film was prepared in the same manner except for using the hard coat layer-forming composition prepared in Example 3.
<비교예 6>Comparative Example 6
상기 실시예 4에서, 비교예 1에서 제조된 하드코팅층 형성용 조성물을 사용한 것을 제외하고 동일한 방법으로 하드코팅 필름을 제조하였다.
In Example 4, a hard coat film was prepared in the same manner except for using the composition for forming a hard coat layer prepared in Comparative Example 1.
<비교예 7>≪ Comparative Example 7 &
상기 실시예 4에서, 비교예 2에서 제조된 하드코팅층 형성용 조성물을 사용한 것을 제외하고 동일한 방법으로 하드코팅 필름을 제조하였다.
In Example 4, a hard coat film was prepared in the same manner except for using the composition for forming a hard coat layer prepared in Comparative Example 2.
<비교예 8>≪ Comparative Example 8 >
상기 실시예 4에서, 비교예 3에서 제조된 하드코팅층 형성용 조성물을 사용한 것을 제외하고 동일한 방법으로 하드코팅 필름을 제조하였다.
In Example 4, a hard coat film was prepared in the same manner except for using the composition for forming a hard coat layer prepared in Comparative Example 3.
<비교예 9>≪ Comparative Example 9 &
상기 실시예 4에서, 비교예 4에서 제조된 하드코팅층 형성용 조성물을 사용한 것을 제외하고 동일한 방법으로 하드코팅 필름을 제조하였다.
In Example 4, a hard coat film was prepared in the same manner except for using the composition for forming a hard coat layer prepared in Comparative Example 4.
<비교예 10>≪ Comparative Example 10 &
상기 실시예 4에서, 비교예 5에서 제조된 하드코팅층 형성용 조성물을 사용한 것을 제외하고 동일한 방법으로 하드코팅 필름을 제조하였다.
In Example 4, a hard coat film was prepared in the same manner except for using the composition for forming a hard coat layer prepared in Comparative Example 5.
상기 실시예 및 비교예에서 제조된 하드코팅 필름을 다음과 같이 물성평가하였으며, 그 결과는 표 1에 나타내었다.
The physical properties of the hard coat film prepared in Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 1.
(1) 연필경도(1) pencil hardness
상기 실시예 및 비교예에서 제조된 하드코팅 필름을 일본 IMOTO사의 연필경도 측정기를 사용하여 경도를 측정하였다.The hardness of the hard coat film prepared in the above Examples and Comparative Examples was measured using a pencil hardness meter manufactured by IMOTO, Japan.
[측정조건][Measuring conditions]
a. 30mm/min의 속도a. Speed of 30mm / min
b. 하중은 500gf 및 750gfb. The load is 500gf and 750gf
c. 일본 IMOTO사의 연필경도 측정기
c. Pencil hardness measuring instrument of IMOTO, Japan
(2) 내스크래치성(2) scratch resistance
상기 실시예 및 비교예의 하드코팅 필름을 일본 IMOTO사의 Big Heart 테스트 장치에 의한 기본 무게를 사용하여 최소한의 압력을 가하였을 때, 하드코팅 필름의 스크래치 발생여부를 측정하였다. 스크래치 발생에 의한 손상의 정도는 육안으로 판단하였으며 기준을 다음과 같다.When the hard coating films of the Examples and Comparative Examples were subjected to minimal pressure using a basic weight by a Big Heart test apparatus manufactured by IMOTO, Japan, the scratches of the hard coating films were measured. The degree of damage due to scratching was visually determined and the criteria are as follows.
내스크래치성 나쁨 ← X ＜△＜○＜◎ → 내스크래치성 우수
Bad scratch resistance ← X <△ <○ <◎ → Excellent scratch resistance
division
(㎛)Thickness
(Μm)
Scratch resistance
상기 물성 평가 결과, 본 발명의 실시예 4 내지 실시예 6에 의한 하드코팅 필름은 경도 및 내스크래치성이 우수한 것으로 나타났다. 특히, 경도 측정시 하중 500gf 및 750gf일 경우의 경도가 모두 3H로 나타나, 디스플레이를 보호하기 위한 보호필름으로서 요구되는 물성인 우수한 강도를 확보할 수 있음을 기대할 수 있다. As a result of the physical property evaluation, the hard coat film according to Examples 4 to 6 of the present invention was found to be excellent in hardness and scratch resistance. In particular, when the hardness is measured when the load 500gf and 750gf load is all 3H, it can be expected that excellent strength, which is a physical property required as a protective film for protecting the display can be secured.
이에 비하여, 실시예 4 내지 실시예 6에 의한 하드코팅 필름에 비해 사슬연장제인 트리메틸롤프로판의 함량이 적은 비교예 5에 의한 하드코팅 필름은 경도가 낮은 것으로 나타났으며, 실시예 4 내지 실시예 6에 의한 하드코팅 필름에 비해 사슬연장제인 트리메틸롤프로판의 함량이 많은 비교예 7에 의한 하드코팅 필름은 경도는 동일하게 나왔으나, 제조시 겔링 현상이 일어나 하드코팅 필름 제조가 용이하지 않은 문제점이 있었다.On the contrary, the hard coat film according to Comparative Example 5 having a smaller content of trimethylolpropane as a chain extender than the hard coat films according to Examples 4 to 6 was found to have a low hardness, and Examples 4 to Examples. Hard coating film according to Comparative Example 7, which has a higher content of trimethylolpropane, which is a chain extender than the hard coating film according to 6, has the same hardness, but due to the gelling phenomenon during manufacturing, it is not easy to manufacture the hard coating film. there was.
또한, 비교예 8 내지 비교예 10에 의한 하드코팅 필름은 실시예 4 내지 실시예 6에 의한 하드코팅 필름에 비해 낮은 경도 및 내스크래치성을 가져 디스플레이를 보호하기 위한 필름의 용도로 사용시 덜 최적할 것임을 알 수 있었다.In addition, the hard coating film according to Comparative Examples 8 to 10 has a lower hardness and scratch resistance than the hard coating film according to Examples 4 to 6 would be less optimal when used as a film for protecting the display. It could be seen that.
따라서, 우레탄 아크릴레이트 올리고머를 포함하는 하드코팅층 형성용 조성물을 이용하여 제조된 하드코팅 필름은 강도가 요구되는 디스플레이 보호용 필름으로서 적용이 가능하며, 특히 사슬연장제를 포함하는 우레탄 아크릴레이트 올리고머를 이용하는 실시예 4 내지 실시예 6에 의한 하드코팅 필름이 최적한 것임을 알 수 있었다.
Therefore, the hard coat film prepared using the composition for forming a hard coat layer containing a urethane acrylate oligomer can be applied as a display protective film requiring strength, in particular, the implementation using a urethane acrylate oligomer containing a chain extender. It was found that the hard coat film according to Examples 4 to 6 was optimal.
Claims (5)
상기 우레탄 아크릴레이트 올리고머는 사슬연장제를 포함하는 것을 특징으로 하는 하드코팅층 형성용 조성물.
In the composition for forming a hard coat layer comprising a photocurable material and a photopolymerization initiator other than the urethane acrylate oligomer, urethane acrylate oligomer,
The urethane acrylate oligomer is a composition for forming a hard coating layer comprising a chain extender.
According to claim 1, wherein the chain extender is composed of glycerin, trimethylol ethane (trimethylol ethane), trimethylol propane and 1,2,6-hexane triol (1,2,6-hexane triol) Hard coating layer forming composition, characterized in that selected from the group.
The composition of claim 1, wherein the urethane acrylate oligomer comprising the chain extender has a molecular weight of 6,000 to 10,000.
According to claim 1, wherein the content of the chain extender is a composition for forming a hard coat layer, characterized in that 2 to 6% by weight.
상기 우레탄 아크릴레이트 올리고머는 사슬연장제를 포함하는 것을 특징으로 하는 하드코팅 필름.
A hard coating film comprising a composition for forming a hard coating layer made of a photocurable material other than a urethane acrylate oligomer and a urethane acrylate oligomer and a photopolymerization initiator,
The urethane acrylate oligomer is a hard coating film, characterized in that it comprises a chain extender.
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| US9567479B2 (en) | 2012-08-23 | 2017-02-14 | Lg Chem, Ltd. | Hard coating film |
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| WO2013180514A1 (en) * | 2012-05-31 | 2013-12-05 | 주식회사 엘지화학 | Hard coating film and method for manufacturing same |
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| US9884977B2 (en) | 2012-05-31 | 2018-02-06 | Lg Chem, Ltd. | Hard coating composition |
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| US9765234B2 (en) | 2012-08-23 | 2017-09-19 | Lg Chem, Ltd. | Laminated hard coating film |
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| US10280330B2 (en) | 2012-08-23 | 2019-05-07 | Lg Chem, Ltd. | Hard coating film |
| KR20160088000A (en) | 2015-01-15 | 2016-07-25 | 동우 화인켐 주식회사 | Multi-functional (meta)acryl alkoxy silane oligomer, method for preparing thereof and composition for optical film comprising the same and its use |
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