KR20170134577A - Curable composition for repellent coating - Google Patents

Curable composition for repellent coating Download PDF

Info

Publication number
KR20170134577A
KR20170134577A KR1020177031631A KR20177031631A KR20170134577A KR 20170134577 A KR20170134577 A KR 20170134577A KR 1020177031631 A KR1020177031631 A KR 1020177031631A KR 20177031631 A KR20177031631 A KR 20177031631A KR 20170134577 A KR20170134577 A KR 20170134577A
Authority
KR
South Korea
Prior art keywords
group
hard coat
meth
mass
poly
Prior art date
Application number
KR1020177031631A
Other languages
Korean (ko)
Other versions
KR102345843B1 (en
Inventor
마사유키 하라구치
모토노부 마츠야마
Original Assignee
닛산 가가쿠 고교 가부시키 가이샤
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 닛산 가가쿠 고교 가부시키 가이샤 filed Critical 닛산 가가쿠 고교 가부시키 가이샤
Publication of KR20170134577A publication Critical patent/KR20170134577A/en
Application granted granted Critical
Publication of KR102345843B1 publication Critical patent/KR102345843B1/en

Links

Classifications

    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • 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
    • 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
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D7/12—
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • 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
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • 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
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • 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
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Paints Or Removers (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)

Abstract

[과제] 방현성이 우수하고, 또한 높은 내찰상성을 발현하는 하드코트층의 형성재료를 제공하는 것이다.
[해결수단] (a)활성에너지선 경화성 다관능모노머 100질량부, (b)폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 양말단에, 폴리(옥시알킬렌)기를 개재하거나 또는 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 이 순으로 개재하여 활성에너지선 중합성기를 갖는 퍼플루오로폴리에테르 0.1~10질량부, (c)1~10μm의 평균입경을 갖는 유기미립자 8~30질량부, (d)활성에너지선에 의해 라디칼을 발생하는 중합개시제 1~20질량부, 및 (e)유기용매를 포함하는 경화성 조성물, 및 이 조성물로부터 형성되는 하드코트층을 구비하는 하드코트필름.[PROBLEMS] To provide a material for forming a hard coat layer that exhibits excellent antifogging property and high scratch resistance.
(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (b) a poly (oxyalkylene) group interposed between both ends of a molecular chain containing a poly (oxyperfluoroalkylene) 0.1 to 10 parts by mass of perfluoropolyether having an active energy linear polymerizable group interposed therebetween in the order of poly (oxyalkylene) group and one urethane bond, (c) organic fine particles 8 having an average particle diameter of 1 to 10 μm To 30 parts by mass of a radical initiator, (d) 1 to 20 parts by mass of a polymerization initiator which generates a radical by an active energy ray, and (e) a curing composition comprising an organic solvent, and a hard coat layer formed from the composition Coat film.

Description

방현성 코팅용 경화성 조성물Curable composition for repellent coating

본 발명은, 터치패널 디스플레이, 액정디스플레이 등의 각종 표시소자 등의 표면에 적용되는 하드코트층의 형성재료로서 유용한 경화성 조성물에 관한 것으로, 특히 방현성(防眩性)(안티글레어기능)이 우수한 하드코트층을 형성가능한 경화성 조성물에 관한 것이다.The present invention relates to a curable composition useful as a material for forming a hard coat layer applied to surfaces of various display elements such as a touch panel display, a liquid crystal display, etc., and particularly relates to a curable composition which is excellent in antiglare property (anti glare function) To a curable composition capable of forming a hard coat layer.

퍼스널컴퓨터, 휴대전화, 휴대게임기기, ATM 등의 플랫패널디스플레이에 터치패널이 탑재된 제품이 상당히 수많이 상품화되어 있다. 특히, 스마트폰이나 태블릿PC의 등장으로 인해, 멀티터치기능을 갖는 정전용량식 터치패널이 단숨에 그 탑재수를 늘리고 있다.A considerable number of products in which a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a portable game device, and an ATM have been commercialized. In particular, due to the emergence of smartphones and tablet PCs, capacitive touch panels with multi-touch functions are increasingly being installed at a glance.

이들 터치패널 디스플레이 표면에는, 그 화면에 외부광이 비치는 것에 의한 시인성의 저하를 방지하기 위하여, 표면에 요철이 형성된 수μm 정도의 하드코트층을 구비하는 방현성 하드코트필름을 접합하는 방법이 이용되고 있다. 표면에 요철을 형성하는 수법으로는, 수μm 정도의 입경을 갖는 미립자를 하드코트층에 함유하는 방법이 일반적으로 이용되고 있다.In order to prevent deterioration of visibility due to external light shining on the screen, there is provided a method of bonding a light-scattering hard coat film having a hard coat layer having a thickness of several micrometers, . As a method of forming irregularities on the surface, a method of containing fine particles having a particle diameter of several micrometers in the hard coat layer is generally used.

그런데, 정전용량식 터치패널에서는 인간의 손가락으로 접촉하는 것에 의해 조작을 행한다. 이 때문에, 조작을 행할 때마다 터치패널의 표면에 지문이 부착되어, 디스플레이의 화상의 시인성이 현저히 손상되거나, 디스플레이의 외관이 손상된다는 문제가 발생하고 있다. 지문에는 땀 유래의 수분 및 피지 유래의 유분이 포함되어 있으며, 이들 모두 부착되기 어렵게 하기 위해, 디스플레이 표면의 하드코트층에는 발수성 및 발유성을 부여하는 것이 강하게 요구되고 있다.By the way, in the capacitive touch panel, the operation is performed by touching with a human finger. For this reason, fingerprints are attached to the surface of the touch panel every time the operation is performed, so that the visibility of the image on the display is remarkably impaired and the appearance of the display is damaged. The fingerprint contains moisture derived from sweat and oil derived from sebum, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the surface of the display in order to make them hard to adhere.

그러나, 정전용량식 터치패널에서는, 사람이 매일 손가락으로 접촉하기 때문에, 초기의 방오성은 상당한 레벨에 도달해 있다고 하더라도, 사용 중에 흠집이 생김으로써 이들 기능이 저하되는 경우가 많다. 특히 방현성 하드코트층에서는, 그 표면에 요철을 가지는 점에서, 걸림이 발생하기 쉬워, 흠집이 생기기 쉽다. 이에 따라, 사용과정에서의 방오성의 내구성이 과제였다.However, in a capacitive touch panel, since a person touches with a finger every day, even if the initial antifouling property reaches a considerable level, these functions often deteriorate due to scratches during use. Particularly, in the non-light-sensitive hard coat layer, the surface of the hard coat layer has irregularities, so that the hard coat layer is easily caught and easily scratched. Accordingly, the durability of the antifouling property during use was a problem.

지금까지, 방현성 및 내찰상성을 갖는 하드코트층으로서, 방오성 및 내찰상성을 하드코트층 표면에 부여하는 성분으로서, 분자내에 폴리(옥시퍼플루오로알킬렌)구조 및 (메트)아크릴로일기를 갖는 표면개질제, 나아가 방현성을 하드코트층에 부여하는 성분으로서, 메타크릴산메틸-스티렌 공중합체(MS)수지 미립자를 이용한 기술이 개시되어 있다(특허문헌 1).Until now, as a hard coat layer having antifogging property and scratch resistance, a poly (oxyperfluoroalkylene) structure and a (meth) acryloyl group in the molecule as a component imparting antifouling property and scratch resistance to the surface of the hard coat layer (MS) resin microparticles as a surface modifier having a high hardness and a surface modifier and further imparting a flash-resistant property to the hard coat layer (Patent Document 1).

일본특허공개 2013-257359호 공보Japanese Patent Application Laid-Open No. 2013-257359

특허문헌 1에 구체적으로 기재된 방법에서는, 분자내에 폴리(옥시퍼플루오로알킬렌)구조 및 (메트)아크릴로일기를 갖는 표면개질제의 불소함유량이 낮고, 충분한 방오성 및 내찰상성을 얻지 못한다는 과제가 있었다. 또한, 내찰상성을 얻으려고 MS수지입자의 첨가량을 저감하면 충분한 방현성을 얻지 못하고, 충분한 방현성이 얻어질 정도로 MS수지입자를 첨가한 경우에는 내찰상성이 현저히 저하된다는 과제가 있었다. 나아가, 하드코트층 중에 있어서의 수지입자의 분산성이 나빠서, 응집물이 되어 도막의 외관을 손상시키는 것도 과제였다. 즉, 방현성이 우수하고, 또한 높은 내찰상성을 발현하는 하드코트층이 요구되고 있었다.In the method specifically disclosed in Patent Document 1, there is a problem that the fluorine content of the surface modifier having a poly (oxyperfluoroalkylene) structure and a (meth) acryloyl group in the molecule is low and sufficient antifouling property and scratch resistance are not obtained there was. In addition, when the addition amount of the MS resin particles is reduced to obtain the scratch resistance, sufficient antifogging property is not obtained, and when the MS resin particles are added to such an extent that satisfactory repellency is obtained, there is a problem that the scratch resistance is remarkably lowered. Furthermore, the dispersibility of the resin particles in the hard coat layer is poor, and it is a problem that the appearance of the coating film is impaired due to aggregation. Namely, there has been a demand for a hard coat layer which exhibits excellent antireflection property and exhibits high scratch resistance.

본 발명자들은, 상기 목적을 달성하기 위하여 예의 검토를 거듭한 결과, 폴리(옥시퍼플루오로알킬렌)구조를 포함하는 분자쇄의 양말단에, 폴리(옥시알킬렌)기를 개재하거나 또는 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 개재하여, 활성에너지선 중합성기를 갖는 화합물을, 불소계 표면개질제로서 이용하고, 나아가 그것에 유기미립자를 첨가한 경화성 조성물을 채용함으로써, 우수한 방현성 및 높은 내찰상성을 갖는 하드코트층을 형성가능한 것을 발견하고, 본 발명을 완성시켰다.DISCLOSURE OF THE INVENTION As a result of intensive investigations to achieve the above object, the present inventors have found that a poly (oxyalkylene) group is interposed between both ends of a molecular chain containing a poly (oxyperfluoroalkylene) Alkylene) group and one urethane bond as a fluorine surface modifier, and further employing a curable composition comprising an organic fine particle added thereto, it is possible to provide a composition having excellent antifogging properties and high scratch resistance Can be formed, and the present invention has been accomplished.

즉 본 발명은, 제1 관점으로서,That is, the present invention, as a first aspect,

(a) 활성에너지선 경화성 다관능모노머 100질량부,(a) 100 parts by mass of active energy ray-curable polyfunctional monomer,

(b) 폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 양말단에, 폴리(옥시알킬렌)기를 개재하거나 또는 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 이 순으로 개재하여, 활성에너지선 중합성기를 갖는 퍼플루오로폴리에테르 0.1~10질량부,(oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order in the both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group, (b) 0.1 to 10 parts by mass of a perfluoropolyether having an active energy linear polymerizable group,

(c) 1~10μm의 평균입경을 갖는 유기미립자 8~30질량부,(c) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 m,

(d) 활성에너지선에 의해 라디칼을 발생하는 중합개시제 1~20질량부, 및(d) 1 to 20 parts by mass of a polymerization initiator which generates a radical by an active energy ray, and

(e) 유기용매(e) an organic solvent

를 포함하는 경화성 조성물에 관한 것이다.≪ / RTI >

제2 관점으로서, 상기 폴리(옥시퍼플루오로알킬렌)기가, -[OCF2]- 및 -[OCF2CF2]-를 반복단위로서 갖는 기인, 제1 관점에 기재된 경화성 조성물에 관한 것이다.As a second aspect, the present invention relates to the curable composition described in the first aspect, wherein the poly (oxyperfluoroalkylene) group is a group having - [OCF 2 ] - and - [OCF 2 CF 2 ] - as repeating units.

제3 관점으로서, 상기 폴리(옥시알킬렌)기가 폴리(옥시에틸렌)기인, 제1 관점 또는 제2 관점에 기재된 경화성 조성물에 관한 것이다.As a third aspect, the present invention relates to the curable composition described in the first or second aspect, wherein the poly (oxyalkylene) group is a poly (oxyethylene) group.

제4 관점으로서, 상기 성분(a)의 다관능모노머가, 다관능(메트)아크릴레이트 화합물 및 다관능우레탄(메트)아크릴레이트 화합물로 이루어진 군으로부터 선택되는 적어도 1개인, 제1 관점 내지 제3 관점 중 어느 하나에 기재된 경화성 조성물에 관한 것이다.As a fourth aspect, it is preferable that the polyfunctional monomer of the component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) The present invention relates to a curable composition as described above.

제5 관점으로서, 상기 성분(c)의 유기미립자가 진구상(眞球狀) 입자인, 제1 관점 내지 제4 관점 중 어느 하나에 기재된 경화성 조성물에 관한 것이다.As a fifth aspect, the present invention relates to the curable composition according to any one of the first to fourth aspects, wherein the organic fine particles of the component (c) are spherical particles.

제6 관점으로서, 상기 성분(c)의 유기미립자가 폴리메타크릴산메틸입자인, 제1 관점 내지 제5 관점 중 어느 하나에 기재된 경화성 조성물에 관한 것이다.As a sixth aspect, the present invention relates to the curable composition according to any one of the first to fifth aspects, wherein the organic fine particles of the component (c) are polymethyl methacrylate particles.

제7 관점으로서, 상기 성분(d)의 중합개시제가 알킬페논류인, 제1 관점 내지 제6 관점 중 어느 하나에 기재된 경화성 조성물에 관한 것이다.As a seventh aspect, the present invention relates to the curable composition according to any one of the first to sixth aspects, wherein the polymerization initiator of the component (d) is an alkylphenone compound.

제8 관점으로서, 제1 관점 내지 제7 관점 중 어느 하나에 기재된 경화성 조성물로부터 얻어지는 경화막에 관한 것이다.An eighth aspect relates to a cured film obtained from the curable composition according to any one of the first to seventh aspects.

제9 관점으로서, 필름기재의 적어도 일방의 면에 하드코트층을 구비하는 하드코트필름으로서, 이 하드코트층이 제8 관점에 기재된 경화막으로 이루어진, 하드코트필름에 관한 것이다.As a ninth aspect, the present invention relates to a hard coat film comprising a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film according to the eighth aspect.

제10 관점으로서, 필름기재의 적어도 일방의 면에 하드코트층을 구비하는 하드코트필름으로서, 이 하드코트층이, 제1 관점 내지 제7 관점 중 어느 하나에 기재된 경화성 조성물을 필름기재 상에 도포하고 도막을 형성하는 공정과, 이 도막에 활성에너지선을 조사하고 경화하는 공정을 포함하는 방법에 의해 형성되어 이루어진, 하드코트필름에 관한 것이다.As a tenth aspect, there is provided a hard coat film comprising a hard coat layer on at least one side of a film substrate, wherein the hard coat layer is formed by applying the curable composition according to any one of the first to seventh aspects onto a film substrate And a hard coat film formed by a method comprising a step of forming a coating film and a step of irradiating the coating film with an active energy ray and curing the coating film.

제11 관점으로서, 상기 하드코트층이, 상기 유기미립자의 평균입경에 비해 1배~10/7배의 두께를 갖는, 제9 관점 또는 제10 관점에 기재된 하드코트필름에 관한 것이다.As an eleventh aspect, the hard coat film according to the ninth or tenth aspect is characterized in that the hard coat layer has a thickness of 1 to 10/7 times the average particle diameter of the organic fine particles.

제12 관점으로서, 상기 하드코트층이 1~20μm의 막두께를 갖는, 제9 관점 내지 제11 관점 중 어느 하나에 기재된 하드코트필름에 관한 것이다.As a twelfth aspect, the present invention relates to the hard coat film according to any one of the ninth to eleventh aspects, wherein the hard coat layer has a film thickness of 1 to 20 탆.

제13 관점으로서, 상기 하드코트층이 3~10μm의 막두께를 갖는, 제12 관점에 기재된 하드코트필름에 관한 것이다.In a thirteenth aspect, the hard coat film according to the twelfth aspect is characterized in that the hard coat layer has a film thickness of 3 to 10 mu m.

본 발명에 따르면, 두께 1~10μ 정도의 박막에 있어서도 우수한 내찰상성 및 높은 방현성을 갖고 외관도 우수한 경화막 및 하드코트층의 형성에 유용한 경화성 조성물을 제공할 수 있다.According to the present invention, it is possible to provide a curable composition useful for forming a cured film and a hard coat layer having excellent scratch resistance and high antifogging property and excellent appearance even in a thin film having a thickness of about 1 to 10 mu m.

또한, 본 발명에 따르면, 상기 경화성 조성물로부터 얻어지는 경화막 또는 이로부터 형성되는 하드코트층이 표면에 부여된 하드코트필름을 제공할 수 있고, 방현성, 내찰상성 및 외관이 우수한 하드코트필름을 제공할 수 있다.Further, according to the present invention, it is possible to provide a hard coat film which can provide a cured film obtained from the curable composition or a hard coat film having a hard coat layer formed therefrom on the surface thereof, and which has excellent flame retardance, scratch resistance and appearance can do.

<경화성 조성물>&Lt; Curable composition >

본 발명의 경화성 조성물은, 상세하게는,The curable composition of the present invention, specifically,

(a) 활성에너지선 경화성 다관능모노머 100질량부,(a) 100 parts by mass of active energy ray-curable polyfunctional monomer,

(b) 폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 양말단에, 폴리(옥시알킬렌)기를 개재하거나 또는 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 이 순으로 개재하여, 활성에너지선 중합성기를 갖는 퍼플루오로폴리에테르 0.1~10질량부,(oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order in the both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group, (b) 0.1 to 10 parts by mass of a perfluoropolyether having an active energy linear polymerizable group,

(c) 1~10μm의 평균입경을 갖는 유기미립자 8~30질량부,(c) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 m,

(d) 활성에너지선에 의해 라디칼을 발생하는 중합개시제 1~20질량부, 및(d) 1 to 20 parts by mass of a polymerization initiator which generates a radical by an active energy ray, and

(e) 유기용매(e) an organic solvent

를 포함하는 경화성 조성물에 관한 것이다.&Lt; / RTI &gt;

이하, 우선 상기 (a)~(e)의 각 성분에 대하여 설명한다.Hereinafter, each of the components (a) to (e) will be described.

[(a) 활성에너지선 경화성 다관능모노머][(a) Active Energy ray curable polyfunctional monomer]

활성에너지선 경화성 다관능모노머란, 자외선 등의 활성에너지선을 조사함으로써 중합반응이 진행되고, 경화하는 모노머를 가리킨다.The active energy ray-curable multifunctional monomer refers to a monomer that undergoes polymerization reaction by curing an active energy ray such as ultraviolet rays and hardens.

본 발명의 경화성 조성물에 있어서 바람직한 (a)활성에너지선 경화성 다관능모노머로는, 다관능(메트)아크릴레이트 화합물 및 다관능우레탄(메트)아크릴레이트 화합물로 이루어진 군으로부터 선택되는 모노머이다.The active energy ray-curable polyfunctional monomer (a) in the curable composition of the present invention is preferably a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.

한편, 본 발명에 있어서 (메트)아크릴레이트 화합물이란, 아크릴레이트 화합물과 메타크릴레이트 화합물의 양방을 말한다. 예를 들어 (메트)아크릴산은, 아크릴산과 메타크릴산을 말한다.On the other hand, in the present invention, the (meth) acrylate compound means both of an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

상기 다관능(메트)아크릴레이트 화합물로는, 예를 들어, 트리메틸올프로판트리(메트)아크릴레이트, 디트리메틸올프로판테트라(메트)아크릴레이트, 펜타에리스리톨디(메트)아크릴레이트, 펜타에리스리톨트리(메트)아크릴레이트, 펜타에리스리톨테트라(메트)아크릴레이트, 디펜타에리스리톨펜타(메트)아크릴레이트, 디펜타에리스리톨헥사(메트)아크릴레이트, 글리세린트리(메트)아크릴레이트, 에톡시화트리메틸올프로판트리(메트)아크릴레이트, 에톡시화펜타에리스리톨테트라(메트)아크릴레이트, 에톡시화디펜타에리스리톨헥사(메트)아크릴레이트, 에톡시화글리세린트리(메트)아크릴레이트, 에톡시화비스페놀A디(메트)아크릴레이트, 1,3-프로판디올디(메트)아크릴레이트, 1,3-부탄디올디(메트)아크릴레이트, 1,4-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 2-메틸-1,8-옥탄디올디(메트)아크릴레이트, 1,9-노난디올디(메트)아크릴레이트, 1,10-데칸디올디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 트리에틸렌글리콜디(메트)아크릴레이트, 테트라에틸렌글리콜디(메트)아크릴레이트, 프로필렌글리콜디(메트)아크릴레이트, 디프로필렌글리콜디(메트)아크릴레이트, 비스(2-하이드록시에틸)이소시아누레이트디(메트)아크릴레이트, 트리스(2-하이드록시에틸)이소시아누레이트트리(메트)아크릴레이트, 트리시클로[5.2.1.02,6]데칸디메탄올디(메트)아크릴레이트, 디옥산글리콜디(메트)아크릴레이트, 2-하이드록시-1-아크릴로일옥시-3-메타크릴로일옥소프로판, 2-하이드록시-1,3-디(메트)아크릴로일옥소프로판, 9,9-비스[4-(2-(메트)아크릴로일옥시에톡시)페닐]플루오렌, 비스[4-(메트)아크릴로일졔페닐]설파이드, 비스[2-(메트)아크릴로일티오에틸]설파이드, 1,3-아다만탄디올디(메트)아크릴레이트, 1,3-아다만탄디메탄올디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 폴리프로필렌글리콜디(메트)아크릴레이트 등을 들 수 있다.Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, ethoxylated trimethylolpropane tri (Meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, ethoxylated glycerine tri (meth) acrylate, ethoxylated bisphenol A di Butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hex (Meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, Acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Tri (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decanedimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy- - methacryloyloxopropane, 2-hydroxy-1,3-di (meth) acryloyloxy Propane, bis [4- (meth) acryloylphenyl] sulfide, bis [2- (meth) acryloyloxyphenyl] Adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, and the like.

그 중에서도 바람직한 것으로서, 펜타에리스리톨트리(메트)아크릴레이트, 펜타에리스리톨테트라(메트)아크릴레이트, 디펜타에리스리톨펜타(메트)아크릴레이트, 디펜타에리스리톨헥사(메트)아크릴레이트 등을 들 수 있다.Among them, preferred are pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

상기 다관능우레탄(메트)아크릴레이트 화합물은, 1분자내에 아크릴로일기 또는 메타크릴로일기를 복수 갖고, 우레탄결합(-NHCOO-)을 하나 이상 갖는 화합물이다.The polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryloyl or methacryloyl groups in one molecule and having at least one urethane bond (-NHCOO-).

예를 들어 상기 다관능우레탄(메트)아크릴레이트로는, 다관능이소시아네이트와 하이드록시기를 갖는 (메트)아크릴레이트와의 반응에 의해 얻어지는 것, 다관능이소시아네이트와 하이드록시기를 갖는 (메트)아크릴레이트와 폴리올과의 반응에 의해 얻어지는 것 등을 들 수 있으나, 본 발명에서 사용가능한 다관능우레탄(메트)아크릴레이트 화합물은 이러한 예시만으로 한정되는 것은 아니다.Examples of the above polyfunctional urethane (meth) acrylate include those obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxy group, a (meth) acrylate having a polyfunctional isocyanate and a hydroxy group (Meth) acrylate compounds which can be used in the present invention are not limited to these examples.

또한 상기 다관능이소시아네이트로는, 예를 들어, 톨릴렌디이소시아네이트, 이소포론디이소시아네이트, 자일릴렌디이소시아네이트, 헥사메틸렌디이소시아네이트 등을 들 수 있다.Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and the like.

또한 상기 하이드록시기를 갖는 (메트)아크릴레이트로는, 예를 들어, (메트)아크릴산2-하이드록시에틸, (메트)아크릴산2-하이드록시프로필, 펜타에리스리톨트리(메트)아크릴레이트, 디펜타에리스리톨펜타(메트)아크릴레이트, 트리펜타에리스리톨헵타(메트)아크릴레이트 등을 들 수 있다.Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Penta (meth) acrylate, and tripentaerythritol hepta (meth) acrylate.

그리고 상기 폴리올으로는, 예를 들어, 에틸렌글리콜, 프로필렌글리콜, 네오펜틸글리콜, 1,4-부탄디올, 1,6-헥산디올, 디에틸렌글리콜, 디프로필렌글리콜 등의 디올류; 이들 디올류와 숙신산, 말레산, 아디프산 등의 지방족 디카르본산류 또는 디카르본산무수물류와의 반응생성물인 폴리에스테르폴리올; 폴리에테르폴리올; 폴리카보네이트디올 등을 들 수 있다.Examples of the polyol include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol; Polyester polyols which are reaction products of these diols with aliphatic dicarboxylic acids such as succinic acid, maleic acid and adipic acid or dicarboxylic anhydrides; Polyether polyols; And polycarbonate diol.

본 발명에서는, 상기 (a)활성에너지선 경화성 다관능모노머로서, 상기 다관능(메트)아크릴레이트 화합물 및 상기 다관능우레탄(메트)아크릴레이트 화합물로 이루어진 군으로부터 1종을 단독으로, 혹은 2종 이상을 조합하여 사용할 수 있다. 얻어지는 경화물의 내찰상성의 관점에서, 다관능(메트)아크릴레이트 화합물 및 다관능우레탄(메트)아크릴레이트 화합물을 병용하는 것이 바람직하다. 또한, 상기 다관능(메트)아크릴레이트 화합물로서, 5관능 이상의 다관능(메트)아크릴레이트 화합물 및 4관능 이하의 다관능(메트)아크릴레이트 화합물을 병용하는 것이 바람직하다.In the present invention, it is preferable that, as the active energy ray-curable polyfunctional monomer (a), one kind selected from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) These can be used in combination. From the viewpoint of scratch resistance of the obtained cured product, it is preferable to use a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound in combination. As the polyfunctional (meth) acrylate compound, it is preferable to use a combination of a polyfunctional (meth) acrylate compound having five or more functional groups and a polyfunctional (meth) acrylate compound having four or less functional groups.

또한, 상기 다관능(메트)아크릴레이트 화합물과 상기 다관능우레탄(메트)아크릴레이트 화합물을 조합하여 사용하는 경우, 다관능(메트)아크릴레이트 화합물 100질량부에 대하여, 다관능우레탄(메트)아크릴레이트 화합물 20~100질량부를 사용하는 것이 바람직하고, 30~70질량부를 사용하는 것이 보다 바람직하다.When the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound are used in combination, it is preferable that the polyfunctional (meth) acrylate compound is used in combination with 100 parts by mass of the polyfunctional (meth) It is preferable to use 20 to 100 parts by mass of the compound, more preferably 30 to 70 parts by mass.

나아가, 상기 다관능(메트)아크릴레이트 화합물에 있어서, 상기 5관능 이상의 다관능(메트)아크릴레이트 화합물과 상기 4관능 이하의 다관능(메트)아크릴레이트 화합물을 조합하여 사용하는 경우, 5관능 이상의 다관능(메트)아크릴레이트 화합물 100질량부에 대하여, 4관능 이하의 다관능(메트)아크릴레이트 화합물 10~100질량부를 사용하는 것이 바람직하고, 20~60질량부를 사용하는 것이 보다 바람직하다.Further, in the above polyfunctional (meth) acrylate compound, when the pentafunctional or higher polyfunctional (meth) acrylate compound and the tetrafunctional or below polyfunctional (meth) acrylate compound are used in combination, It is preferable to use 10 to 100 parts by mass of the tetrafunctional or less polyfunctional (meth) acrylate compound per 100 parts by mass of the polyfunctional (meth) acrylate compound, more preferably 20 to 60 parts by mass.

또한, 다관능(메트)아크릴레이트 화합물 100질량부에 대하여 다관능우레탄(메트)아크릴레이트 화합물 20~100질량부 또한 5관능 이상의 다관능(메트)아크릴레이트 화합물 100질량부에 대하여 4관능 이하의 다관능(메트)아크릴레이트 화합물 10~100질량부로 사용하는 것,Further, it is preferable that 20 to 100 parts by mass of the polyfunctional urethane (meth) acrylate compound is added to 100 parts by mass of the polyfunctional (meth) acrylate compound, and the amount of the polyfunctional (meth) (Meth) acrylate compound in an amount of 10 to 100 parts by mass,

다관능(메트)아크릴레이트 화합물 100질량부에 대하여 다관능우레탄(메트)아크릴레이트 화합물 20~100질량부 또한 5관능 이상의 다관능(메트)아크릴레이트 화합물 100질량부에 대하여 4관능 이하의 다관능(메트)아크릴레이트 화합물 20~60질량부로 사용하는 것,(Meth) acrylate compound per 100 parts by mass of the polyfunctional (meth) acrylate compound is added to 100 parts by mass of the polyfunctional (meth) acrylate compound with a polyfunctional (Meth) acrylate compound in an amount of 20 to 60 parts by mass,

다관능(메트)아크릴레이트 화합물 100질량부에 대하여 다관능우레탄(메트)아크릴레이트 화합물 30~70질량부 또한 5관능 이상의 다관능(메트)아크릴레이트 화합물 100질량부에 대하여 4관능 이하의 다관능(메트)아크릴레이트 화합물 10~100질량부로 사용하는 것,30 to 70 parts by mass of a polyfunctional urethane (meth) acrylate compound per 100 parts by mass of the polyfunctional (meth) acrylate compound is added to 100 parts by mass of a polyfunctional (meth) (Meth) acrylate compound in an amount of 10 to 100 parts by mass,

다관능(메트)아크릴레이트 화합물 100질량부에 대하여 다관능우레탄(메트)아크릴레이트 화합물 30~70질량부 또한 5관능 이상의 다관능(메트)아크릴레이트 화합물 100질량부에 대하여 4관능 이하의 다관능(메트)아크릴레이트 화합물 20~60질량부로 사용하는 것이 바람직하다.30 to 70 parts by mass of a polyfunctional urethane (meth) acrylate compound per 100 parts by mass of the polyfunctional (meth) acrylate compound is added to 100 parts by mass of a polyfunctional (meth) (Meth) acrylate compound is preferably used in an amount of 20 to 60 parts by mass.

[(b) 폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 양말단에, 폴리(옥시알킬렌)기를 개재하거나 또는 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 이 순으로 개재하여, 활성에너지선 중합성기를 갖는 퍼플루오로폴리에테르][(b) A poly (oxyalkylene) group or a poly (oxyalkylene) group and a urethane bond are interposed in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) , Perfluoropolyether having an active energy pre-polymerizable group]

본 발명에서는, (b)성분으로서, 폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 양말단에, 폴리(옥시알킬렌)기를 개재하거나 또는 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 이 순으로 개재하여, 활성에너지선 중합성기를 갖는 퍼플루오로폴리에테르(이후, 간단히 「(b)양말단에 중합성기를 갖는 퍼플루오로폴리에테르」라고도 칭함)를 사용한다. (b)성분은, 본 발명의 경화성 조성물을 적용하는 하드코트층에 있어서의 표면개질제로서의 역할을 한다.In the present invention, as the component (b), a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane (oxyalkylene) group are bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) (Hereinafter, simply referred to as (b) perfluoropolyether having a polymerizable group at both ends thereof) having an active energy linear polymerizable group interposed therebetween in this order. The component (b) serves as a surface modifier in the hard coat layer to which the curable composition of the present invention is applied.

상기 폴리(옥시퍼플루오로알킬렌)기에 있어서의 알킬렌기의 탄소원자수는 특별히 한정되지 않으나, 바람직하게는 탄소원자수 1~4인 것이 바람직하다. 즉, 상기 폴리(옥시퍼플루오로알킬렌)기는, 탄소원자수 1~4의 2가의 불화탄소기와 산소원자가 교호로 연결된 구조를 갖는 기를 가리키고, 옥시퍼플루오로알킬렌기는 탄소원자수 1~4의 2가의 불화탄소기와 산소원자가 연결된 구조를 갖는 기를 가리킨다. 구체적으로는, -[OCF2]-(옥시퍼플루오로메틸렌기), -[OCF2CF2]-(옥시퍼플루오로에틸렌기), -[OCF2CF2CF2]-(옥시퍼플루오로프로판-1,3-디일기), -[OCF2C(CF3)F]-(옥시퍼플루오로프로판-1,2-디일기) 등의 기를 들 수 있다.The number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the poly (oxyperfluoroalkylene) group refers to a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and oxygen atoms are alternately linked, and the oxyperfluoroalkylene group has 2 to 4 carbon atoms Quot; refers to a group having a structure in which a fluorocarbon group and an oxygen atom are connected to each other. Specific examples thereof include - [OCF 2 ] - (oxyperfluoromethylene group), - [OCF 2 CF 2 ] - (oxyperfluoroethylene group), - [OCF 2 CF 2 CF 2 ] - Diethyl group), - [OCF 2 C (CF 3 ) F] - (oxy perfluoropropane-1,2-diyl group), and the like.

상기 옥시퍼플루오로알킬렌기는, 1종을 단독으로 사용할 수도 있고, 혹은 2종 이상을 조합하여 사용할 수도 있고, 그 경우, 복수종의 옥시퍼플루오로알킬렌기의 결합은 블록결합 및 랜덤결합의 어느 것이어도 된다.The oxyperfluoroalkylene group may be used singly or in combination of two or more kinds. In this case, the oxyperfluoroalkylene group may be bonded to the oxyperfluoroalkylene group through a block bond or a random bond. Either way.

이들 중에서도, 내찰상성이 양호해지는 경화막이 얻어지는 관점에서, 폴리(옥시퍼플루오로알킬렌)기로서, -[OCF2]-(옥시퍼플루오로메틸렌기)와 -[OCF2CF2]-(옥시퍼플루오로에틸렌기)의 쌍방을 반복단위로서 갖는 기를 이용하는 것이 바람직하다.Of these, from the viewpoint of obtaining a cured film having excellent scratch resistance, it is preferable to use - [OCF 2 ] - (oxyperfluoromethylene group) and - [OCF 2 CF 2 ] - (oxyperfluoroalkylene group) Oxy perfluoroethylene group) as a repeating unit is preferably used.

그 중에서도 상기 폴리(옥시퍼플루오로알킬렌)기로서, 반복단위:-[OCF2]-와 -[OCF2CF2]-가, 몰비율로 [반복단위:-[OCF2]-]:[반복단위:-[OCF2CF2]-]=2:1~1:2가 되는 비율로 포함하는 기인 것이 바람직하고, 약 1:1이 되는 비율로 포함하는 기인 것이 보다 바람직하다. 이들 반복단위의 결합은, 블록결합 및 랜덤결합의 어느 것이어도 된다.Among them, the repeating units: - [OCF 2 ] - and - [OCF 2 CF 2 ] - as the poly (oxyperfluoroalkylene) group are represented by repeating units: - [OCF 2 ] -] Is preferably a group containing a repeating unit represented by the formula: - [OCF 2 CF 2 ] -] = 2: 1 to 1: 2, more preferably a group containing the repeating unit at a ratio of about 1: 1. The bonding of these repeating units may be either a block bonding or a random bonding.

상기 옥시퍼플루오로알킬렌기의 반복단위수는, 그 반복단위수의 총계로서 5~30의 범위인 것이 바람직하고, 7~21의 범위인 것이 보다 바람직하다.The number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21 as the total number of the repeating unit.

또한, 상기 폴리(옥시퍼플루오로알킬렌)기의 겔 침투 크로마토그래피에 의한 폴리스티렌 환산으로 측정되는 중량평균분자량(Mw)은, 1,000~5,000, 바람직하게는 1,500~2,000이다.The weight average molecular weight (Mw) of the poly (oxyperfluoroalkylene) group measured by gel permeation chromatography in terms of polystyrene is 1,000 to 5,000, preferably 1,500 to 2,000.

상기 폴리(옥시알킬렌)기에 있어서의 알킬렌기의 탄소원자수는 특별히 한정되지 않으나, 바람직하게는 탄소원자수 1~4인 것이 바람직하다. 즉, 상기 폴리(옥시알킬렌)기는, 탄소원자수 1~4의 알킬렌기와 산소원자가 교호로 연결된 구조를 갖는 기를 가리키고, 옥시알킬렌기는 탄소원자수 1~4의 2가의 알킬렌기와 산소원자가 연결된 구조를 갖는 기를 가리킨다. 상기 알킬렌기로는, 에틸렌기, 1-메틸에틸렌기, 트리메틸렌기, 테트라메틸렌기 등을 들 수 있다.The number of carbon atoms of the alkylene group in the poly (oxyalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the poly (oxyalkylene) group refers to a group having a structure in which an alkylene group having 1 to 4 carbon atoms and an oxygen atom are alternately linked, and the oxyalkylene group has a structure in which oxygen is bonded to a bivalent alkylene group having 1 to 4 carbon atoms &Lt; / RTI &gt; Examples of the alkylene group include an ethylene group, a 1-methylethylene group, a trimethylene group, and a tetramethylene group.

상기 옥시알킬렌기는, 1종을 단독으로 사용할 수도 있고, 혹은 2종 이상을 조합하여 사용할 수도 있고, 그 경우, 복수종의 옥시알킬렌기의 결합은 블록결합 및 랜덤결합의 어느 것이어도 된다.These oxyalkylene groups may be used singly or in combination of two or more. In this case, the oxyalkylene groups may be bonded to each other through a block bond or a random bond.

그 중에서도, 상기 폴리(옥시알킬렌)기는, 폴리(옥시에틸렌)기인 것이 바람직하다.Among them, the poly (oxyalkylene) group is preferably a poly (oxyethylene) group.

상기 폴리(옥시알킬렌)기에 있어서의 옥시알킬렌기의 반복단위수는, 예를 들어 1~15의 범위이며, 예를 들어 5~12의 범위, 예를 들어 7~12의 범위인 것이 보다 바람직하다.The number of repeating units of the oxyalkylene group in the poly (oxyalkylene) group is, for example, in the range of 1 to 15, for example, in the range of 5 to 12, for example, in the range of 7 to 12 Do.

상기 폴리(옥시알킬렌)기를 개재하거나 또는 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 이 순으로 개재하여 결합하는 활성에너지선 중합성기로는, (메트)아크릴로일기, 우레탄(메트)아크릴로일기, 비닐기 등을 들 수 있다.Examples of the active energy prepolymerizable group interposed between the poly (oxyalkylene) group or the poly (oxyalkylene) group and one urethane bond in this order include a (meth) acryloyl group, a urethane (meth) An acryloyl group, and a vinyl group.

상기 활성에너지선 중합성기는, (메트)아크릴로일부분 등의 활성에너지선 중합성 부분을 1개 갖는 것으로 한정되지 않고, 2개 이상의 활성에너지선 중합성 부분을 갖는 것일 수도 있고, 예를 들어, 이하에 나타낸 A1~A5의 구조, 및 이들 구조 중의 아크릴로일기를 메타크릴로일기로 치환한 구조를 들 수 있다.The active energy pre-polymerizable group is not limited to having one active energy pre-polymerizable moiety such as a part of (meth) acrylo, but may have two or more active energy pre-polymerizable moieties. For example, Structures A1 to A5 shown below, and structures obtained by substituting methacryloyl groups for acryloyl groups in these structures.

[화학식 1][Chemical Formula 1]

Figure pct00001
Figure pct00001

이러한 (b)양말단에 중합성기를 갖는 퍼플루오로폴리에테르로서, 공업적 제조가 용이하다는 점에서, 이하에 나타낸 화합물 및 이들 화합물 중의 아크릴로일기를 메타크릴로일기로 치환한 화합물을 바람직한 예로서 들 수 있다. 한편, 구조식 중, A는 상기 식[A1]~식[A5]로 표시되는 구조 중의 1개를 나타내고, PFPE는 상기 폴리(옥시퍼플루오로알킬렌)기를 나타내고, n은 각각 독립적으로 옥시에틸렌기의 반복단위수를 나타내고, 바람직하게는 1~15의 수를 나타내고, 보다 바람직하게는 5~12의 수를 나타내고, 더욱 바람직하게는 7~12의 수를 나타낸다.Such (b) perfluoropolyethers having a polymerizable group at both ends thereof are preferably the compounds shown below and the compounds in which the acryloyl group is substituted with a methacryloyl group, from the viewpoint of easy industrial production . In the structural formulas, A represents one of the structures represented by the above-mentioned formulas [A1] to [A5], PFPE represents the poly (oxyperfluoroalkylene) group, n represents an oxyethylene group , Preferably represents a number of 1 to 15, more preferably represents a number of 5 to 12, and further preferably represents a number of 7 to 12.

[화학식 2](2)

Figure pct00002
Figure pct00002

그 중에서도, 본 발명의 (b)양말단에 중합성기를 갖는 퍼플루오로폴리에테르는, 폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 양말단에, 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 이 순으로 개재하여, 즉, 폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 양말단에 폴리(옥시알킬렌)기가 각각 결합하고, 이 양단의 각 폴리(옥시알킬렌)기에 각각 우레탄결합이 1개 결합하고, 그리고 이 양단의 각 우레탄결합에 활성에너지선 중합성기가 각각 결합한 퍼플루오로폴리에테르인 것이 바람직하다. 나아가, 상기 퍼플루오로폴리에테르에 있어서, 활성에너지선 중합성기가 적어도 2개 이상의 활성에너지선 중합성 부분을 갖는 기인 퍼플루오로폴리에테르인 것이 바람직하다.Among them, the perfluoropolyether having a polymerizable group at both ends of the (b) end of the present invention is preferably a poly (oxyalkylene) group and a poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) A poly (oxyalkylene) group is bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group, and each of the poly (oxyalkyl Is preferably a perfluoropolyether in which one urethane bond is bonded to each of the urethane bonds, and the active energy prepolymerizable groups are bonded to the urethane bonds at both ends, respectively. Further, in the perfluoropolyether, it is preferable that the active energy pre-polymerizable group is a perfluoropolyether which is a group having at least two active energy pre-polymerizable moieties.

본 발명에 있어서 (b)양말단에 중합성기를 갖는 퍼플루오로폴리에테르는, 상기 서술한 (a)활성에너지선 경화성 다관능모노머 100질량부에 대하여, 0.1~10질량부, 바람직하게는 0.2~5질량부의 비율로 사용하는 것이 바람직하다.In the present invention, perfluoropolyether (b) having a polymerizable group at both ends is used in an amount of 0.1 to 10 parts by mass, preferably 0.2 (parts by mass) per 100 parts by mass of the above-mentioned active energy ray- To 5 parts by mass.

상기 (b)양말단에 중합성기를 갖는 퍼플루오로폴리에테르는, 예를 들어, 폴리(옥시퍼플루오로알킬렌)기의 양말단에 폴리(옥시알킬렌)기를 개재하여 하이드록시기를 갖는 화합물에 있어서, 그 양단의 하이드록시기에 대하여 2-(메트)아크릴로일옥시에틸이소시아네이트나 1,1-비스((메트)아크릴로일옥시메틸)에틸이소시아네이트 등의 중합성기를 갖는 이소시아네이트 화합물을 우레탄화반응시키는 방법, (메트)아크릴산클로라이드 또는 클로로메틸스티렌을 탈염산반응시키는 방법, (메트)아크릴산을 탈수반응시키는 방법, 무수이타콘산을 에스테르화반응시키는 방법 등에 의해 얻어진다.The perfluoropolyether having a polymerizable group at both ends of the above (b) can be obtained, for example, by reacting a compound having a hydroxy group via a poly (oxyalkylene) group at both terminals of the poly (oxyperfluoroalkylene) group An isocyanate compound having a polymerizable group such as 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate with respect to the hydroxyl groups at both ends thereof, A method in which (meth) acrylic acid chloride or chloromethylstyrene is dehydrochlorinated, a method in which (meth) acrylic acid is dehydrated, a method in which itaconic anhydride is esterified, and the like.

그 중에서도, 폴리(옥시퍼플루오로알킬렌)기의 양말단에 폴리(옥시알킬렌)기를 개재하여 하이드록시기를 갖는 화합물에 있어서, 그 양단의 하이드록시기에 대하여, 2-(메트)아크릴로일옥시에틸이소시아네이트나 1,1-비스((메트)아크릴로일옥시메틸)에틸이소시아네이트 등의 중합성기를 갖는 이소시아네이트 화합물을 우레탄화반응시키는 방법, 혹은, 이 하이드록시기에 대하여 (메트)아크릴산클로라이드 또는 클로로메틸스티렌을 탈염산반응시키는 방법이, 반응이 용이한 점에서 특히 바람직하다.Among them, in the case of a compound having a hydroxy group via a poly (oxyalkylene) group at both terminals of the poly (oxyperfluoroalkylene) group, it is preferable to use 2- (meth) acryloyl (Meth) acryloyloxymethyl) ethyl isocyanate, or a method in which an isocyanate compound having a polymerizable group such as 1,1-bis ((meth) acryloyloxymethyl) Or a method in which chloromethylstyrene is subjected to a dehydrochlorination reaction is particularly preferable in that the reaction is easy.

한편 본 발명의 경화성 조성물에는, (b)폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 양말단에, 폴리(옥시알킬렌)기를 개재하거나 또는 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 이 순으로 개재하여, 활성에너지선 중합성기를 갖는 퍼플루오로폴리에테르에 더하여, 폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 일단에 폴리(옥시알킬렌)기를 개재하거나 또는 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 이 순으로 개재하여, 활성에너지선 중합성기를 갖고, 또한 그 타단에 폴리(옥시알킬렌)기를 개재하여 하이드록시기를 갖는 퍼플루오로폴리에테르나, 폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 양단에 폴리(옥시알킬렌)기를 개재하여 하이드록시기를 하는 퍼플루오로폴리에테르[활성에너지선 중합성기를 갖지 않는 화합물]가 포함되어 있을 수도 있다.In the curable composition of the present invention, the poly (oxyalkylene) group or the poly (oxyalkylene) group and the poly (oxyalkylene) group are bonded to both ends of the molecular chain containing the poly (oxyperfluoroalkylene) (Oxyalkylene) group is bonded to one end of the molecular chain including the poly (oxyperfluoroalkylene) group in addition to the perfluoropolyether having the active energy pre-polymerizable group interposed therebetween in the order of Or poly (oxyalkylene) group and one urethane bond in this order, and having an active energy pre-polymerizable group at the other end thereof and a hydroxy group-containing perfluoropolyether , And a perfluoropolyether having a hydroxyl group via a poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group [compound having no active energy pre-polymerizable group] May be included.

[(c) 1~10μm의 평균입경을 갖는 유기미립자][(c) Organic fine particles having an average particle size of 1 to 10 m]

본 발명의 경화성 조성물에 있어서, 1~10μm의 평균입경을 갖는 유기미립자(이하, 간단히 「(c)유기미립자」라고도 칭함)는, 이 경화성 조성물로부터 형성되는 하드코트층의 표면을 요철형상으로 하여 방현성을 부여한다.In the curable composition of the present invention, the organic fine particles having an average particle diameter of 1 to 10 mu m (hereinafter, simply referred to as "(c) organic fine particles") have a surface of the hard coat layer formed of the curable composition It gives a sense of repulsion.

또한 유기미립자는, 그 굴절률과 하드코트층형성재료인 경화성 조성물의 굴절률의 차이를 제어함으로써, 하드코트층의 헤이즈값을 제어하는 역할도 할 수 있다.The organic fine particles can also control the haze value of the hard coat layer by controlling the difference between the refractive index and the refractive index of the curable composition as the hard coat layer forming material.

상기 유기미립자의 형상은 특별히 한정되지 않으나, 예를 들어, 비즈상의 대략 구형일 수도 있고, 분말 등의 부정형인 것일 수도 있는데, 대략 구형인 것이 바람직하고, 보다 바람직하게는, 애스펙트비가 1.5 이하인 대략 구형의 입자이며, 가장 바람직하게는 진구상 입자이다.The shape of the organic fine particles is not particularly limited. For example, the shape of the organic fine particles may be a substantially spherical shape of a bead shape, or a shape of an irregular shape such as a powder, but is preferably a substantially spherical shape. More preferably, Particles, and most preferably a true spherical particle.

상기 유기미립자로는, 예를 들어, 폴리메타크릴산메틸입자(PMMA입자), 실리콘입자, 폴리스티렌입자, 폴리카보네이트입자, 아크릴스티렌입자, 벤조구아나민입자, 멜라민입자, 폴리올레핀입자, 폴리에스테르입자, 폴리아미드입자, 폴리이미드입자, 폴리불화에틸렌입자 등을 들 수 있다. 이들 유기미립자는, 1종류를 단독으로 사용할 수도 있고, 2종류 이상을 병용할 수도 있다.The organic fine particles include, for example, polymethyl methacrylate particles (PMMA particles), silicon particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, Polyamide particles, polyimide particles, polyfluorinated ethylene particles, and the like. These organic fine particles may be used singly or in combination of two or more kinds.

그 중에서도, 상기 유기미립자로서 폴리메타크릴산메틸입자를 호적하게 이용할 수 있다.Among them, polymethyl methacrylate particles can be suitably used as the organic fine particles.

본 발명에서 사용하는 상기 유기미립자의 평균입경은 1~10μm의 범위이며, 바람직하게는 3~8μm의 범위인 것이 바람직하다. 여기서 평균입경(μm)이란, Mie이론에 기초한 레이저 회절·산란법에 의해 측정하여 얻어지는 50%체적직경(미디언직경)이다. 상기 유기미립자의 평균입경이 상기 수치범위보다 커지면, 디스플레이의 화상선명성이 저하되고, 또한 상기 수치범위보다 작으면, 충분한 방현성을 얻을 수 없고, 눈부심도 커진다는 문제가 생기기 쉬워진다. 한편 상기 유기미립자는, 그 입도분포에 대해서는 특별히 한정되지 않으나, 입경이 갖추어진 단분산의 미립자인 것이 바람직하다.The average particle diameter of the organic fine particles used in the present invention is in the range of 1 to 10 mu m, preferably 3 to 8 mu m. Here, the average particle diameter (μm) is a 50% volume diameter (median diameter) obtained by laser diffraction / scattering method based on the Mie theory. When the average particle diameter of the organic fine particles is larger than the above-mentioned range, the image sharpness of the display is deteriorated. When the average particle diameter is smaller than the above-mentioned range, sufficient diffusibility can not be obtained and the problem of increased glare is likely to occur. On the other hand, the particle size distribution of the organic fine particles is not particularly limited, but is preferably monodisperse fine particles having a particle diameter.

상기 유기미립자는, 상기 (a)활성에너지선 경화성 다관능모노머의 경화물과의 굴절률차가 0~0.20인 굴절률을 가지고 이루어지는 유기미립자인 것이 바람직하고, 상기 굴절률차가 0~0.10인 것이 더욱 바람직하다.The organic fine particles are preferably organic fine particles having a refractive index with a difference in refractive index between the (a) active energy ray-curable polyfunctional monomer and the cured product being 0 to 0.20, and more preferably the refractive index difference is 0 to 0.10.

또한, 상기 유기미립자는, 그 평균입경이, 후술하는 본 발명의 경화성 조성물로부터 얻어지는 경화막의 막두께에 대하여, 유기미립자의 평균입경b/막두께a=0.7~1.0의 범위를 만족시키도록 선택하는 것이 바람직하다.The average particle diameter of the organic fine particles is selected so as to satisfy the range of the average particle diameter b / the thickness a of the organic fine particles a = 0.7 to 1.0 with respect to the film thickness of the cured film obtained from the curable composition of the present invention .

상기 유기미립자는, 시판품을 호적하게 이용할 수 있고, 예를 들어, 테크폴리머(등록상표)MBX시리즈, SBX시리즈, MSX시리즈, SMX시리즈, SSX시리즈, BMX시리즈, ABX시리즈, ARX시리즈, AFX시리즈, MB시리즈, MBP시리즈, MB-C시리즈, ACX시리즈, ACP시리즈[이상, 세키수이화성품공업(주)제]; 토스펄(등록상표)시리즈[모멘티브·퍼포먼스·마테리얼즈·재팬(동)제]; 에포스타(등록상표)시리즈, MA시리즈, ST시리즈, MX시리즈[이상, (주)일본촉매제]; 옵트비즈(등록상표)시리즈[닛산화학공업(주)제]; 플로우비즈시리즈[스미토모세이카(주)제]; 트레팔(등록상표)PPS, PAI, PES, EP[이상, 토레이(주)제]; 3M(등록상표) 다이니온TF마이크로파우더시리즈[3M사제]; 케미스노우(등록상표)MX시리즈, MZ시리즈, MR시리즈, KMR시리즈, KSR시리즈, MP시리즈, SX시리즈, SGP시리즈[이상, 소켄화학(주)제]; 태프틱(등록상표)AR650시리즈, AR-750시리즈, FH-S시리즈, A-20, YK시리즈, ASF시리즈, HU시리즈, F시리즈, C시리즈, WS시리즈[이상, 토요보(주)제]; 아트펄(등록상표)GR시리즈, SE시리즈, G시리즈, GS시리즈, J시리즈, MF시리즈, BE시리즈[이상, 네가미공업(주)제]; 신에쯔실리콘(등록상표)KMP시리즈[신에쯔화학공업(주)제] 등을 이용할 수 있다.The organic fine particles may be commercially available products and can be suitably used for various applications such as, for example, TECH POLYMER (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, ARX series, AFX series, MB series, MBP series, MB-C series, ACX series, and ACP series (manufactured by Sekisui Chemical Co., Ltd.); Tospel (registered trademark) series [Momentive Performance Materials, Japan (trade name)]; EPOSTAR (registered trademark) series, MA series, ST series, MX series (manufactured by Nippon Kogyo Co., Ltd.); Optobiz (registered trademark) series (manufactured by Nissan Chemical Industries, Ltd.); Flow beads series (manufactured by Sumitomo Seika Co., Ltd.); PPS, PAI, PES, EP (trade names, manufactured by Toray Industries, Inc.); 3M (registered trademark) Dynion TF Micro Powder Series [manufactured by 3M Co.]; KMY Snow (registered trademark) MX series, MZ series, MR series, KMR series, KSR series, MP series, SX series, SGP series (manufactured by Soeken Chemical Co., Ltd.); F-series, A-20, YK series, ASF series, HU series, F series, C series and WS series [manufactured by Toyobo Co., Ltd.] ; Art Pearl (registered trademark) GR series, SE series, G series, GS series, J series, MF series, BE series (manufactured by Negami Kogyo Co., Ltd.); Shinetsu Silicone (registered trademark) KMP series (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be used.

본 발명에 있어서 (c)유기미립자는, 상기 서술한 (a)활성에너지선 경화성 다관능모노머 100질량부에 대하여, 8~30질량부, 바람직하게는 8~20질량부의 비율로 사용하는 것이 바람직하다.In the present invention, (c) the organic fine particles are preferably used in a proportion of 8 to 30 parts by mass, preferably 8 to 20 parts by mass, per 100 parts by mass of the above-mentioned active energy ray-curable polyfunctional monomer (a) Do.

[(d)활성에너지선에 의해 라디칼을 발생하는 중합개시제][(d) Polymerization initiator which generates a radical by an active energy ray]

본 발명의 경화성 조성물에 있어서 바람직한 활성에너지선에 의해 라디칼을 발생하는 중합개시제(이하, 간단히 「(d)중합개시제」라고도 칭함)는, 예를 들어, 전자선, 자외선, X선 등의 활성에너지선에 의해, 특히 자외선조사에 의해 라디칼을 발생하는 중합개시제이다.The polymerization initiator (hereinafter, simply referred to as &quot; (d) polymerization initiator &quot;) which generates a radical by a preferred activation energy ray in the curable composition of the present invention is, for example, an active energy ray such as electron beam, ultraviolet ray, In particular, a polymerization initiator that generates radicals by ultraviolet irradiation.

상기 (d)중합개시제로는, 예를 들어 벤조인류, 알킬페논류, 티옥산톤류, 아조류, 아지드류, 디아조류, o-퀴논디아지드류, 아실포스핀옥사이드류, 옥심에스테르류, 유기과산화물, 벤조페논류, 비스쿠마린류, 비스이미다졸류, 티타노센류, 티올류, 할로겐화탄화수소류, 트리클로로메틸트리아진류, 혹은 요오드늄염, 설포늄염 등의 오늄염류 등을 들 수 있다. 이들은 1종 단독으로 혹은 2종 이상을 혼합하여 이용할 수도 있다.Examples of the polymerization initiator (d) include, for example, organic peroxides such as benzoin, alkylphenols, thioxanthones, azo dyes, azides, diazo dyes, o-quinonediazides, acylphosphine oxides, oxime esters, Peroxides, benzophenones, biscumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyl triazine, and onium salts such as iodonium salts and sulfonium salts. These may be used singly or in combination of two or more.

그 중에서도 본 발명에서는, 투명성, 표면경화성, 박막경화성의 관점에서 (d)중합개시제로서, 알킬페논류를 사용하는 것이 바람직하다. 알킬페논류를 사용함으로써, 내찰상성이 보다 향상된 경화막을 얻을 수 있다.Among them, in the present invention, it is preferable to use alkylphenols as the polymerization initiator (d) from the viewpoints of transparency, surface hardenability and thin film curability. By using alkylphenols, a cured film having improved scratch resistance can be obtained.

상기 알킬페논류로는, 예를 들어, 1-하이드록시시클로헥실=페닐=케톤, 2-하이드록시-2-메틸-1-페닐프로판-1-온, 2-하이드록시-1-(4-(2-하이드록시에톡시)페닐)-2-메틸프로판-1-온, 2-하이드록시-1-(4-(4-(2-하이드록시-2-메틸프로피오닐)벤질)페닐)-2-메틸프로판-1-온 등의 α-하이드록시알킬페논류; 2-메틸-1-(4-(메틸티오)페닐)-2-몰포리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-몰포리노페닐)부탄-1-온 등의 α-아미노알킬페논류; 2,2-디메톡시-1,2-디페닐에탄-1-온; 페닐글리옥실산메틸 등을 들 수 있다.The alkylphenols include, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan- 2-methylpropan-1-one, and other? -Hydroxyalkylphenones; 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2-benzyl- Alpha -aminoalkylphenes; 2,2-dimethoxy-1,2-diphenylethan-1-one; And methyl phenylglyoxylate.

본 발명에 있어서 (d)중합개시제는, 상기 서술한 (a)활성에너지선 경화성 다관능모노머 100질량부에 대하여, 1~20질량부, 바람직하게는 2~10질량부의 비율로 사용하는 것이 바람직하다.In the present invention, the polymerization initiator (d) is preferably used in a proportion of 1 to 20 parts by mass, preferably 2 to 10 parts by mass, per 100 parts by mass of the above-mentioned active energy ray-curable polyfunctional monomer (a) Do.

[(e)용매][(e) Solvent]

본 발명의 경화성 조성물은, 추가로 (e)용매를 포함하고, 즉 바니시(막형성재료)의 형태로 할 수 있다.The curable composition of the present invention may further include (e) a solvent, that is, in the form of a varnish (film forming material).

상기 용매로는, 상기 (a)~(d)성분을 용해·분산하고, 또한 후술하는 경화막(하드코트층) 형성에 따른 도공시의 작업성이나 경화전후의 건조성 등을 고려하여 적당히 선택하면 되고, 예를 들어, 벤젠, 톨루엔, 자일렌, 에틸벤젠, 테트라인 등의 방향족 탄화수소류; n-헥산, n-헵탄, 미네랄스피릿, 시클로헥산 등의 지방족 또는 지환식 탄화수소류; 염화메틸, 브롬화메틸, 요오드화메틸, 디클로로메탄, 클로로포름, 사염화탄소, 트리클로로에틸렌, 퍼클로로에틸렌, o-디클로로벤젠 등의 할로겐화물류; 아세트산에틸, 아세트산프로필, 아세트산부틸, 메톡시부틸아세테이트, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 프로필렌글리콜모노메틸에테르아세테이트 등의 에스테르류 또는 에스테르에테르류; 디에틸에테르, 테트라하이드로푸란, 1,4-디옥산, 메틸셀로솔브, 에틸셀로솔브, 부틸셀로솔브, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 프로필렌글리콜모노-n-프로필에테르, 프로필렌글리콜모노이소프로필에테르, 프로필렌글리콜모노-n-부틸에테르 등의 에테르류; 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 디-n-부틸케톤, 시클로헥사논 등의 케톤류; 메탄올, 에탄올, n-프로판올, 이소프로필알코올, n-부탄올, 이소부틸알코올, tert-부틸알코올, 2-에틸헥실알코올, 벤질알코올, 에틸렌글리콜 등의 알코올류; N,N-디메틸포름아미드, N,N-디메틸아세트아미드 등의 아미드류; 디메틸설폭시드 등의 설폭시드류; N-메틸-2-피롤리돈 등의 복소환식 화합물류, 그리고 이들의 2종 이상의 혼합용매를 들 수 있다.As the solvent, it is preferable to dissolve and disperse the components (a) to (d) and appropriately select in consideration of workability at the time of coating and dryness before and after curing due to formation of a cured film (hard coat layer) For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetraene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit and cyclohexane; Halogenated products such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, perchlorethylene and o-dichlorobenzene; Esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate and propylene glycol monomethyl ether acetate; Diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , Propylene glycol monoisopropyl ether, and propylene glycol mono-n-butyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; Alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol and ethylene glycol; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Sulfoxides such as dimethyl sulfoxide; Methyl-2-pyrrolidone and the like, and mixed solvents of two or more thereof.

또한, 도공 후의 건조시에 있어서의 상기 미립자의 분산성을 제어하는 목적으로, 고비점의 용매를 사용할 수도 있다.Further, for the purpose of controlling the dispersibility of the fine particles at the time of drying after coating, a solvent having a high boiling point may be used.

이러한 용매로는, 예를 들어, 아세트산시클로헥실, 프로필렌글리콜디아세테이트, 1,3-부틸렌글리콜디아세테이트, 1,4-부탄디올디아세테이트, 1,6-헥산디올디아세테이트, 에틸렌글리콜모노부틸에테르아세테이트, 디에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜모노부틸에테르아세테이트, 디프로필렌글리콜메틸에테르아세테이트, 3-메톡시부틸아세테이트, 에틸렌글리콜, 디에틸렌글리콜, 프로필렌글리콜, 1,3-부틸렌글리콜, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노프로필에테르, 디에틸렌글리콜모노부틸에테르, 디프로필렌글리콜모노메틸에테르, 트리프로필렌글리콜모노메틸에테르, 트리프로필렌글리콜모노에틸에테르, 트리프로필렌글리콜모노프로필에테르, 트리프로필렌글리콜모노부틸에테르, 3-메톡시부탄올, 디프로필렌글리콜디메틸에테르, 디프로필렌글리콜=메틸=프로필=에테르 등을 들 수 있다.Such solvents include, for example, cyclohexyl acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, ethylene glycol monobutyl ether Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol, Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tri Propylene glycol monobutyl ether, 3-methoxybutanol, dipropylene Recall dimethyl ether, dipropylene glycol methyl = = = propyl ether and the like can be given.

이들 (e)용매의 사용량은 특별히 한정되지 않으나, 예를 들어, 본 발명의 경화성 조성물에 있어서의 고형분 농도가 1~70질량%, 바람직하게는 5~50질량%가 되는 농도로 사용한다. 여기서 고형분 농도(불휘발분 농도라고도 칭함)란, 본 발명의 경화성 조성물의 상기 (a)~(e)성분(및 필요에 따라 기타 첨가제)의 총질량(합계질량)에 대한 고형분(전체 성분으로부터 용매성분을 제외한 것)의 함유량을 나타낸다.The amount of the solvent (e) to be used is not particularly limited. For example, the concentration of the solid content in the curable composition of the present invention is 1 to 70% by mass, preferably 5 to 50% by mass. Here, the solid concentration (also referred to as a non-volatile matter concentration) refers to a solid content (total mass) of the total mass (total mass) of the components (a) to (e) of the curable composition of the present invention (Excluding the component).

[기타 첨가물][Other additives]

또한, 본 발명의 경화성 조성물에는, 본 발명의 효과를 손상시키지 않는 한, 필요에 따라 일반적으로 첨가되는 첨가제, 예를 들어, 중합금지제, 광증감제, 레벨링제, 계면활성제, 밀착성 부여제, 가소제, 자외선흡수제, 산화방지제, 저장안정제, 대전방지제, 무기충전제, 안료, 염료 등을 적당히 배합할 수 있다.The curable composition of the present invention may contain additives generally added as needed, for example, a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an adhesion imparting agent, A plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like.

또한, 경화막의 헤이즈값을 제어하는 목적으로, 산화티탄 등의 무기미립자를 배합할 수도 있다.For the purpose of controlling the haze value of the cured film, inorganic fine particles such as titanium oxide may also be blended.

<경화막><Cured film>

본 발명의 경화성 조성물은, 기재 상에 도포(코팅)하여 도막을 형성하고, 이 도막에 활성에너지선을 조사하여 중합(경화)시킴으로써, 경화막을 형성할 수 있다. 이 경화막도 본 발명의 대상이다. 또한 후술하는 하드코트필름에 있어서의 하드코트층을 이 경화막으로 이루어진 것으로 할 수 있다.The curable composition of the present invention can be formed by coating (coating) a coating film on a base material, and irradiating the coating film with active energy rays to polymerize (cure) the cured film. This cured film is also an object of the present invention. Further, the hard coat layer in the hard coat film described later can be made of this cured film.

이 경우의 상기 기재로는, 예를 들어, 각종 수지(폴리카보네이트, 폴리메타크릴레이트, 폴리스티렌, 폴리에틸렌테레프탈레이트(PET)나 폴리에틸렌나프탈레이트(PEN) 등의 폴리에스테르, 폴리올레핀, 폴리아미드, 폴리이미드, 에폭시수지, 멜라민수지, 트리아세틸셀룰로오스, 아크릴로니트릴-부타디엔-스티렌 공중합체(ABS), 아크릴로니트릴-스티렌 공중합체(AS), 노보넨계 수지 등), 금속, 목재, 종이, 유리, 슬레이트 등을 들 수 있다. 이들 기재의 형상은 판상, 필름상 또는 3차원 성형체여도 된다.In this case, the above substrate may be a substrate made of various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin, polyamide, polyimide (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin, etc.), metal, wood, paper, glass, slate And the like. The shape of these substrates may be a plate-like, film-like or three-dimensional formed body.

상기 기재 상에의 도포방법은, 캐스트코트법, 스핀코트법, 블레이드코트법, 딥코트법, 롤코트법, 스프레이코트법, 바코트법, 다이코트법, 잉크젯법, 인쇄법(볼록판, 오목판, 평판, 스크린인쇄 등) 등을 적당히 선택할 수 있고, 그 중에서도 롤·투·롤(roll-to-roll)법에 이용할 수 있고, 또한 박막도포성의 관점에서, 볼록판인쇄법, 특히 그래비어코트법을 이용하는 것이 바람직하다. 또한 사전에 구멍직경이 0.2μm 정도인 필터 등을 이용하여 경화성 조성물을 여과한 후, 도포에 제공하는 것이 바람직하다. 한편 도포할 때, 필요에 따라 이 경화성 조성물에 용제를 추가로 첨가할 수도 있다. 이 경우의 용제로는 상기 서술한 [(e)용매]에서 든 다양한 용매를 들 수 있다.The coating method on the substrate can be carried out by a known method such as a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, , A flat plate, a screen printing, etc.) can be appropriately selected. Among them, it can be used for a roll-to-roll method and from the viewpoint of thin film coating, It is preferable to use the method. Further, it is preferable to filter the curable composition by using a filter having a pore diameter of about 0.2 mu m or the like, and then to provide it for application. On the other hand, a solvent may be further added to the curable composition when necessary. Examples of the solvent in this case include various solvents from the above-mentioned [(e) solvent].

기재 상에 경화성 조성물을 도포하고 도막을 형성한 후, 필요에 따라 핫플레이트 또는 오븐 등으로 도막을 예비건조하여 용매를 제거한다(용매제거공정). 이때의 가열건조의 조건으로는, 예를 들어, 40~120℃에서, 30초~10분 정도로 하는 것이 바람직하다.After the curable composition is applied on the substrate to form a coating film, the coating is preliminarily dried by a hot plate or an oven to remove the solvent (solvent removal step). The heating and drying conditions at this time are preferably, for example, 40 to 120 DEG C for 30 seconds to 10 minutes.

건조 후, 자외선 등의 활성에너지선을 조사하여, 도막을 경화시킨다. 활성에너지선으로는, 자외선, 전자선, X선 등을 들 수 있고, 특히 자외선이 바람직하다. 자외선조사에 이용하는 광원으로는, 태양광선, 케미칼램프, 저압수은등, 고압수은등, 메탈할라이드램프, 크세논램프, UV-LED 등을 사용할 수 있다.After drying, an active energy ray such as ultraviolet rays is irradiated to cure the coating film. Examples of the active energy ray include ultraviolet rays, electron rays and X-rays, and ultraviolet rays are particularly preferable. As a light source used for ultraviolet irradiation, a sun ray, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED and the like can be used.

나아가 그 후, 포스트베이크를 행함으로써, 구체적으로는 핫플레이트, 오븐 등을 이용하여 가열함으로써 중합을 완결시켜도 된다.Thereafter, post-baking may be performed to complete the polymerization, specifically by heating using a hot plate, an oven, or the like.

한편, 형성되는 경화막의 두께는, 건조, 경화 후에 있어서, 통상 0.01~50μm, 바람직하게는 0.05~20μm이다.On the other hand, the thickness of the formed cured film is usually 0.01 to 50 占 퐉, preferably 0.05 to 20 占 퐉 after drying and curing.

<하드코트필름><Hard Coat Film>

본 발명의 경화성 조성물을 이용하여, 필름기재의 적어도 일방의 면(표면)에 하드코트층을 구비하는 하드코트필름을 제조할 수 있다. 이 하드코트필름도 본 발명의 대상이며, 이 하드코트필름은, 예를 들어 터치패널이나 액정디스플레이 등의 각종 표시소자 등의 표면을 보호하기 위하여 호적하게 이용된다.By using the curable composition of the present invention, it is possible to produce a hard coat film having a hard coat layer on at least one surface (surface) of a film substrate. This hard coat film is also an object of the present invention. This hard coat film is used to protect the surface of various display elements such as a touch panel or a liquid crystal display, for example.

본 발명의 하드코트필름에 있어서의 하드코트층은, 상기 서술한 본 발명의 경화성 조성물을 필름기재 상에 도포하여 도막을 형성하는 공정과, 이 도막에 자외선 등의 활성에너지선을 조사하고 이 도막을 경화시키는 공정을 포함하는 방법에 의해 형성할 수 있다.The hard coat layer in the hard coat film of the present invention may be obtained by a process comprising the steps of applying the curable composition of the present invention described above onto a film substrate to form a coating film and irradiating this coating film with an active energy ray such as ultraviolet rays, And a step of curing the resin.

상기 필름기재로는, 상기 서술한 <경화막>에서 든 기재 중, 광학용도로 사용가능한 각종의 투명한 수지제 필름이 이용된다. 바람직하게는 예를 들어, 폴리에틸렌테레프탈레이트(PET), 폴리부틸렌테레프탈레이트(PBT), 폴리에틸렌나프탈레이트(PEN) 등의 폴리에스테르, 폴리카보네이트, 폴리메타크릴레이트, 폴리스티렌, 폴리올레핀, 폴리아미드, 폴리이미드, 트리아세틸셀룰로오스 등으로부터 선택되는 수지제 필름을 들 수 있다.As the film substrate, various transparent resin films usable for optical use among the substrates in the <cured film> described above are used. Preferably, for example, a polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, Amide, triacetyl cellulose, and the like.

또한 상기 필름기재 상에의 경화성 조성물의 도포방법(도막형성공정) 및 도막에의 활성에너지선 조사방법(경화공정)은, 상기 서술한 <경화막>에 든 방법을 이용할 수 있다. 또한 도막형성공정 후, 필요에 따라 이 도막을 건조하고 용매제거하는 공정을 포함할 수 있다. 그 경우, 상기 서술한 <경화막>에 든 도막의 건조방법(용매제거공정)을 이용할 수 있다.The method described above for the &quot; cured film &quot; can be used for the coating method (film forming step) of the curable composition on the film substrate and the method of irradiating the coating film with active energy rays (curing step). Further, after the coating film forming step, the coating film may be dried and the solvent may be removed if necessary. In this case, a drying method (solvent removal step) of the coating film in the above-described <cured film> can be used.

이리 하여 얻어진 하드코트층은, 상기 유기미립자의 평균입경에 비해 1배~10/7배의 두께가 되도록 설정하는 것이 바람직하다. 예를 들어 상기 하드코트층의 두께는, 바람직하게는 1~20μm, 보다 바람직하게는 3~10μm이다.The hard coat layer thus obtained is preferably set to have a thickness of 1 to 10/7 times the average particle diameter of the organic fine particles. For example, the thickness of the hard coat layer is preferably 1 to 20 占 퐉, more preferably 3 to 10 占 퐉.

실시예Example

이하, 실시예를 들어, 본 발명을 보다 구체적으로 설명하나, 본 발명은 하기의 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.

한편, 실시예에 있어서, 시료의 조제 및 물성의 분석에 이용한 장치 및 조건은, 이하와 같다.On the other hand, in the examples, the apparatus and conditions used for preparation of the sample and analysis of the physical properties are as follows.

(1) 바코트도포(1) Barcoat application

장치: (주)에스엠티제 PM-9050MCDevice: PM-9050MC manufactured by SMT Co., Ltd.

바1: OSG시스템프로덕츠(주)제 A-Bar OSP-30, 최대 웨트막두께 30μm(와이어바#12 상당)Bar 1: A-Bar OSP-30 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 30 μm (equivalent to wire bar # 12)

바2: OSG시스템프로덕츠(주)제 A-Bar OSP-22, 최대 웨트막두께 22μm(와이어바#9 상당)Bar 2: A-Bar OSP-22 manufactured by OSG System Products Co., Ltd., maximum wet film thickness 22 탆 (equivalent to wire bar # 9)

도포속도: 4m/분Application speed: 4 m / min

(2) 오븐(2) Ovens

장치: 애드밴텍토요(주)제 무진건조기 DRC433FADevice: Made by ADVANTECH TOYOTA CO., LTD. Dryer DRC433FA

(3) UV경화(3) UV curing

장치: 헤레우스(주)제 CV-110QC-GApparatus: CV-110QC-G manufactured by Heraeus Co., Ltd.

램프: 헤레우스(주)제 고압수은램프H-bulbLamp: High pressure mercury lamp made by Heraeus Co., Ltd. H-bulb

(4) 막두께(4) Thickness

장치: (주)니콘제 디지털측장기 디지마이크로 MH-15M + 카운터TC-101Device: Digitron MH-15M + counter TC-101 (manufactured by Nikon Corporation)

(5) 광택도(5) Glossiness

장치: 코니카미놀타(주)제 광택계 GM-268PlusApparatus: Polishing system made by Konica Minolta Co., Ltd. GM-268Plus

측정각도: 60도Measuring angle: 60 degrees

(6) 찰상시험(6) Scratch test

장치: 신토과학(주)제 왕복마모시험기 TRIBOGEAR TYPE: 30SDevice: a reciprocating abrasion tester made by Shinto Scientific Co., Ltd. TRIBOGEAR TYPE: 30S

주사속도: 3,000mm/분Scanning speed: 3,000 mm / min

주사거리: 50mmScanning distance: 50mm

(7) 전광선투과율, 헤이즈(7) Total light transmittance, haze

장치: 일본전색공업(주)제 헤이즈미터 NDH5000Apparatus: Haze meter NDH5000 manufactured by Fuming Kogyo Co., Ltd.

(8) 접촉각(8) Contact angle

장치: 쿄와계면과학(주)제 DropMaster DM-501Apparatus: DropMaster DM-501 made by Kyowa Interface Science Co., Ltd.

측정온도: 20℃Measuring temperature: 20 ° C

또한, 약기호는 이하의 의미를 나타낸다.In addition, the weak symbols indicate the following meanings.

PFPE1: 양말단에 폴리(옥시알킬렌)기(반복단위수 8~9)를 개재하여 하이드록시기를 갖는 퍼플루오로폴리에테르[솔베이스페셜리티폴리머즈사제 Fluorolink 5147X]PFPE1: Perfluoropolyether having a hydroxy group (Fluorolink 5147X manufactured by Solvay Specialty Polymers) via a poly (oxyalkylene) group (number of repeating units: 8 to 9)

PFPE2: 양말단에 폴리(옥시알킬렌)기(반복단위수 5~6)를 개재하여 하이드록시기를 갖는 퍼플루오로폴리에테르[솔베이스페셜리티폴리머즈사제 Fluorolink 5158X]PFPE2: Perfluoropolyether having a hydroxy group (Fluorolink 5158X, manufactured by Solvay Specialty Polymers) via a poly (oxyalkylene) group (number of repeating units: 5 to 6)

PFPE3: 양말단에 하이드록시기를 갖는 퍼플루오로폴리에테르[솔베이스페셜리티폴리머즈사제 Fluorolink D]PFPE3: Perfluoropolyether having a hydroxy group at both terminals (Fluorolink D, manufactured by Solvay Specialty Polymers)

BEI: 1,1-비스(아크릴로일옥시메틸)에틸이소시아네이트[쇼와덴코(주)제 카렌즈(등록상표)BEI]BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate [CALENS (registered trademark) BEI manufactured by Showa Denko Co., Ltd.]

DBTDL: 디라우르산디부틸주석[도쿄화성공업(주)제]DBTDL: Dibutyl tin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

DPHA: 디펜타에리스리톨펜타아크릴레이트/디펜타에리스리톨헥사아크릴레이트 혼합물[일본화약(주)제 KAYALAD(등록상표)DPHA]DPHA: a mixture of dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate (KAYALAD (registered trademark) DPHA, manufactured by Nippon Gakuen Co., Ltd.)

PETA: 펜타에리스리톨트리아크릴레이트/펜타에리스리톨테트라아크릴레이트 혼합물[신나카무라화학공업(주)제 NK에스테르 A-TMM-3LM-N]PETA: a mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate (NK Ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd.)

UA: 6관능 지방족 우레탄아크릴레이트올리고머[다이셀·올넥스(주)제 EBECRYL(등록상표)5129]UA: hexafunctional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129 manufactured by Daicel Allynx Co., Ltd.)

SM4: 퍼플루오로폴리에테르구조를 갖는 UV반응형 불소계 표면개질제[DIC(주)제 메가팍(등록상표)RS-75, 유효성분 40질량%MEK/MIBK용액]SM4: UV reaction type fluorine surface modifier having a perfluoropolyether structure [Megapak (registered trademark) RS-75 manufactured by DIC Corporation, active ingredient 40% by mass MEK / MIBK solution]

FP1: 가교폴리메타크릴산메틸 진구상 입자[세키수이화성품공업(주)제 테크폴리머(등록상표)SSX-105, 평균입자경 5μm]FP1: Crosslinked polymethyl methacrylate spherical particles [Tech polymer (registered trademark) SSX-105 manufactured by Sekisui Densi Industry Co., Ltd., average particle size: 5 m]

FP2: 가교폴리메타크릴산메틸 진구상 입자[세키수이화성품공업(주)제 테크폴리머(등록상표)SSX-103, 평균입자경 3μm]FP2: Crosslinked polymethacrylate methylsulfide particles (TECH POLYMER (registered trademark) SSX-103 manufactured by Sekisui Chemical Co., Ltd., average particle size: 3 m)

FP3: 멜라민수지·실리카복합 진구상 입자[닛산화학공업(주)제 옵트비즈(등록상표)2000M, 평균입자경 2μm]FP3: melamine resin-silica complex spherical particles [Optobiz (registered trademark) 2000M, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 2 m]

FP4: 가교실리콘 진구상 입자[모멘티브·퍼포먼스·마테리얼즈(동)제 토스펄(등록상표)120, 평균입자경 2μm]FP4: Crosslinked silicone spherical particles [Mothermive Performance Materials (trade name: Jotospearl (registered trademark) 120, average particle size: 2 m)

FP5: 가교실리콘 진구상 입자[모멘티브·퍼포먼스·마테리얼즈(동)제제 토스펄(등록상표)145, 평균입자경 4.5μm]FP5: Cross-linked silicone spherical particles [Momentive Performance Materials (trade name) manufactured by Tohp Pearl (registered trademark) 145, average particle diameter 4.5 m)

FP6: 폴리오가노실세스퀴옥산 진구상 입자[신에쯔화학공업(주)제 신에쯔실리콘(등록상표)KMP-590, 평균입자경 2μm]FP6: polyorganosilsesquioxane gum spherical particles (Shin-Etsu Silicone (registered trademark) KMP-590 manufactured by Shin-Etsu Chemical Co., Ltd., average particle diameter 2 m)

IP1: 루틸형 산화티탄입자[테이카(주)제 JR-600E, 평균입자경 0.27μm]IP1: rutile titanium oxide particles (JR-600E, manufactured by Teika, average particle diameter: 0.27 m)

I2959: 2-하이드록시-1-(4-(2-하이드록시에톡시)페닐)-2-메틸프로판-1-온[BASF재팬(주)제 IRGACURE(등록상표)2959]I2959: 2-Hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [IRGACURE (registered trademark) 2959, BASF Japan)

EPA: p-디메틸아미노안식향산에틸[일본화약(주)제 KAYACURE(등록상표)EPA]EPA: Ethyl p-dimethylaminobenzoate (KAYACURE (registered trademark) EPA manufactured by Japan Chemical Industry Co., Ltd.)

PET: 양면이접착처리 폴리에틸렌테레프탈레이트(PET)필름[토레이(주)제 루밀러(등록상표)U403, 두께 100μm]PET: polyethylene terephthalate (PET) film (RUILLER (registered trademark) U403 made by Toray Co., Ltd., thickness: 100 m)

PC: 양면이접착처리 폴리카보네이트(PC)필름[미쯔비시가스화학(주)제 유피론(등록상표)·필름 FE-2000, 두께 100μm]PC: Adhesion-treated polycarbonate (PC) film on both sides (manufactured by Mitsubishi Gas Chemical Co., Ltd. U.Philon (registered trademark), film FE-2000,

TAC: 양면이접착처리 셀룰로오스트리아세테이트(TAC)필름[후지필름(주)제 후지택(등록상표)TD80ULM, 두께 80μm]TAC: Both sides of a cellulose acetate triacetate (TAC) film (Fujifilm (registered trademark) TD80ULM, thickness: 80 m)

AcOPr: 아세트산프로필AcOPr: Acetic acid propyl acetate

MEK: 메틸에틸케톤MEK: methyl ethyl ketone

MIBK: 메틸이소부틸케톤MIBK: methyl isobutyl ketone

PGME: 프로필렌글리콜모노메틸에테르PGME: Propylene glycol monomethyl ether

[합성예 1] 양말단에 폴리(옥시알킬렌)기를 개재하여 아크릴로일기를 갖는 퍼플루오로폴리에테르SM1의 제조[Synthesis Example 1] Preparation of perfluoropolyether SM1 having an acryloyl group via a poly (oxyalkylene) group at both terminals

스크류관에, PFPE1 1.05g(0.5mmol), BEI 0.26g(1.0mmol), DBTDL 0.01g(0.02mmol), 및 MEK 1.30g을 투입하였다. 이 혼합물을, 스터러칩을 이용하여 실온(약 23℃)에서 24시간 교반하였다. 이 반응혼합물을 MEK 3.93g으로 희석하여, 목적화합물인 SM1의 20질량% MEK용액을 얻었다.1.05 g (0.5 mmol) of PFPE1, 0.26 g (1.0 mmol) of BEI, 0.01 g (0.02 mmol) of DBTDL and 1.30 g of MEK were fed into a screw tube. This mixture was stirred at room temperature (about 23 ° C) for 24 hours using a stirrer. This reaction mixture was diluted with 3.93 g of MEK to obtain a 20 mass% MEK solution of the target compound SM1.

[합성예 2] 양말단에 폴리(옥시알킬렌)기를 개재하여 아크릴로일기를 갖는 퍼플루오로폴리에테르SM2의 제조[Synthesis Example 2] Preparation of perfluoropolyether SM2 having an acryloyl group via a poly (oxyalkylene) group at both terminals

스크류관에, PFPE2 1.89g(1.0mmol), BEI 0.52g(2.0mmol), DBTDL 0.01g(0.02mmol), 및 MEK 2.41g을 투입하였다. 이 혼합물을, 스터러칩을 이용하여 실온(약 23℃)에서 24시간 교반하여, 목적화합물인 SM2의 50질량% MEK용액을 얻었다.1.89 g (1.0 mmol) of PFPE2, 0.52 g (2.0 mmol) of BEI, 0.01 g (0.02 mmol) of DBTDL and 2.41 g of MEK were charged into a screw tube. This mixture was stirred at room temperature (about 23 ° C) for 24 hours using a stirrer chip to obtain a 50 mass% MEK solution of the target compound SM2.

[합성예 3] 양말단에 아크릴로일기를 갖는 퍼플루오로폴리에테르SM3의 제조[Synthesis Example 3] Preparation of perfluoropolyether SM3 having an acryloyl group at both ends

스크류관에, PFPE3 2.0g(1.0mmol), BEI 0.52g(2.0mmol), DBTDL 0.01g(0.02mmol), 및 MEK 2.52g을 투입하였다. 이 혼합물을, 스터러칩을 이용하여 실온(약 23℃)에서 24시간 교반하여, 목적화합물인 SM3의 50질량% MEK용액을 얻었다.2.0 g (1.0 mmol) of PFPE3, 0.52 g (2.0 mmol) of BEI, 0.01 g (0.02 mmol) of DBTDL and 2.52 g of MEK were fed into a screw tube. This mixture was stirred at room temperature (about 23 DEG C) for 24 hours using a stirrer chip to obtain a 50 mass% MEK solution of the objective compound SM3.

[실시예 1~5, 비교예 1~6][Examples 1 to 5, Comparative Examples 1 to 6]

표 1의 기재에 따라서 이하의 각 성분을 혼합하고, 표 1에 기재된 고형분 농도의 경화성 조성물을 조제하였다. 한편, 여기서 고형분이란 용매 이외의 성분을 가리킨다. 또한, 표 중, [부]란 [질량부]를 나타낸다.The following components were mixed according to the description of Table 1 to prepare a curing composition having the solid content concentration shown in Table 1. Here, the solid content refers to components other than the solvent. In the table, [part] means [part by mass].

(1) 다관능모노머: DPHA 50질량부, UA 30질량부, 및 PETA 20질량부(1) Multifunctional monomer: 50 parts by mass of DPHA, 30 parts by mass of UA, and 20 parts by mass of PETA

(2) 표면개질제: 표 1에 기재된 표면개질제를 표 1에 기재된 양(고형분 또는 유효성분환산)(2) Surface modifier: The surface modifier shown in Table 1 was added in an amount (in terms of solid content or effective ingredient)

(3) 유기미립자: 표 1에 기재된 유기미립자를 표 1에 기재된 양(3) Organic fine particles: The organic fine particles shown in Table 1 were added in the amounts shown in Table 1

(4) 중합개시제: I2959 5질량부(4) Polymerization initiator: I2959 5 parts by mass

(5) 용매: PGME 표 1에 기재된 양(5) Solvent: PGME The amount shown in Table 1

이 경화성 조성물을, A4사이즈의 양면이접착처리 PET필름[토레이(주)제 루밀러(등록상표)U403, 두께 100μm] 상에, 표 2에 기재된 바를 사용하여 바코트도포하여 도막을 얻었다. 이 도막을 120℃의 오븐에서 3분간 건조시켜 용매를 제거하였다. 얻어진 막을, 질소분위기하, 노광량 500mJ/cm2의 UV광을 조사하여 노광함으로써, 표 2에 나타낸 두께의 하드코트층(경화막)을 갖는 하드코트필름을 제작하였다.This curable composition was applied to a bar coater on A4 size, both sides of which were subjected to a bonding treatment PET film (RUMLERER (registered trademark) U403 (thickness: 100 m), manufactured by Toray Co., Ltd.) to obtain a coated film. The coating film was dried in an oven at 120 캜 for 3 minutes to remove the solvent. The resultant film was exposed to UV light with an exposure amount of 500 mJ / cm 2 under a nitrogen atmosphere to produce a hard coat film having a hard coat layer (cured film) having a thickness shown in Table 2. [

[실시예 6~12][Examples 6 to 12]

표 1의 기재에 따라 이하의 각 성분을 혼합하고, 고형분 농도 40질량%의 경화성 조성물을 조제하였다.The following components were mixed according to the description of Table 1 to prepare a curable composition having a solid content concentration of 40 mass%.

(1) 다관능모노머: DPHA 50질량부, UA 30질량부, 및 PETA 20질량부(1) Multifunctional monomer: 50 parts by mass of DPHA, 30 parts by mass of UA, and 20 parts by mass of PETA

(2) 표면개질제: SM1 1질량부(고형분환산)(2) Surface modifier: SM1 1 part by mass (in terms of solid content)

(3) 유기미립자: 표 1에 기재된 유기미립자를 표 1에 기재된 양(3) Organic fine particles: The organic fine particles shown in Table 1 were added in the amounts shown in Table 1

(4) 무기미립자: 표 1에 기재된 무기미립자를 표 1에 기재된 양(4) Inorganic fine particles: The inorganic fine particles listed in Table 1 were added to the amounts shown in Table 1

(5) 중합개시제: I2959 5질량부(5) Polymerization initiator: I2959 5 parts by mass

(6) 중합촉진제: EPA 0.1질량부(6) Polymerization accelerator: 0.1 parts by mass of EPA

(7) 용매: 표 1에 기재된 용매를 표 1에 기재된 양(7) Solvent: The solvents listed in Table 1 were added to the amounts shown in Table 1

이 경화성 조성물을, A4사이즈의 표 2에 기재된 필름 상에, 바 1을 사용하여 바코트도포하여 도막을 얻었다. 이 도막을 표 2에 기재된 조건으로 오븐에서 건조시켜 용매를 제거하였다. 얻어진 막을, 질소분위기하, 노광량 500mJ/cm2의 UV광을 조사하고 노광함으로써, 표 2에 나타낸 두께의 하드코트층(경화막)을 갖는 하드코트필름을 제작하였다.This curable composition was coated on a film shown in Table 2 of A4 size using a bar 1 to obtain a coated film. This coating film was dried in an oven under the conditions shown in Table 2 to remove the solvent. The resultant film was exposed to UV light having an exposure dose of 500 mJ / cm 2 under a nitrogen atmosphere and exposed to produce a hard coat film having a hard coat layer (cured film) having a thickness shown in Table 2.

얻어진 하드코트필름의, 외관, 방현성, 내찰상성, 전광선투과율, 헤이즈, 그리고 물 및 올레산의 접촉각을 평가하였다. 외관, 방현성, 내찰상성, 및 접촉각의 평가의 순서를 이하에 나타낸다. 또한, 결과를 표 3에 함께 나타낸다.The apparent hardness, hardness, scratch resistance, total light transmittance, haze, and contact angle of water and oleic acid were evaluated. The evaluation of the appearance, repellency, scratch resistance, and contact angle will be described below. The results are also shown in Table 3.

[외관][Exterior]

하드코트필름의 외관을 육안으로 확인하고, 이하의 기준에 따라 평가하였다.The appearance of the hard coat film was visually confirmed and evaluated according to the following criteria.

A: 하드코트층 전체면에 걸쳐 얼룩이 없음A: No spots on the entire surface of the hard coat layer

C: 하드코트층 전체면에 응집물이 석출되어 반상의 얼룩이 눈에 띔C: Aggregates were precipitated on the entire surface of the hard coat layer,

[방현성][Bang]

얻어진 하드코트필름을 광택도Gs(60°)가 11.8인 흑색의 대에 싣고, 하드코트층 표면의 광택도Gs(60°)를 측정하고, 이하의 기준에 따라 평가하였다. 한편 하드코트층으로서 실제 사용을 상정한 경우, 적어도 B인 것이 요구되고, A인 것이 바람직하다.The obtained hard coat film was placed on a black bench having a gloss of Gs (60 DEG) of 11.8, and the glossiness Gs (60 DEG) of the surface of the hard coat layer was measured and evaluated according to the following criteria. On the other hand, when it is assumed that the hard coat layer is actually used, it is required to be at least B, and it is preferable that it is A.

A: Gs(60°)≤120A: Gs (60 DEG)? 120

B: 120<Gs(60°)≤125B: 120 < Gs (60 DEG)? 125

C: Gs(60°)>125C: Gs (60) > 125

[내찰상성][Scratch resistance]

하드코트층 표면을, 왕복마모시험기에 부착한 스틸울[본스타 판매(주)제 본스타(등록상표)#0000(초극세)]로 1kg/cm2의 하중을 가하여 1,000왕복 문지르고, 그 문지른 부분에 유성마커[지브라(주)제 맥키극세(청), 세측을 사용]로 선을 그렸다. 계속해서 그린 선을 부직포와이퍼[아사히카세이섬유(주)제 BEMCOT M-1]로 닦아내고, 흠집 정도를 육안으로 확인하여 이하의 기준에 따라 평가하였다. 한편 하드코트층으로서 실제의 사용을 상정한 경우, 적어도 B인 것이 요구되고, A인 것이 바람직하다.The surface of the hard coat layer was subjected to 1,000 reciprocating rubs by applying a load of 1 kg / cm 2 with a steel wool (BONSTAR (registered trademark) # 0000 (ultrafine) manufactured by BONSTAR Co., Ltd.) attached to a reciprocating abrasion tester, (Using Zebra's Mackie Ultra (blue), three sides). Subsequently, the green line was wiped with a nonwoven fabric wiper (BEMCOT M-1, manufactured by Asahi Kasei Fibers Co., Ltd.), and the degree of scratches was visually confirmed and evaluated according to the following criteria. On the other hand, when it is assumed that the hard coat layer is actually used, it is required to be at least B, and it is preferable that it is A.

A: 흠집이 생기지 않고 유성마커로 그린 선이 깨끗이 닦아내짐A: No scratches, clean lines wiped with oil-based markers

B: 약간 흠집이 생겼으나 유성마커로 그린 선이 깨끗이 닦아내짐B: A few scratches were found, but the lines drawn by the oil markers were cleanly wiped off

C: 유성마커의 잉크가 흠집에 들어가 닦아내지지 않음C: The ink of the oil-based marker does not get wiped in the scratches

[접촉각][Contact angle]

물 또는 올레산 1μL를 하드코트층 표면에 부착시키고, 그 5초 후의 접촉각θ을 5점에서 측정하고, 그 평균값을 접촉각값으로 하였다.1 占 물 of water or oleic acid was attached to the surface of the hard coat layer, and the contact angle? After 5 seconds was measured at five points, and the average value was regarded as the contact angle value.

[표 1][Table 1]

Figure pct00003
Figure pct00003

[표 2][Table 2]

Figure pct00004
Figure pct00004

[표 3][Table 3]

Figure pct00005
Figure pct00005

표 1 내지 표 3에 나타낸 바와 같이, 하드코트층에 있어서의 표면개질제로서 양말단에 폴리(옥시알킬렌)기를 개재하여 아크릴로일기를 갖는 퍼플루오로폴리에테르SM1 및 SM2를 이용하고, 또한 유기미립자를 배합한 실시예 1 내지 실시예 12의 경화성 조성물을 이용하여 제작한 각 하드코트필름은, 막두께 4~6μm로 내찰상성이 우수하고, 얼룩이 없는 외관을 얻을 수 있었다. 또한 방현성에 대해서도, 후술하는 비교예에 비해, 실제 사용을 고려한 경우의 기준을 전부 만족시키는 것이었다.As shown in Tables 1 to 3, perfluoropolyethers SM1 and SM2 having an acryloyl group via a poly (oxyalkylene) group at both ends were used as the surface modifier in the hard coat layer, Each of the hard coat films prepared using the curable compositions of Examples 1 to 12 in which fine particles were blended had excellent scratch resistance with a film thickness of 4 to 6 mu m and an appearance free from unevenness was obtained. In addition, as for the anti-glare properties, the standards for the actual use were all satisfied as compared with the comparative examples described later.

한편, 유기미립자의 첨가량을 본 발명에 있어서 정하는 수치범위 미만으로 한 비교예 1 및 비교예 2, 그리고 유기미립자를 미첨가로 한 비교예 6에 있어서는, 원하는 방현성이 얻어지지 않았다.On the other hand, in Comparative Example 1 and Comparative Example 2 in which the amount of the organic fine particles added was less than the numerical range defined in the present invention, and Comparative Example 6 in which the organic fine particles were not added, the desired antireflection property was not obtained.

또한 하드코트층의 표면개질제로서, 양말단에 폴리(옥시알킬렌)기를 개재하여 아크릴로일기를 갖는 퍼플루오로폴리에테르를 대신하여, 양말단에 폴리(옥시알킬렌)기를 개재하지 않고 아크릴로일기를 갖는 퍼플루오로폴리에테르SM3을 이용한 비교예 3은, 실시예에 비해 내찰상성이 뒤떨어지고, 또한 하드코트층 전체면에 응집물이 석출되어 반상의 얼룩이 눈에 띄는 외관을 나타냈다.Further, as a surface modifier for the hard coat layer, a perfluoropolyether having an acryloyl group via a poly (oxyalkylene) group at both ends was used instead of the poly (oxyalkylene) group at both ends, Comparative Example 3 using perfluoropolyether SM3 having a diarrhea exhibited poor scratch resistance as compared with the Examples, and aggregates were precipitated on the entire surface of the hard coat layer, and appearance of the surface was noticeable.

또한, 표면개질제로서 퍼플루오로폴리에테르구조를 갖는 UV반응형 불소계 표면개질제SM4를 이용한 비교예 4 및 비교예 5는, 내찰상성이 크게 뒤떨어지는 결과가 되었다.Further, Comparative Example 4 and Comparative Example 5 using a UV-reactive fluorine-based surface modifier SM4 having a perfluoropolyether structure as a surface modifier had poor scratch resistance.

이상, 실시예의 결과에 나타낸 바와 같이, 표면개질제로서 이용하는 퍼플루오로폴리에테르의 말단의 구조가 약간 상이한 것만으로, 하드코트층의 내찰상성 그리고 외관에 있어서 만족한 결과를 얻는 것이 곤란하며, 또한, 유기미립자의 첨가량을 소정범위 외로 하면 방현성을 얻을 수 없고, 본 발명의 경화성 조성물만이 이러한 성능을 전부 만족시키는 하드코트필름을 얻을 수 있다.As described above, as shown in the results of the examples, it is difficult to obtain satisfactory results in scratch resistance and appearance of the hard coat layer only by slightly different structures of the terminals of the perfluoropolyether used as the surface modifier, When the addition amount of the organic fine particles is outside of a predetermined range, the film can not obtain a desired durability, and only the curable composition of the present invention can obtain a hard coat film satisfying all of these performances.

Claims (13)

(a) 활성에너지선 경화성 다관능모노머 100질량부,
(b) 폴리(옥시퍼플루오로알킬렌)기를 포함하는 분자쇄의 양말단에, 폴리(옥시알킬렌)기를 개재하거나 또는 폴리(옥시알킬렌)기 및 1개의 우레탄결합을 이 순으로 개재하여 활성에너지선 중합성기를 갖는 퍼플루오로폴리에테르 0.1~10질량부,
(c) 1~10μm의 평균입경을 갖는 유기미립자 8~30질량부,
(d) 활성에너지선에 의해 라디칼을 발생하는 중합개시제 1~20질량부, 및
(e) 유기용매
를 포함하는 경화성 조성물.
(a) 100 parts by mass of active energy ray-curable polyfunctional monomer,
(oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order in the both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group, (b) 0.1 to 10 parts by mass of a perfluoropolyether having an active energy linear polymerizable group,
(c) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 m,
(d) 1 to 20 parts by mass of a polymerization initiator which generates a radical by an active energy ray, and
(e) an organic solvent
&Lt; / RTI &gt;
제1항에 있어서,
상기 폴리(옥시퍼플루오로알킬렌)기가, -[OCF2]- 및 -[OCF2CF2]-를 반복단위로서 갖는 기인, 경화성 조성물.
The method according to claim 1,
Wherein the poly (oxyperfluoroalkylene) group is a group having - [OCF 2 ] - and - [OCF 2 CF 2 ] - as repeating units.
제1항 또는 제2항에 있어서,
상기 폴리(옥시알킬렌)기가 폴리(옥시에틸렌)기인, 경화성 조성물.
3. The method according to claim 1 or 2,
Wherein the poly (oxyalkylene) group is a poly (oxyethylene) group.
제1항 내지 제3항 중 어느 한 항에 있어서,
상기 성분(a)의 다관능모노머가, 다관능(메트)아크릴레이트 화합물 및 다관능우레탄(메트)아크릴레이트 화합물로 이루어진 군으로부터 선택되는 적어도 1개인, 경화성 조성물.
4. The method according to any one of claims 1 to 3,
Wherein the polyfunctional monomer of the component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.
제1항 내지 제4항 중 어느 한 항에 있어서,
상기 성분(c)의 유기미립자가 진구상 입자인, 경화성 조성물.
5. The method according to any one of claims 1 to 4,
Wherein the organic fine particles of the component (c) are spherical particles.
제1항 내지 제5항 중 어느 한 항에 있어서,
상기 성분(c)의 유기미립자가 폴리메타크릴산메틸입자인, 경화성 조성물.
6. The method according to any one of claims 1 to 5,
Wherein the organic fine particles of the component (c) are polymethyl methacrylate particles.
제1항 내지 제6항 중 어느 한 항에 있어서,
상기 성분(d)의 중합개시제가 알킬페논류인, 경화성 조성물.
7. The method according to any one of claims 1 to 6,
Wherein the polymerization initiator of the component (d) is an alkylphenone compound.
제1항 내지 제7항 중 어느 한 항에 기재된 경화성 조성물로부터 얻어지는 경화막.
A cured film obtained from the curable composition according to any one of claims 1 to 7.
필름기재의 적어도 일방의 면에 하드코트층을 구비한 하드코트필름으로서, 이 하드코트층이 제8항에 기재된 경화막으로 이루어진, 하드코트필름.
A hard coat film having a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film according to claim 8.
필름기재의 적어도 일방의 면에 하드코트층을 구비한 하드코트필름으로서, 이 하드코트층이, 제1항 내지 제7항 중 어느 한 항에 기재된 경화성 조성물을 필름기재 상에 도포하고 도막을 형성하는 공정과, 이 도막에 활성에너지선을 조사하여 경화하는 공정을 포함하는 방법에 의해 형성되어 이루어진, 하드코트필름.
A hard coat film having a hard coat layer on at least one side of a film substrate, wherein the hard coat layer is formed by applying the curable composition according to any one of claims 1 to 7 on a film substrate and forming a coat And a step of irradiating the coating film with an active energy ray to cure the coating film.
제9항 또는 제10항에 있어서,
상기 하드코트층이, 상기 유기미립자의 평균입경에 비해 1배~10/7배의 두께를 갖는, 하드코트필름.
11. The method according to claim 9 or 10,
Wherein the hard coat layer has a thickness of 1 to 10/7 times the average particle diameter of the organic fine particles.
제9항 내지 제11항 중 어느 한 항에 있어서,
상기 하드코트층이 1~20μm의 막두께를 갖는, 하드코트필름.
12. The method according to any one of claims 9 to 11,
Wherein the hard coat layer has a film thickness of 1 to 20 占 퐉.
제12항에 있어서,
상기 하드코트층이 3~10μm의 막두께를 갖는, 하드코트필름.
13. The method of claim 12,
Wherein the hard coat layer has a film thickness of 3 to 10 mu m.
KR1020177031631A 2015-04-07 2016-04-07 Curable composition for anti-glare coating KR102345843B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JPJP-P-2015-078814 2015-04-07
JP2015078814 2015-04-07
PCT/JP2016/061438 WO2016163478A1 (en) 2015-04-07 2016-04-07 Curable composition for use in antiglare coating

Publications (2)

Publication Number Publication Date
KR20170134577A true KR20170134577A (en) 2017-12-06
KR102345843B1 KR102345843B1 (en) 2021-12-31

Family

ID=57071835

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020177031631A KR102345843B1 (en) 2015-04-07 2016-04-07 Curable composition for anti-glare coating

Country Status (5)

Country Link
JP (1) JP6806048B2 (en)
KR (1) KR102345843B1 (en)
CN (1) CN107960080B (en)
TW (1) TWI695866B (en)
WO (1) WO2016163478A1 (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017071735A (en) * 2015-10-09 2017-04-13 ナガセケムテックス株式会社 Resin composition and cured product sheet
CN110770025B (en) 2017-05-10 2022-05-31 理研科技株式会社 Hard coat laminated film
CN111741848B (en) * 2018-02-22 2023-08-18 理研科技株式会社 Anti-dazzle hard coating laminated film
JP2019203931A (en) * 2018-05-21 2019-11-28 株式会社ダイセル Anti-glare film, and manufacturing method and application of the same
KR20210029724A (en) * 2018-07-05 2021-03-16 닛산 가가쿠 가부시키가이샤 Method of manufacturing scratch-resistant hard coat film
JP7082810B2 (en) * 2018-07-19 2022-06-09 十条ケミカル株式会社 Manufacturing method of UV curable resin composition, UV curable resin molded product, and UV curable resin molded product
WO2020162323A1 (en) * 2019-02-06 2020-08-13 日産化学株式会社 Curable composition for flexible hard coating
CN113396190B (en) * 2019-02-06 2023-05-02 日产化学株式会社 Curable composition for antiglare flexible hard coat layer
CN113423749A (en) * 2019-02-06 2021-09-21 日产化学株式会社 Curable composition for antiglare hardcoat
WO2020162326A1 (en) * 2019-02-06 2020-08-13 日産化学株式会社 Curable composition for flexible hard coat
WO2020162329A1 (en) * 2019-02-06 2020-08-13 日産化学株式会社 Curable composition for hard coating

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005126453A (en) * 2003-10-21 2005-05-19 Tdk Corp Hard coating agent composition and optical information medium using the same
JP2011053455A (en) * 2009-09-02 2011-03-17 Nof Corp Glare-proof hard coat film
CN103102793A (en) * 2011-09-30 2013-05-15 Tdk株式会社 Hard coat agent composition and hard coat film using the same
JP2013257359A (en) 2012-06-11 2013-12-26 Nippon Paper Industries Co Ltd Antidazzle hard coat film
JP2014070165A (en) * 2012-09-28 2014-04-21 Fujifilm Corp Polymerizable composition and antireflection film, polarizing plate, image display device, and water-repellent or oil-repellent film using the same

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3161552B2 (en) * 1992-01-31 2001-04-25 大日本インキ化学工業株式会社 Curable composition and insulated wire
JP2001272507A (en) * 2000-03-28 2001-10-05 Omron Corp Microlens array
KR100487025B1 (en) * 2002-02-28 2005-05-11 주식회사 루밴틱스 Photo-curable resin composition for optical waveguide and optical waveguide prepared therefrom
TWI378128B (en) * 2004-09-27 2012-12-01 Fujifilm Corp Coating composition, optical film, anti-reflection film, polarizing plate, and display unit using them
US7390854B2 (en) * 2004-11-05 2008-06-24 E. I. Dupont De Nemours And Company Low shrinkage, low optical absorbance, low refractive index adhesive composition
WO2007046275A1 (en) * 2005-10-19 2007-04-26 Konica Minolta Opto, Inc. Glareless film, polarizing plate and display
CN101910247B (en) * 2007-12-12 2014-10-22 3M创新有限公司 Hardcoats comprising perfluoropolyether polymers with poly(alkylene oxide) repeat units
JP5415742B2 (en) * 2008-11-07 2014-02-12 帝人デュポンフィルム株式会社 Anti-glare hard coat film
EP2221664A1 (en) * 2009-02-19 2010-08-25 Solvay Solexis S.p.A. Nanolithography process
KR20110019979A (en) * 2009-08-21 2011-03-02 동우 화인켐 주식회사 Colored photosensitive resin composition, color filter and liquid crystal display device prepared by using the same
JP5690491B2 (en) * 2010-02-24 2015-03-25 リンテック株式会社 Anti-glare hard coat film and polarizing plate using the same
TWI541301B (en) * 2010-12-01 2016-07-11 日產化學工業股份有限公司 Curable composition for coating comprising fluorine-containing highly branched polymer
JP6062680B2 (en) * 2012-08-01 2017-01-18 スリーエム イノベイティブ プロパティズ カンパニー Antifouling hard coat and antifouling hard coat precursor
JP6371032B2 (en) * 2012-08-01 2018-08-08 スリーエム イノベイティブ プロパティズ カンパニー Anti-reflective hard coat and anti-reflective article
JP6057121B2 (en) * 2012-11-02 2017-01-11 Dic株式会社 Active energy ray curable composition, cured product thereof and article having cured coating film thereof
JP6402643B2 (en) * 2014-03-31 2018-10-10 信越化学工業株式会社 Fluorine-containing acrylic compound, method for producing the same, curable composition, and substrate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005126453A (en) * 2003-10-21 2005-05-19 Tdk Corp Hard coating agent composition and optical information medium using the same
JP2011053455A (en) * 2009-09-02 2011-03-17 Nof Corp Glare-proof hard coat film
CN103102793A (en) * 2011-09-30 2013-05-15 Tdk株式会社 Hard coat agent composition and hard coat film using the same
JP2013257359A (en) 2012-06-11 2013-12-26 Nippon Paper Industries Co Ltd Antidazzle hard coat film
JP2014070165A (en) * 2012-09-28 2014-04-21 Fujifilm Corp Polymerizable composition and antireflection film, polarizing plate, image display device, and water-repellent or oil-repellent film using the same

Also Published As

Publication number Publication date
WO2016163478A1 (en) 2016-10-13
TW201708426A (en) 2017-03-01
JPWO2016163478A1 (en) 2018-02-01
TWI695866B (en) 2020-06-11
CN107960080B (en) 2020-11-24
JP6806048B2 (en) 2021-01-06
CN107960080A (en) 2018-04-24
KR102345843B1 (en) 2021-12-31

Similar Documents

Publication Publication Date Title
KR102345843B1 (en) Curable composition for anti-glare coating
TWI736530B (en) Coating curable composition having marring resistance
KR102507695B1 (en) Anti-glare hard coat laminate
WO2015060458A1 (en) Polymerizable composition containing perfluoropolyether having hydroxyl group
JP6982280B2 (en) High hardness hardcourt laminate
JPWO2018070438A1 (en) Light resistant hard coat material
CN109715685B (en) Scratch-resistant hard coating material
JP2010174125A (en) Composition for use in hard coat layer, and hard coat film
JP7332989B2 (en) Curable composition for antiglare hard coat
TWI850326B (en) Curable composition for glare proof hard coating
KR20230156827A (en) Curable composition for hard coats

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant