KR102345843B1 - Curable composition for anti-glare coating - Google Patents

Curable composition for anti-glare coating Download PDF

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KR102345843B1
KR102345843B1 KR1020177031631A KR20177031631A KR102345843B1 KR 102345843 B1 KR102345843 B1 KR 102345843B1 KR 1020177031631 A KR1020177031631 A KR 1020177031631A KR 20177031631 A KR20177031631 A KR 20177031631A KR 102345843 B1 KR102345843 B1 KR 102345843B1
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hard coat
film
meth
poly
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KR20170134577A (en
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마사유키 하라구치
모토노부 마츠야마
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닛산 가가쿠 가부시키가이샤
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • 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
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    • 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
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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.[Problem] To provide a material for forming a hard coat layer that is excellent in anti-glare properties and exhibits high scratch resistance.
[Solutions] (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (b) a poly(oxyalkylene) group is interposed at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, or 0.1 to 10 parts by mass of a perfluoropolyether having an active energy ray polymerizable group via a poly(oxyalkylene) group and one urethane bond in this order, (c) organic fine particles having an average particle diameter of 1 to 10 μm 8 ~ 30 parts by mass, (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, and (e) a curable composition comprising an organic solvent, and a hard coat layer formed from the composition. coat film.

Description

방현성 코팅용 경화성 조성물Curable composition for anti-glare 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 the surface of various display elements such as a touch panel display and a liquid crystal display, and in particular, excellent in anti-glare properties (anti-glare function). It relates 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 large number of products equipped with a touch panel in flat panel displays such as personal computers, mobile phones, mobile game devices, and ATMs have been commercialized. In particular, with the advent of smartphones and tablet PCs, the number of capacitive touch panels having a multi-touch function is increasing at once.

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.A method of bonding an anti-glare hard coat film having a hard coat layer of about several μm with irregularities formed on the surface is used on the surface of these touch panel displays to prevent a decrease in visibility due to external light shining on the screen. is becoming As a method of forming the unevenness on the surface, a method of containing fine particles having a particle size of about several μm 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 a capacitive touch panel, operation is performed by contact with a human finger. For this reason, whenever an operation is performed, a fingerprint adheres to the surface of a touch panel, and the problem that the visibility of the image of a display is significantly impaired or the external appearance of a display is damaged arises. Fingerprints contain sweat-derived moisture and sebum-derived oil, and in order to make both of them difficult to adhere, it is strongly demanded to impart water-repellent and oil-repellent properties to the hard coat layer on the display surface.

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 the capacitive touch panel, since a person touches it with their fingers every day, even if the initial antifouling property has reached a considerable level, these functions are often deteriorated due to scratches during use. In particular, in the anti-glare hard-coat layer, since it has an unevenness|corrugation on the surface, it is easy to generate|occur|produce a jamming and it is easy to generate|occur|produce a flaw. Accordingly, the durability of antifouling properties 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).Up to now, as a hard coat layer having anti-glare and abrasion resistance, as a component imparting antifouling and scratch resistance to the surface of the hard coat layer, a poly(oxyperfluoroalkylene) structure and (meth)acryloyl group in the molecule A technique using methyl methacrylate-styrene copolymer (MS) resin microparticles is disclosed as a component for imparting a surface modifier having anti-glare properties to the hard coat layer (Patent Document 1).

일본특허공개 2013-257359호 공보Japanese Patent 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 described in Patent Document 1, the surface modifier having a poly(oxyperfluoroalkylene) structure and a (meth)acryloyl group in the molecule has a low fluorine content, and the problem that sufficient stain resistance and scratch resistance cannot be obtained there was. In addition, when the amount of MS resin particles added is reduced to obtain scratch resistance, sufficient anti-glare properties cannot be obtained. Furthermore, the dispersibility of the resin particle in a hard-coat layer was bad, and it was a subject that it becomes an aggregate and impairs the external appearance of a coating film. That is, the hard-coat layer which was excellent in anti-glare property and expresses high abrasion resistance was calculated|required.

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.As a result of repeated intensive studies to achieve the above object, the present inventors have either interposed a poly(oxyalkylene) group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) structure, or A compound having an active energy ray polymerizable group through an alkylene) group and one urethane bond is used as a fluorine-based surface modifier, and further, by employing a curable composition in which organic fine particles are added, excellent anti-glare properties and high scratch resistance It was found that it was possible to form a hard coat layer having a, and completed the present invention.

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 an 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,(b) at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, a poly(oxyalkylene) group or a poly(oxyalkylene) group and one urethane bond are interposed in this order , 0.1 to 10 parts by mass of perfluoropolyether having an active energy ray 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 μm;

(d) 활성에너지선에 의해 라디칼을 발생하는 중합개시제 1~20질량부, 및(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, and

(e) 유기용매(e) organic solvents

를 포함하는 경화성 조성물에 관한 것이다.It relates to a curable composition comprising a.

제2 관점으로서, 상기 폴리(옥시퍼플루오로알킬렌)기가, -[OCF2]- 및 -[OCF2CF2]-를 반복단위로서 갖는 기인, 제1 관점에 기재된 경화성 조성물에 관한 것이다.A second aspect relates to the curable composition according to 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.A third aspect relates to the curable composition according to the first aspect or the 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, the polyfunctional monomer of the component (a) is at least one selected from the group consisting of polyfunctional (meth) acrylate compounds and polyfunctional urethane (meth) acrylate compounds, first to third It relates to the curable composition described in any one of the viewpoints.

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.A fifth aspect 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.A sixth aspect 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.A seventh aspect 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.

제8 관점으로서, 제1 관점 내지 제7 관점 중 어느 하나에 기재된 경화성 조성물로부터 얻어지는 경화막에 관한 것이다.As an 8th viewpoint, it is related with the cured film obtained from the curable composition in any one of a 1st viewpoint - a 7th viewpoint.

제9 관점으로서, 필름기재의 적어도 일방의 면에 하드코트층을 구비하는 하드코트필름으로서, 이 하드코트층이 제8 관점에 기재된 경화막으로 이루어진, 하드코트필름에 관한 것이다.A ninth aspect 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, a hard coat film having a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer is coated with the curable composition according to any one of the first to seventh aspects on the film substrate And it relates to a hard coat film formed by a method comprising a step of forming a coating film, and a step of irradiating and curing the coating film with active energy rays.

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 layer relates to the hard coat film according to the ninth or tenth aspect, wherein 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 viewpoint, it relates to the hard coat film in any one of a ninth viewpoint to an eleventh viewpoint in which the said hard-coat layer has a film thickness of 1-20 micrometers.

제13 관점으로서, 상기 하드코트층이 3~10μm의 막두께를 갖는, 제12 관점에 기재된 하드코트필름에 관한 것이다.As a thirteenth aspect, it relates to the hard coat film according to the twelfth aspect, wherein the hard coat layer has a film thickness of 3 to 10 µm.

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 anti-glare properties even in a thin film having a thickness of about 1 to 10 μm, and having excellent appearance.

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.In addition, according to the present invention, it is possible to provide a hard coat film provided with a cured film obtained from the curable composition or a hard coat layer formed therefrom on the surface, and a hard coat film having excellent anti-glare properties, scratch resistance and appearance. can do.

<경화성 조성물><Curable composition>

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

(a) 활성에너지선 경화성 다관능모노머 100질량부,(a) 100 parts by mass of an 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,(b) at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, a poly(oxyalkylene) group or a poly(oxyalkylene) group and one urethane bond are interposed in this order , 0.1 to 10 parts by mass of perfluoropolyether having an active energy ray 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 μm;

(d) 활성에너지선에 의해 라디칼을 발생하는 중합개시제 1~20질량부, 및(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, and

(e) 유기용매(e) organic solvents

를 포함하는 경화성 조성물에 관한 것이다.It relates to a curable composition comprising a.

이하, 우선 상기 (a)~(e)의 각 성분에 대하여 설명한다.Hereinafter, each component of said (a)-(e) is demonstrated first.

[(a) 활성에너지선 경화성 다관능모노머][(a) active energy ray-curable polyfunctional monomer]

활성에너지선 경화성 다관능모노머란, 자외선 등의 활성에너지선을 조사함으로써 중합반응이 진행되고, 경화하는 모노머를 가리킨다.An active energy ray-curable polyfunctional monomer refers to a monomer which a polymerization reaction advances and hardens by irradiating active energy rays, such as an ultraviolet-ray.

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

한편, 본 발명에 있어서 (메트)아크릴레이트 화합물이란, 아크릴레이트 화합물과 메타크릴레이트 화합물의 양방을 말한다. 예를 들어 (메트)아크릴산은, 아크릴산과 메타크릴산을 말한다.In addition, in this invention, a (meth)acrylate compound means both an acrylate compound and a methacrylate compound. For example, (meth)acrylic acid means 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, ditrimethylol propane 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 glycerin tri (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, 1, 3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2- Methyl-1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentylglycol di(meth)acrylate , ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene 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 ]decane dimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxopropane, 2- Hydroxy-1,3-di(meth)acryloyloxopropane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, bis[4-(meth) Acryloylphenyl]sulfide, bis[2-(meth)acryloylthioethyl]sulfide, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantane dimethanol di(meth)acryl a rate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. are mentioned.

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

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 groups or methacryloyl groups in one molecule and 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.For example, as said polyfunctional urethane (meth)acrylate, what is obtained by reaction of polyfunctional isocyanate and (meth)acrylate which has a hydroxyl group, polyfunctional isocyanate and (meth)acrylate which has a hydroxyl group, and those obtained by reaction with a polyol, but the polyfunctional urethane (meth)acrylate compound usable in the present invention is not limited to these examples.

또한 상기 다관능이소시아네이트로는, 예를 들어, 톨릴렌디이소시아네이트, 이소포론디이소시아네이트, 자일릴렌디이소시아네이트, 헥사메틸렌디이소시아네이트 등을 들 수 있다.Moreover, as said polyfunctional isocyanate, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate etc. are mentioned, for example.

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.Moreover, as (meth)acrylate which has the said hydroxyl group, for example, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, pentaerythritol tri(meth)acrylate, dipentaerythritol Penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, etc. are mentioned.

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.And as said polyol, For example, Diols, such as ethylene glycol, propylene glycol, neopentyl glycol, 1, 4- butanediol, 1, 6- hexanediol, diethylene glycol, 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 acid anhydrides; polyether polyols; Polycarbonate diol etc. are mentioned.

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, as the (a) active energy ray-curable polyfunctional monomer, one type alone or two types from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound A combination of the above can be used. It is preferable to use together a polyfunctional (meth)acrylate compound and a polyfunctional urethane (meth)acrylate compound from a viewpoint of the abrasion resistance of the hardened|cured material obtained. Moreover, as said polyfunctional (meth)acrylate compound, it is preferable to use together the polyfunctional (meth)acrylate compound of pentafunctional or less and the polyfunctional (meth)acrylate compound of tetrafunctional or less.

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.In addition, when using the polyfunctional (meth) acrylate compound in combination with the polyfunctional urethane (meth) acrylate compound, with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound, polyfunctional urethane (meth) acryl It is preferable to use 20-100 mass parts of rate compounds, and it is more preferable to use 30-70 mass parts.

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.Furthermore, in the polyfunctional (meth) acrylate compound, when using a combination of the pentafunctional or higher polyfunctional (meth) acrylate compound and the tetrafunctional or lower polyfunctional (meth) acrylate compound, pentafunctional or more It is preferable to use 10-100 mass parts of tetrafunctional or less polyfunctional (meth)acrylate compounds with respect to 100 mass parts of polyfunctional (meth)acrylate compounds, and it is more preferable to use 20-60 mass parts.

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,In addition, with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound, 20 to 100 parts by mass of the polyfunctional urethane (meth) acrylate compound, and 100 parts by mass of the polyfunctional (meth) acrylate compound having more than 5 functionalities, the amount of tetrafunctional or less What is used in an amount of 10 to 100 parts by mass of a polyfunctional (meth)acrylate compound,

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,With respect to 100 parts by mass of the polyfunctional (meth) acrylate compound, 20 to 100 parts by mass of the polyfunctional urethane (meth) acrylate compound, and 100 parts by mass of the polyfunctional (meth) acrylate compound having a function of 5 or more and a polyfunctionality of tetrafunctional or less (meth) acrylate compound used 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,With respect to 100 parts by mass of the polyfunctional (meth) acrylate compound, 30 to 70 parts by mass of the polyfunctional urethane (meth) acrylate compound, and 100 parts by mass of the polyfunctional (meth) acrylate compound having a function of 5 or more, polyfunctional or less polyfunctional. (meth) acrylate compound used 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.With respect to 100 parts by mass of the polyfunctional (meth) acrylate compound, 30 to 70 parts by mass of the polyfunctional urethane (meth) acrylate compound, and 100 parts by mass of the polyfunctional (meth) acrylate compound having a function of 5 or more, polyfunctional or less polyfunctional. It is preferable to use in 20-60 mass parts of (meth)acrylate compounds.

[(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 is interposed at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, or a poly(oxyalkylene) group and one urethane bond are interposed in this order Thus, perfluoropolyether having an active energy ray 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 component (b), a poly(oxyalkylene) group is interposed at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, or a poly(oxyalkylene) group and one urethane The bonds are interposed in this order to use a perfluoropolyether having an active energy ray polymerizable group (hereinafter also simply referred to as “(b) a perfluoropolyether having a polymerizable group at both ends”). (b) Component plays a role as a surface modifier in the hard-coat layer to which the curable composition of this 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 in the alkylene group in the poly(oxyperfluoroalkylene) group is not particularly limited, but preferably has 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 an oxygen atom are alternately connected, and the oxyperfluoroalkylene group is 2 having 1 to 4 carbon atoms. It refers to a group having a structure in which a valent fluorocarbon group and an oxygen atom are linked. Specifically, -[OCF 2 ]-(oxyperfluoromethylene group), -[OCF 2 CF 2 ]-(oxyperfluoroethylene group), -[OCF 2 CF 2 CF 2 ]-(oxyperfluoro and groups such as lopropane-1,3-diyl group) and -[OCF 2 C(CF 3 )F]-(oxyperfluoropropane-1,2-diyl group).

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 said oxyperfluoroalkylene group may be used individually by 1 type, or may be used in combination of 2 or more types, In that case, the bonding of multiple types of oxyperfluoroalkylene groups is a block bond and a random bond. Any may be sufficient.

이들 중에서도, 내찰상성이 양호해지는 경화막이 얻어지는 관점에서, 폴리(옥시퍼플루오로알킬렌)기로서, -[OCF2]-(옥시퍼플루오로메틸렌기)와 -[OCF2CF2]-(옥시퍼플루오로에틸렌기)의 쌍방을 반복단위로서 갖는 기를 이용하는 것이 바람직하다.Among these, from the viewpoint of obtaining a cured film with good scratch resistance, as poly(oxyperfluoroalkylene) groups, -[OCF 2 ]-(oxyperfluoromethylene group) and -[OCF 2 CF 2 ]-( It is preferable to use a group having both oxyperfluoroethylene groups) as repeating units.

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, as the poly(oxyperfluoroalkylene) group, repeating units: -[OCF 2 ]- and -[OCF 2 CF 2 ]- are [repeating units:-[OCF 2 ]-] in a molar ratio: [Repeat unit: -[OCF 2 CF 2 ]-] = It is preferably a group included in a ratio of 2:1 to 1:2, and more preferably a group included in a ratio of about 1:1. The bonding of these repeating units may be either a block bond or a random bond.

상기 옥시퍼플루오로알킬렌기의 반복단위수는, 그 반복단위수의 총계로서 5~30의 범위인 것이 바람직하고, 7~21의 범위인 것이 보다 바람직하다.It is preferable that it is the range of 5-30, and, as for the number of repeating units of the said oxyperfluoroalkylene group, it is more preferable that it is the range of 7-21 as a total of the number of repeating units.

또한, 상기 폴리(옥시퍼플루오로알킬렌)기의 겔 침투 크로마토그래피에 의한 폴리스티렌 환산으로 측정되는 중량평균분자량(Mw)은, 1,000~5,000, 바람직하게는 1,500~2,000이다.In addition, the weight average molecular weight (Mw) of the poly(oxyperfluoroalkylene) group measured in terms of polystyrene by gel permeation chromatography 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 in the alkylene group in the poly(oxyalkylene) group is not particularly limited, but preferably has 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 connected, and the oxyalkylene group is a structure in which a divalent alkylene group having 1 to 4 carbon atoms and an oxygen atom are connected. refers to a group with As said alkylene group, an ethylene group, 1-methylethylene group, a trimethylene group, a tetramethylene group, etc. are mentioned.

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.The said oxyalkylene group may be used individually by 1 type, or may be used in combination of 2 or more type, In that case, either a block bond and a random bond may be sufficient as the bond of multiple types of oxyalkylene group.

그 중에서도, 상기 폴리(옥시알킬렌)기는, 폴리(옥시에틸렌)기인 것이 바람직하다.Especially, it is preferable that the said poly(oxyalkylene) group is 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, more preferably 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 ray polymerizable group bonding through the poly(oxyalkylene) group or through the poly(oxyalkylene) group and one urethane bond in this order include a (meth)acryloyl group, urethane (meth) An acryloyl group, a vinyl group, etc. are mentioned.

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 ray polymerizable group is not limited to having one active energy ray polymerizable moiety such as a (meth) acryloyl moiety, and may have two or more active energy ray polymerizable moieties, for example, The structures of A1 - A5 shown below and the structure which substituted the acryloyl group in these structures with the methacryloyl group are mentioned.

[화학식 1][Formula 1]

Figure 112017107958293-pct00001
Figure 112017107958293-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.Preferred examples of (b) perfluoropolyethers having polymerizable groups at both terminals are the compounds shown below and compounds in which acryloyl groups are substituted with methacryloyl groups from the viewpoint of easy industrial production. can be heard as Meanwhile, in the structural formula, A represents one of the structures represented by the formulas [A1] to [A5], PFPE represents the poly(oxyperfluoroalkylene) group, and n is each independently an oxyethylene group represents the number of repeating units, preferably the number of 1 to 15, more preferably the number of 5 to 12, and still more preferably the number of 7 to 12.

[화학식 2][Formula 2]

Figure 112017107958293-pct00002
Figure 112017107958293-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 terminals (b) of the present invention includes a poly(oxyalkylene) group and One urethane bond is interposed in this order, that is, poly(oxyalkylene) groups are bonded to both ends of a molecular chain containing poly(oxyperfluoroalkylene) groups, respectively, and each poly(oxyalkylene) group at both ends It is preferable that it is a perfluoropolyether in which one urethane bond is bonded to each ren) group, and an active energy ray polymerizable group is bonded to each urethane bond at both ends. Furthermore, in the perfluoropolyether, the active energy ray polymerizable group is preferably a perfluoropolyether having at least two or more active energy ray 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, (b) the perfluoropolyether having a polymerizable group at both terminals is 0.1 to 10 parts by mass, preferably 0.2 to 100 parts by mass of the active energy ray-curable polyfunctional monomer (a) described above. It is preferable to use it in the ratio of -5 mass parts.

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 (b) perfluoropolyether having a polymerizable group at both terminals is, for example, a compound having a hydroxyl group through a poly(oxyalkylene) group at both ends of the poly(oxyperfluoroalkylene) group In the urethane compound, 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 It is obtained by a chemical reaction method, a method of dehydrochlorination reaction of (meth)acrylic acid chloride or chloromethylstyrene, a method of dehydration reaction of (meth)acrylic acid, a method of esterification reaction of itaconic anhydride, 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 a compound having a hydroxyl group through a poly(oxyalkylene) group at both ends of the poly(oxyperfluoroalkylene) group, 2-(meth)acryloyl with respect to the hydroxyl group at both ends A method of urethanating an isocyanate compound having a polymerizable group, such as yloxyethyl isocyanate or 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, or (meth)acrylic acid chloride with respect to this hydroxyl group Alternatively, a method in which chloromethylstyrene is subjected to a dehydrochloric acid reaction is particularly preferable from the viewpoint of easy reaction.

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.On the other hand, in the curable composition of the present invention, (b) a poly(oxyalkylene) group is interposed at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, or a poly(oxyalkylene) group and one A urethane bond is interposed in this order, in addition to the perfluoropolyether having an active energy ray polymerizable group, a poly(oxyalkylene) group is interposed at one end of the molecular chain containing a poly(oxyperfluoroalkylene) group, or or a perfluoropolyether having an active energy ray polymerizable group through a poly(oxyalkylene) group and one urethane bond in this order, and having a hydroxyl group through a poly(oxyalkylene) group at the other end B, perfluoropolyether [compound not having an active energy ray polymerizable group] having a hydroxyl group via a poly(oxyalkylene) group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group is included. it may have been

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

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 μm (hereinafter also simply referred to as “(c) organic fine particles”) are formed by making the surface of the hard coat layer formed from the curable composition in a concave-convex shape. Gives anti-glare properties.

또한 유기미립자는, 그 굴절률과 하드코트층형성재료인 경화성 조성물의 굴절률의 차이를 제어함으로써, 하드코트층의 헤이즈값을 제어하는 역할도 할 수 있다.The organic fine particles can also serve to 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 serving 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, but, for example, may be approximately spherical in the form of beads or may be amorphous such as powder, preferably approximately spherical, and more preferably approximately spherical with an aspect ratio of 1.5 or less. of particles, and most preferably spherical particles.

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), silicone particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, polyamide particles, polyimide particles, polyethylene fluoride particles, and the like. These organic particulates may be used individually by 1 type, and may use 2 or more types together.

그 중에서도, 상기 유기미립자로서 폴리메타크릴산메틸입자를 호적하게 이용할 수 있다.Among them, polymethyl methacrylate particles can be preferably 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 μm, preferably in the range of 3 to 8 μm. Here, the average particle diameter (μm) is a 50% volume diameter (median diameter) obtained by measuring by a laser diffraction/scattering method based on the Mie theory. If the average particle diameter of the organic fine particles is larger than the above numerical range, the image clarity of the display is lowered. If the average particle diameter is smaller than the above numerical range, sufficient anti-glare properties cannot be obtained and glare is increased easily. Meanwhile, the organic fine particles are not particularly limited in terms of their particle size distribution, but are preferably monodisperse fine particles having a uniform particle size.

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 difference of 0 to 0.20 with respect to the cured product of the active energy ray-curable polyfunctional monomer (a), and more preferably 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.In addition, the organic fine particles are selected so that their average particle diameter satisfies the range of average particle diameter b/film thickness a = 0.7 to 1.0 with respect to the film thickness of a cured film obtained from the curable composition of the present invention to be described later. it is preferable

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.Commercially available particles can be suitably used for the organic particulates, for example, Techpolymer (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, ACP series [above, manufactured by Sekisui Chemical Industry Co., Ltd.]; Tospearl (registered trademark) series [Made in Momentive Performance Materials Japan (Bronze)]; Eposta (registered trademark) series, MA series, ST series, MX series [above, made by Nippon Catalyst]; Optbiz (registered trademark) series [manufactured by Nissan Chemical Industry Co., Ltd.]; Flowbiz series [manufactured by Sumitomo Seika Co., Ltd.]; Trefal (registered trademark) PPS, PAI, PES, EP [above, manufactured by Toray Co., Ltd.]; 3M (registered trademark) Dinion TF micropowder series [manufactured by 3M]; Cheminow (registered trademark) MX series, MZ series, MR series, KMR series, KSR series, MP series, SX series, SGP series [above, manufactured by Soken Chemical Co., Ltd.]; Taftik (registered trademark)AR650 series, AR-750 series, FH-S series, A-20, YK series, ASF series, HU series, F series, C series, WS series [above, manufactured by Toyobo Corporation] ; Art Pearl (registered trademark) GR series, SE series, G series, GS series, J series, MF series, BE series [above, manufactured by Negami Industrial Co., Ltd.]; Shin-Etsu Silicone (registered trademark) KMP series (manufactured by Shin-Etsu Chemical Co., Ltd.) or 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) organic fine particles are used in an amount of 8 to 30 parts by mass, preferably 8 to 20 parts by mass, based on 100 parts by mass of the active energy ray-curable polyfunctional monomer (a) described above. do.

[(d)활성에너지선에 의해 라디칼을 발생하는 중합개시제][(d) Polymerization initiator that generates radicals by active energy rays]

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.In the curable composition of the present invention, a polymerization initiator that generates radicals by an active energy ray preferable (hereinafter also simply referred to as “(d) polymerization initiator”) is, for example, active energy rays such as electron beams, ultraviolet rays, and X-rays. It is a polymerization initiator that generates radicals by, in particular, 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.As the (d) polymerization initiator, for example, benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic and onium salts such as peroxides, benzophenones, biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and iodonium salts and sulfonium salts. These can also be used individually by 1 type or in mixture of 2 or more types.

그 중에서도 본 발명에서는, 투명성, 표면경화성, 박막경화성의 관점에서 (d)중합개시제로서, 알킬페논류를 사용하는 것이 바람직하다. 알킬페논류를 사용함으로써, 내찰상성이 보다 향상된 경화막을 얻을 수 있다.Especially, in this invention, it is preferable to use alkylphenones as (d) a polymerization initiator from a viewpoint of transparency, surface hardening property, and thin film curability. By using alkylphenones, the cured film which abrasion resistance improved more 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.Examples of the alkylphenones include 1-hydroxycyclohexyl=phenyl=ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-(4- (2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)- α-hydroxyalkylphenones such as 2-methylpropan-1-one; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, etc. of α-aminoalkylphenones; 2,2-dimethoxy-1,2-diphenylethan-1-one; Methyl phenylglyoxylate, etc. are mentioned.

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 1 to 20 parts by mass, preferably 2 to 10 parts by mass, with respect to 100 parts by mass of the active energy ray-curable polyfunctional monomer (a) described above. 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 further contains the (e) solvent, that is, it can be 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, the components (a) to (d) are dissolved and dispersed, and the workability at the time of coating according to the formation of a cured film (hard coat layer) described later, dryness before and after curing, etc., and the like are appropriately selected. What may be done, for example, aromatic hydrocarbons, such as benzene, toluene, xylene, ethylbenzene, tetrain; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit and cyclohexane; halides such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene 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 , ethers such as 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; Heterocyclic compounds, such as N-methyl- 2-pyrrolidone, and these 2 or more types of mixed solvent are mentioned.

또한, 도공 후의 건조시에 있어서의 상기 미립자의 분산성을 제어하는 목적으로, 고비점의 용매를 사용할 수도 있다.Moreover, in order to control the dispersibility of the said microparticles|fine-particles at the time of drying after coating, you can also use a high boiling point solvent.

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.Examples of the solvent include cyclohexyl acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, and ethylene glycol monobutyl ether. Acetate, 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, tripropylene glycol Propylene glycol monobutyl ether, 3-methoxybutanol, dipropylene glycol dimethyl ether, dipropylene glycol = methyl = propyl = ether, etc. are mentioned.

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.Although the usage-amount of these (e) solvent is not specifically limited, For example, the solid content concentration in the curable composition of this invention is 1-70 mass %, Preferably it uses at the density|concentration used as 5-50 mass %. Here, the solid content concentration (also referred to as non-volatile matter concentration) refers to the solid content (from all components) to the total mass (total mass) of the components (a) to (e) (and other additives as necessary) of the curable composition of the present invention. component) is shown.

[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.In addition, additives generally added as needed to the curable composition of the present invention as long as the effects of the present invention are not impaired, for example, polymerization inhibitors, photosensitizers, leveling agents, surfactants, adhesion imparting agents, A plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like can be appropriately blended.

또한, 경화막의 헤이즈값을 제어하는 목적으로, 산화티탄 등의 무기미립자를 배합할 수도 있다.Moreover, inorganic fine particles, such as a titanium oxide, can also be mix|blended for the purpose of controlling the haze value of a cured film.

<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 this invention can form a cured film by apply|coating (coating) to a base material, forming a coating film, irradiating an active energy ray to this coating film, and superposing|polymerizing (curing). This cured film is also the object of this invention. Moreover, the hard-coat layer in the hard-coat film mentioned later can be made into what consists 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.As the base material in this case, for example, various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin, polyamide, polyimide) , epoxy resin, melamine resin, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin), metal, wood, paper, glass, slate and the like. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded 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 is 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, an inkjet method, a printing method (convex plate, intaglio plate) , flat plate, screen printing, etc.) can be appropriately selected, and among them, it can be used for a roll-to-roll method, and from the viewpoint of thin film coating properties, a convex plate printing method, particularly gravure coating It is preferable to use the law. Moreover, it is preferable to apply to application|coating after filtering a curable composition in advance using the filter etc. whose pore diameter is about 0.2 micrometer. On the other hand, when apply|coating, you may add a solvent further to this curable composition as needed. As a solvent in this case, the various solvents mentioned in the above-mentioned [(e) solvent] are mentioned.

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 coating the curable composition and forming a coating film on the substrate, if necessary, the coating film is pre-dried using a hot plate or oven to remove the solvent (solvent removal process). As conditions for heat-drying at this time, it is 40-120 degreeC, and it is preferable to set it as about 30 second - about 10 minutes, for example.

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, the coating film is cured by irradiating active energy rays such as ultraviolet rays. As an active energy ray, an ultraviolet-ray, an electron beam, X-ray, etc. are mentioned, Especially an ultraviolet-ray is preferable. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, UV-LED, etc. can be used.

나아가 그 후, 포스트베이크를 행함으로써, 구체적으로는 핫플레이트, 오븐 등을 이용하여 가열함으로써 중합을 완결시켜도 된다.Furthermore, you may complete superposition|polymerization by performing post-baking after that, specifically, by heating using a hotplate, oven, etc.

한편, 형성되는 경화막의 두께는, 건조, 경화 후에 있어서, 통상 0.01~50μm, 바람직하게는 0.05~20μm이다.On the other hand, after drying and hardening, the thickness of the cured film formed is 0.01-50 micrometers normally, Preferably it is 0.05-20 micrometers.

<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.Using the curable composition of the present invention, a hard coat film having a hard coat layer on at least one surface (surface) of the film substrate can be produced. This hard coat film is also a subject of the present invention, and this hard coat film is suitably used, for example, in order to protect the surface of various display elements, such as a touch panel and a liquid crystal display.

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 is formed by applying the above-described curable composition of the present invention on a film substrate to form a coating film, and irradiating the coating film with active energy rays such as ultraviolet rays to the coating film It can be formed by a method including a step of curing.

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 that can be used for optical purposes among the substrates mentioned in the above-mentioned <cured film> are used. Preferably, for example, polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyi and a resin film selected from mead and triacetyl cellulose.

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.In addition, as for the coating method of the curable composition on the said film base material (coating-film formation process), and the method of irradiating an active energy ray to a coating film (curing process), the method mentioned in the <cured film> mentioned above can be used. In addition, after the coating film forming step, if necessary, the coating film may include a step of drying the solvent and removing the solvent. In that case, the drying method (solvent removal process) of the coating film in the <cured film> mentioned above 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 that of the average particle diameter of the organic fine particles. For example, the thickness of the said hard-coat layer becomes like this. Preferably it is 1-20 micrometers, More preferably, it is 3-10 micrometers.

실시예Example

이하, 실시예를 들어, 본 발명을 보다 구체적으로 설명하나, 본 발명은 하기의 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail 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.In addition, in the Example, the apparatus and conditions used for preparation of a sample and analysis of a physical property are as follows.

(1) 바코트도포(1) Bar coat application

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

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

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

도포속도: 4m/분Application speed: 4 m/min

(2) 오븐(2) oven

장치: 애드밴텍토요(주)제 무진건조기 DRC433FADevice: Dust-free dryer DRC433FA manufactured by Advantech Toyo

(3) UV경화(3) UV curing

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

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

(4) 막두께(4) film thickness

장치: (주)니콘제 디지털측장기 디지마이크로 MH-15M + 카운터TC-101Device: Digimicro MH-15M + Counter TC-101, digital measuring instrument made by Nikon Corporation

(5) 광택도(5) Glossiness

장치: 코니카미놀타(주)제 광택계 GM-268PlusDevice: Konica Minolta Co., Ltd. gloss meter GM-268Plus

측정각도: 60도Measuring angle: 60 degrees

(6) 찰상시험(6) Scratch test

장치: 신토과학(주)제 왕복마모시험기 TRIBOGEAR TYPE: 30SDevice: Shinto Science Co., Ltd. reciprocating wear tester TRIBOGEAR TYPE: 30S

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

주사거리: 50mmScanning distance: 50mm

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

장치: 일본전색공업(주)제 헤이즈미터 NDH5000Apparatus: Haze meter NDH5000 manufactured by Nippon Denshik Industries Co., Ltd.

(8) 접촉각(8) contact angle

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

측정온도: 20℃Measuring temperature: 20℃

또한, 약기호는 이하의 의미를 나타낸다.In addition, the abbreviation shows the following meaning.

PFPE1: 양말단에 폴리(옥시알킬렌)기(반복단위수 8~9)를 개재하여 하이드록시기를 갖는 퍼플루오로폴리에테르[솔베이스페셜리티폴리머즈사제 Fluorolink 5147X]PFPE1: Perfluoropolyether having hydroxyl groups via poly(oxyalkylene) groups (number of repeating units 8 to 9) at both terminals [Fluorolink 5147X manufactured by Solbase Specialty Polymers]

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

PFPE3: 양말단에 하이드록시기를 갖는 퍼플루오로폴리에테르[솔베이스페셜리티폴리머즈사제 Fluorolink D]PFPE3: Perfluoropolyether having hydroxyl groups at both ends [Fluorolink D manufactured by Solbase Specialty Polymers]

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

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

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

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

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

SM4: 퍼플루오로폴리에테르구조를 갖는 UV반응형 불소계 표면개질제[DIC(주)제 메가팍(등록상표)RS-75, 유효성분 40질량%MEK/MIBK용액]SM4: UV-reactive fluorine-based surface modifier having a perfluoropolyether structure [DIC Co., Ltd. Megapac (registered trademark) RS-75, active ingredient 40% by mass MEK/MIBK solution]

FP1: 가교폴리메타크릴산메틸 진구상 입자[세키수이화성품공업(주)제 테크폴리머(등록상표)SSX-105, 평균입자경 5μm]FP1: cross-linked polymethyl methacrylate spherical particles [Sekisui Chemical Industry Co., Ltd. Tech Polymer (registered trademark) SSX-105, average particle diameter 5 μm]

FP2: 가교폴리메타크릴산메틸 진구상 입자[세키수이화성품공업(주)제 테크폴리머(등록상표)SSX-103, 평균입자경 3μm]FP2: crosslinked polymethyl methacrylate spherical particles [Sekisui Chemical Industry Co., Ltd. Tech Polymer (registered trademark) SSX-103, average particle diameter 3 μm]

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FP4: 가교실리콘 진구상 입자[모멘티브·퍼포먼스·마테리얼즈(동)제 토스펄(등록상표)120, 평균입자경 2μm]FP4: crosslinked silicone spherical particles [Tospearl (registered trademark) 120 manufactured by Momentive Performance Materials (copper), average particle diameter 2 µm]

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

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 manufactured by BASF Japan Co., Ltd.]

EPA: p-디메틸아미노안식향산에틸[일본화약(주)제 KAYACURE(등록상표)EPA]EPA: p-dimethylamino ethyl benzoate [KAYACURE (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.]

PET: 양면이접착처리 폴리에틸렌테레프탈레이트(PET)필름[토레이(주)제 루밀러(등록상표)U403, 두께 100μm]PET: Double-sided adhesive-treated polyethylene terephthalate (PET) film [Lumiller (registered trademark) U403 manufactured by Toray Co., Ltd., thickness 100 μm]

PC: 양면이접착처리 폴리카보네이트(PC)필름[미쯔비시가스화학(주)제 유피론(등록상표)·필름 FE-2000, 두께 100μm]PC: Double-sided adhesive polycarbonate (PC) film [Mitsubishi Gas Chemical Co., Ltd. Upiron (registered trademark) Film FE-2000, thickness 100μm]

TAC: 양면이접착처리 셀룰로오스트리아세테이트(TAC)필름[후지필름(주)제 후지택(등록상표)TD80ULM, 두께 80μm]TAC: Cellulose triacetate (TAC) film with double-sided adhesive treatment [FUJITAK (registered trademark) TD80ULM manufactured by FUJIFILM Co., Ltd., thickness 80μm]

AcOPr: 아세트산프로필AcOPr: 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.Into the screw tube, 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 added. The mixture was stirred at room temperature (about 23° C.) for 24 hours using a stirrer chip. 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.Into the screw tube, 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 added. 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 acryloyl groups at both terminals

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.Into the screw tube, PFPE3 2.0g (1.0mmol), BEI 0.52g (2.0mmol), DBTDL 0.01g (0.02mmol), and MEK 2.52g were added. 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 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.According to description in Table 1, the following components were mixed, and the curable composition of the solid content concentration of Table 1 was prepared. In addition, solid content refers to components other than a solvent here. In addition, in a table|surface, [part] shows [mass part].

(1) 다관능모노머: DPHA 50질량부, UA 30질량부, 및 PETA 20질량부(1) polyfunctional 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 amount of the surface modifier shown in Table 1 in Table 1 (in terms of solid content or active ingredient)

(3) 유기미립자: 표 1에 기재된 유기미립자를 표 1에 기재된 양(3) Organic fine particles: the amount of the organic particles listed in Table 1 in Table 1

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

(5) 용매: PGME 표 1에 기재된 양(5) solvent: the amount listed in PGME 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 bar-coated using the bars shown in Table 2 on an A4 size double-sided adhesive-treated PET film (Toray Co., Ltd. Lumiler (registered trademark) U403, thickness 100 µm) to obtain a coating film. The coating film was dried in an oven at 120° C. for 3 minutes to remove the solvent. A hard coat film having a hard coat layer (cured film) having a thickness shown in Table 2 was prepared by exposing the obtained film by irradiating UV light with an exposure amount of 500 mJ/cm 2 in a nitrogen atmosphere.

[실시예 6~9][Examples 6-9]

표 1의 기재에 따라 이하의 각 성분을 혼합하고, 고형분 농도 40질량%의 경화성 조성물을 조제하였다.According to description of Table 1, each of the following components was mixed, and the curable composition with a solid content concentration of 40 mass % was prepared.

(1) 다관능모노머: DPHA 50질량부, UA 30질량부, 및 PETA 20질량부(1) polyfunctional 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 amount of the organic particles listed in Table 1 in Table 1

(4) 무기미립자: 표 1에 기재된 무기미립자를 표 1에 기재된 양(4) Inorganic fine particles: the amount of the inorganic fine particles listed in Table 1 in Table 1

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

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

(7) 용매: 표 1에 기재된 용매를 표 1에 기재된 양(7) solvent: the amount of the solvent listed in Table 1 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 bar-coated using the bar 1 on the film of Table 2 of A4 size, and the coating film was obtained. This coating film was dried in an oven under the conditions shown in Table 2 to remove the solvent. The obtained film was irradiated with UV light at an exposure amount of 500 mJ/cm 2 in a nitrogen atmosphere and exposed to prepare 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.Appearance, anti-glare property, scratch resistance, total light transmittance, haze, and contact angle of water and oleic acid of the obtained hard coat film were evaluated. The order of evaluation of an external appearance, anti-glare property, abrasion resistance, and a contact angle is shown below. In addition, a result is shown together 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: There is no stain over the entire surface of the hard coat layer

C: 하드코트층 전체면에 응집물이 석출되어 반상의 얼룩이 눈에 띔C: Agglomerates were precipitated on the entire surface of the hard coat layer, so that the speckle stain was conspicuous.

[방현성][Bang Hyun-seong]

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 mounted on a black stand having a glossiness Gs (60°) of 11.8, and the glossiness Gs (60°) on the surface of the hard coat layer was measured and evaluated according to the following criteria. On the other hand, when actual use is assumed as a hard-coat layer, it is calculated|required that it is at least B, and it is preferable that it is A.

A: Gs(60°)≤120A: Gs(60°)≤120

B: 120<Gs(60°)≤125B: 120<Gs(60°)≤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.Apply a load of 1kg/cm 2 to the surface of the hard coat layer with steel wool [Bonstar (registered trademark) #0000 (ultra-fine)] attached to a reciprocating abrasion tester, rubbing the surface of the hard coat layer 1,000 reciprocally. A line was drawn with an oily marker [using the three sides, Mackie micro-fine (blue) made by Zebra Co., Ltd.]. Subsequently, the drawn line was wiped off with a non-woven fabric wiper [BEMCOT M-1 manufactured by Asahi Kasei Textile Co., Ltd.], and the degree of damage was visually checked and evaluated according to the following criteria. On the other hand, when actual use is assumed as a hard-coat layer, it is calculated|required that it is at least B, and it is preferable that it is A.

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

B: 약간 흠집이 생겼으나 유성마커로 그린 선이 깨끗이 닦아내짐B: Slightly scratched, but the lines drawn with an oil-based marker are wiped clean

C: 유성마커의 잉크가 흠집에 들어가 닦아내지지 않음C: The ink of the oil-based marker enters the scratches and is not wiped off

[접촉각][Contact angle]

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

[표 1][Table 1]

Figure 112021024421392-pct00003
Figure 112021024421392-pct00003

[표 2][Table 2]

Figure 112021024421392-pct00004
Figure 112021024421392-pct00004

[표 3][Table 3]

Figure 112021024421392-pct00005
Figure 112021024421392-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 9의 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 acryloyl groups via poly(oxyalkylene) groups at both ends were used as surface modifiers in the hard coat layer, and organic Each hard coat film produced by using the curable composition of Examples 1 to 9 containing fine particles had a film thickness of 4 to 6 µm, and was excellent in scratch resistance, and a non-uniform appearance was obtained. Moreover, also about anti-glare property, compared with the comparative example mentioned later, it was to satisfy all the criteria in the case of considering actual use.

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 Examples 1 and 2 in which the amount of organic fine particles added was less than the numerical range determined in the present invention, and Comparative Example 6 in which organic fine particles were not added, desired anti-glare properties were 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.In addition, as a surface modifier of the hard coat layer, instead of perfluoropolyether having an acryloyl group through a poly(oxyalkylene) group at both ends, acrylonitrile without a poly(oxyalkylene) group at both ends Comparative Example 3 using perfluoropolyether SM3 having a diary was inferior in abrasion resistance to that of Example, and aggregates were precipitated on the entire surface of the hard coat layer, thereby exhibiting a conspicuous appearance with spots.

또한, 표면개질제로서 퍼플루오로폴리에테르구조를 갖는 UV반응형 불소계 표면개질제SM4를 이용한 비교예 4 및 비교예 5는, 내찰상성이 크게 뒤떨어지는 결과가 되었다.In addition, Comparative Examples 4 and 5 using a UV-reactive fluorine-based surface modifier SM4 having a perfluoropolyether structure as a surface modifier was significantly inferior in 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 Examples, it is difficult to obtain satisfactory results in the scratch resistance and appearance of the hard coat layer only by slightly different structures of the terminals of the perfluoropolyethers used as the surface modifier, When the addition amount of the organic fine particles is outside the predetermined range, anti-glare properties cannot be obtained, and only the curable composition of the present invention can obtain a hard coat film satisfying all these properties.

Claims (13)

(a) 다관능(메트)아크릴레이트 화합물 및 다관능우레탄(메트)아크릴레이트 화합물로 이루어진 군으로부터 선택되는 적어도 1개인 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 가지며, 상기 활성에너지선 경화성 다관능모노머의 경화물과의 굴절률차가 0~0.20인 굴절률을 가지고 이루어지는 유기미립자 8~30질량부,
(d) 활성에너지선에 의해 라디칼을 발생하는 중합개시제 1~20질량부, 및
(e) 유기용매
를 포함하는 경화성 조성물.
(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer which is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound;
(b) at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, a poly(oxyalkylene) group or a poly(oxyalkylene) group and one urethane bond are interposed in this order 0.1 to 10 parts by mass of a perfluoropolyether having an active energy ray polymerizable group;
(c) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 μm and having a refractive index difference of 0 to 0.20 from the cured product of the active energy ray-curable polyfunctional monomer;
(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, and
(e) organic solvents
A curable composition comprising a.
 제1항에 있어서,
상기 폴리(옥시퍼플루오로알킬렌)기가, -[OCF2]- 및 -[OCF2CF2]-를 반복단위로서 갖는 기인, 경화성 조성물.
According to claim 1,
The poly(oxyperfluoroalkylene) group is a group having -[OCF 2 ]- and -[OCF 2 CF 2 ]- as repeating units, the curable composition.
 제1항에 있어서,
상기 폴리(옥시알킬렌)기가 폴리(옥시에틸렌)기인, 경화성 조성물.
According to claim 1,
wherein the poly(oxyalkylene) group is a poly(oxyethylene) group.
 삭제delete 제1항에 있어서,
상기 성분(c)의 유기미립자가 진구상 입자인, 경화성 조성물.
According to claim 1,
The curable composition, wherein the organic fine particles of the component (c) are spherical particles.
 제1항에 있어서,
상기 성분(c)의 유기미립자가 폴리메타크릴산메틸입자 및 실리콘입자로 이루어진 군으로부터 선택되는 적어도 1개인, 경화성 조성물.
According to claim 1,
The curable composition, wherein the organic fine particles of the component (c) is at least one selected from the group consisting of polymethyl methacrylate particles and silicone particles.
 제1항에 있어서,
상기 성분(d)의 중합개시제가 알킬페논류인, 경화성 조성물.
According to claim 1,
The curable composition, wherein the polymerization initiator of the component (d) is alkylphenones.
 제1항에 기재된 경화성 조성물로부터 얻어지는 경화막.
The cured film obtained from the curable composition of Claim 1.
 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, 제1항에 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 surface of a film substrate, wherein the hard coat layer applies the curable composition according to claim 1 on a film substrate to form a coating film; A hard coat film formed by a method comprising a step of curing by irradiating energy rays.
 제9항 또는 제10항에 있어서,
상기 하드코트층이, 상기 유기미립자의 평균입경에 비해 1배~10/7배의 두께를 갖는, 하드코트필름.
11. The method of claim 9 or 10,
The hard coat layer has a thickness of 1 to 10/7 times that of the average particle diameter of the organic fine particles, the hard coat film.
 제9항 또는 제10항에 있어서,
상기 하드코트층이 1~20μm의 막두께를 갖는, 하드코트필름.
11. The method of claim 9 or 10,
The hard coat layer having a film thickness of 1 to 20 μm, a hard coat film.
 제12항에 있어서,
상기 하드코트층이 3~10μm의 막두께를 갖는, 하드코트필름.
13. The method of claim 12,
The hard coat layer having a film thickness of 3 to 10 μm, a hard coat film.
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