KR20180108456A - Active-energy-ray curable hard coating agent, curable coating film, laminated film - Google Patents

Active-energy-ray curable hard coating agent, curable coating film, laminated film Download PDF

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KR20180108456A
KR20180108456A KR1020180030060A KR20180030060A KR20180108456A KR 20180108456 A KR20180108456 A KR 20180108456A KR 1020180030060 A KR1020180030060 A KR 1020180030060A KR 20180030060 A KR20180030060 A KR 20180030060A KR 20180108456 A KR20180108456 A KR 20180108456A
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meth
component
parts
hard coating
acrylate
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KR102350325B1 (en
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호다카 사누키
요시노부 사토
히로토시 고야노
히로시 사와다
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아라까와 가가꾸 고교 가부시끼가이샤
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/67—Particle size smaller than 100 nm

Abstract

Provided is a novel active energy ray curable hard coating agent capable of forming a curable coating films having high surface tension on a surface of various articles. To this end, the active energy ray curable hard coating agent comprises: multifunctional (meth)acrylates (A) composed of a monomeric radical polymer (a1-1) having an epoxy group-containing mono(meta)acrylate, a hydroxyl group-containing (meth)acrylic copolymer (a1) as a reaction product of α,β-unsaturated carboxylic acid (a1-2), and/or a hydroxyl group-containing multifunctional (meth)acrylate (a2) having at least three (meth)acryloyl groups, wherein concentration of the hydroxyl group is at least 0.8 μmol/g; and a hydrophilic silica microparticle (B) whose surface silanol group concentration is 60-200 μmol/g. The weight ratio of solids ((A)/(B)) is 20/80-90/10.

Description

활성에너지선 경화형 하드코팅제, 경화도포막, 적층필름{ACTIVE-ENERGY-RAY CURABLE HARD COATING AGENT, CURABLE COATING FILM, LAMINATED FILM}{ACTIVE-ENERGY-RAY CURABLE HARD COATING AGENT, CURABLE COATING FILM, LAMINATED FILM}

본 발명은, 각종 물품의 표면에 높은 표면장력(表面張力)의 경화도포막을 형성할 수 있는 활성에너지선 경화형 하드코팅제, 및 상기 하드코팅제로부터 얻어지는 경화도포막 및 상기 경화도포막을 구비하는 적층필름에 관한 것이다.The present invention relates to an active energy ray hardening type hard coating agent capable of forming a cured coating film of high surface tension (surface tension) on the surface of various articles, and a laminated film comprising the cured coating film obtained from the hard coating agent and the cured coating film will be.

활성에너지선 경화형 하드코팅제는, 각종 물품에 도포하여 자외선 등의 활성에너지선을 조사함으로써 용이하게 경화되어, 고경도이고 내찰상성, 투명성 등이 우수한 경화도포막(하드코팅 도포막)을 형성한다. 그 때문에 각종 플라스틱, 글라스, 종이 등의 기재의 표면을 보호하기 위해서 널리 사용되고 있다.The active energy rays hardening type hard coating agent is applied to various articles and irradiated with actinic energy rays such as ultraviolet ray to easily cure to form a hardening film (hard coating film) having excellent hardness, scratch resistance and transparency. Therefore, it is widely used for protecting the surfaces of various plastics, glasses, paper, and the like.

그러나 종래의 하드코팅 도포막은 리코팅성이 나쁘고, 점착필름의 점착층을 밀착시키거나, 도료 및 인쇄 잉크 등을 도포하거나 하는 것이 어려웠다(특허문헌1, 2 참조). 그 원인으로서, 일반적으로 하드코팅 도포막은 표면장력이 낮고 점착필름, 도료 및 인쇄 잉크와의 밀착성이 나쁘기 때문이라고 하고 있다.However, the conventional hard coating film has poor recoatability, and it has been difficult to adhere the pressure sensitive adhesive layer of the pressure sensitive adhesive film, or to apply a paint or a printing ink or the like (see Patent Documents 1 and 2). As a cause thereof, it is generally said that the hard coat coating film has a low surface tension and poor adhesion to the adhesive film, paint and printing ink.

상기 과제에 관한 것으로서, 특허문헌3의 적층필름은, 점착층에 접합시키는 하드코팅층에 친수성 첨가제를 포함시킴으로써 상기 하드코팅층의 표면장력을 향상시켜, 양층의 밀착성을 개선하고 있다.In the above-mentioned problem, the laminated film of Patent Document 3 improves the surface tension of the hard coat layer by including a hydrophilic additive in the hard coat layer bonded to the adhesive layer, and improves the adhesion of both layers.

그러나 상기 하드코팅층의 표면장력은 아직 낮은 것이었다. 또한 상기 하드코팅층에 높은 표면장력을 갖게 하기 위해서는, 하드코팅층에 대한 코로나 방전처리나, 친수성 첨가제를 포함한 점착층을 접합시켜 상기 하드코팅층에 대하여 친수성 첨가제를 이행하는 처리가 필요했다.However, the surface tension of the hard coat layer was still low. Further, in order to impart a high surface tension to the hard coat layer, a treatment for corona discharge treatment for the hard coat layer and a process for bonding the adhesive layer containing a hydrophilic additive to the hard coat layer to transfer the hydrophilic additive were required.

일본 공개특허공보 특개2005-170979호 공보Japanese Patent Application Laid-Open No. 2005-170979 일본 공개특허공보 특개2009-161609호 공보Japanese Unexamined Patent Application Publication No. 2009-161609 일본 공개특허공보 특개2016-126451호 공보Japanese Unexamined Patent Application Publication No. 2016-126451

본 발명은, 높은 표면장력을 구비하는 경화도포막을 각종 물품의 표면에 형성할 수 있는 신규의 활성에너지선 경화형 하드코팅제를 제공하는 것을 과제로 한다.It is an object of the present invention to provide a novel active energy ray hardening type hard coating agent capable of forming a cured coating film having a high surface tension on the surface of various articles.

본 발명자는 검토한 결과, 소정의 다관능 아크릴레이트류 및 소정의 친수성 실리카 미립자를, 특정한 질량비로 포함하는 활성에너지선 경화형 하드코팅제에 의하여 상기 과제를 해결할 수 있는 것을 찾아냈다. 즉 본 발명은, 이하의 활성에너지선 경화형 하드코팅제, 상기 하드코팅제로부터 얻어지는 경화도포막 및 상기 경화도포막을 구비하는 적층필름에 관한 것이다.As a result of the investigation, the inventors of the present invention have found that the aforementioned problems can be solved by an active energy ray hardening type hard coating agent containing predetermined polyfunctional acrylates and predetermined hydrophilic silica fine particles at a specific mass ratio. That is, the present invention relates to the following active energy ray-curable hard coating, a cured coating obtained from the hard coating, and a laminated film comprising the cured coating.

1.에폭시기 함유 모노(메타)아크릴레이트를 포함하는 모노머 성분의 라디칼 중합체(a1-1) 및 α,β-불포화 카르복시산(a1-2)의 반응물인 수산기 함유 (메타)아크릴 공중합체(a1), 및/또는 적어도 3개의 (메타)아크릴로일기를 구비하는 수산기 함유 다관능 (메타)아크릴레이트(a2)를 포함하는 수산기 농도가 0.8ｍｍｏｌ/ｇ 이상인 다관능 (메타)아크릴레이트류(A)와,(Meth) acrylic copolymer (a1) which is a reaction product of a monomeric component radical polymer (a1-1) containing an epoxy group-containing mono (meth) acrylate and an?,? - unsaturated carboxylic acid (Meth) acrylate (A) having a hydroxyl group concentration of 0.8 mmol / g or more and / or a hydroxyl group-containing polyfunctional (meth) acrylate (a2) having at least three (meth) acryloyl groups and ,

표면 실라놀기 농도가 60∼200μｍｏｌ/g인 친수성 실리카 미립자(B)를,Hydrophilic silica fine particles (B) having a surface silanol group concentration of 60 to 200 占 퐉 ol / g,

고형분질량비((A)/(B))로 20/80∼90/10 포함하는 활성에너지선 경화형 하드코팅제.And an active energy ray hardening type hard coating agent comprising a solid content ratio ((A) / (B)) of 20/80 to 90/10.

2.(B)성분의 표면 실라놀기 농도가 100∼200μｍｏｌ/g인 상기 항1의 활성에너지선 경화형 하드코팅제.2. The active energy ray hardening type hard coating agent according to item 1, wherein the component (B) has a surface silanol group concentration of 100 to 200 占 퐉 ol / g.

3.(A)성분과 (B)성분의 고형분질량비((A)/(B))가 30/70∼70/30인 상기 항1 또는 2의 활성에너지선 경화형 하드코팅제.3. The active energy ray-curable hard coating according to item 1 or 2, wherein the solid content ratio (A) / (B) of the component (A) and the component (B) is 30/70 to 70/30.

4.(B)성분의 평균1차입경이 10∼50nm인 상기 항1의 활성에너지선 경화형 하드코팅제.4. The active energy ray hardening type hard coating agent according to item 1, wherein the average primary particle diameter of the component (B) is 10 to 50 nm.

5.광중합개시제(C)를 더 함유하는 상기 항1의 활성에너지선 경화형 하드코팅제.5. The active energy ray hardening type hard coating agent according to item 1, further comprising a photopolymerization initiator (C).

6.상기 항1의 하드코팅제의 경화도포막.6. The cured coating of the hard coating of item 1 above.

7.표면장력이 44∼48ｄｙｎ/cm인 상기 항6의 경화도포막.7. The cured film of item 6, wherein the surface tension is 44 to 48 dyn / cm.

8.상기 항6 또는 7의 경화도포막을 구비하는 적층필름.8. A laminated film comprising the cured coating film of item 6 or 7 above.

본 발명의 활성에너지선 경화형 하드코팅제는, 코로나 방전처리 등의 추가공정을 요하지 않고, 예를 들면 44∼48ｄｙｎ/cm 정도의 높은 표면장력의 경화도포막(하드코팅 도포막)을 제공할 수 있다. 그리고 상기 하드코팅 도포막은 내구성도 우수하여, 상기 도포막을 가열처리해서 표면을 알코올 등으로 닦아내어도 높은 표면장력이 지속된다. 또한 상기 하드코팅 도포막의 표면으로부터는 친수성 실리카 미립자의 결락(缺落)도 없다. 또한 상기 하드코팅 도포막은 도포막 표면이 평활해서, 요철표면(오렌지필)(orange peel), 핀홀 등의 발생이 억제되어 있기 때문에, 도포막 외관이 우수하게 된다.The active energy ray hardening type hard coating agent of the present invention can provide a cured coating film (hard coating film) having a high surface tension of, for example, about 44 to 48 dyn / cm without requiring an additional step such as a corona discharge treatment. The hard coating film is excellent in durability, and the surface tension is maintained even if the surface of the coating film is wiped with alcohol or the like. Further, there is no loss of hydrophilic silica fine particles from the surface of the hard coat coating film. Further, since the surface of the coating film of the hard coat coating film is smooth, generation of irregularities (orange peel), pinholes, and the like are suppressed, so that the appearance of the coating film is excellent.

본 발명의 활성에너지선 경화형 하드코팅제에 의하면, 글라스, 종이, 플라스틱 필름 및 성형체 등의 각종 물품에 높은 표면장력의 하드코팅 도포막을 적층할 수 있다. 또한 상기 도포막을 적층한 필름은 양호한 리코팅성을 나타내고, 하드코팅제, 도료, 인쇄 잉크 및 점착층에 대하여 밀착성이 높고, 그들을 적층하는 용도에 있어서 적합한 필름이 될 수 있다.According to the active energy ray hardening type hard coating agent of the present invention, a hard coating film having a high surface tension can be laminated on various articles such as glass, paper, plastic film and molded article. Further, the film laminated with the above coating film exhibits good recoatability and can be a film suitable for applications in which they are highly adhesive to hard coating agents, paints, printing inks and adhesive layers.

본 발명의 활성에너지선 경화형 하드코팅제(이하, 하드코팅제)는, 소정의 다관능 아크릴레이트류(A)(이하, (A)성분) 및 소정의 친수성 실리카 미립자(B)(이하, (B)성분)를, 특정한 질량비로 포함하는 조성물이다.The active energy ray hardening type hard coating agent (hereinafter referred to as a hard coating agent) of the present invention comprises a predetermined polyfunctional acrylate (A) (hereinafter referred to as component (A)) and predetermined hydrophilic silica fine particles (B) Component) at a specific mass ratio.

(A)성분은, 분자내에 수산기를 구비하고 또한 특정한 수산기 농도를 구비하는 다관능 (메타)아크릴레이트류이면, 각종 공지의 것을 특별히 제한없이 사용할 수 있다. 구체적으로는, (A)성분의 수산기 농도가 보통 0.8ｍｍｏｌ/ｇ 이상, 바람직하게는 1.6∼4.7ｍｍｏｌ/ｇ 정도, 더 바람직하게는 2.0∼4.7ｍｍｏｌ/ｇ 정도가 되는 범위이면 좋다. 여기에서 말하는 수산기 농도는, (A)성분 중의 수산기수와 분자량으로부터 산출되는 값이다. 구체적으로는, (A)성분이 폴리머 이외인 경우에는 {(A)성분 1ｍｏｌ 중에 포함되는 수산기 ｍｏｌ수/(A)성분의 분자량}으로부터 산출되는 값이며, 또한 (A)성분이 혼합물인 경우에는 각 함유성분으로 산출한 수산기 농도를 각각의 함유비율로 곱하여 총 더한 값이다. (A)성분이 폴리머이면 {(A)성분의 반복구조 1ｍｏｌ 중에 포함되는 수산기 ｍｏｌ수/(A)성분의 반복구조의 식량(式量)}으로부터 산출되는 값이다. 수산기 농도가 상기 범위이면, 상기 하드코팅제로 형성되는 경화도포막(이하, 하드코팅 도포막)은 높은 표면장력을 구비하고, 또 도포막 외관이 우수한 것이 얻어진다. 이유는 불분명하지만, 상기 도포막 표면에 (A)성분의 수산기가 배향하여 상기 도포막의 표면장력이 높아지기 때문이라고 추정되고, 또 상기 수산기 농도를 구비하는 (A)성분은 (B)성분에 대한 상용성이 양호해져서, 기재에 하드코팅제를 평활하게 도포할 수 있고, 또한 (B)성분의 응집도 억제되기 때문이라고 추정된다.As the component (A), various known compounds can be used without particular limitation, provided that the component (A) is a polyfunctional (meth) acrylate having a hydroxyl group in the molecule and having a specific hydroxyl group concentration. Specifically, it is sufficient that the hydroxyl group concentration of the component (A) is usually 0.8 mmol / g or more, preferably 1.6 to 4.7 mmol / g, and more preferably 2.0 to 4.7 mmol / g. Here, the hydroxyl group concentration is a value calculated from the number of hydroxyl groups in the component (A) and the molecular weight. Specifically, when the component (A) is other than the polymer, it is a value calculated from {the number of moles of hydroxyl group contained in 1 mol of component (A) / the molecular weight of component (A)}. And the hydroxyl group concentration calculated by each containing component is multiplied by the respective content ratios and added together. (The number of moles of hydroxyl groups contained in 1 mol of the repeating structure of the component (A) / the amount of the repeating structure of the component (A)) (formula amount) if the component (A) is a polymer. When the hydroxyl group concentration is within the above range, the cured coating film (hereinafter referred to as the hard coating film) formed from the hard coating agent has a high surface tension and an excellent coating film appearance. The reason for this is unclear, but it is presumed that the hydroxyl group of the component (A) is oriented on the surface of the coating film to increase the surface tension of the coating film. The component (A) , It is presumed that the hard coating agent can be smoothly applied to the substrate and the aggregation of the component (B) is also suppressed.

(A)성분으로서는, 에폭시기 함유 모노(메타)아크릴레이트를 포함하는 모노머 성분의 라디칼 중합체(a1-1)(이하, (a1-1)성분) 및 α,β-불포화 카르복시산(a1-2)(이하, (a1-2)성분)의 부가반응물인 수산기 함유 (메타)아크릴 공중합체(이하, (a1)성분), 및/또는 적어도 3개의 (메타)아크릴로일기를 구비하는 수산기 함유 다관능 (메타)아크릴레이트(a2)(이하, (a2)성분)를 사용한다.(A1-1) (hereinafter referred to as a component (a1-1)) and an alpha, beta -unsaturated carboxylic acid (a1-2) (hereinafter referred to as a component (a1)) containing a mono (meth) (Meth) acrylic copolymer (hereinafter referred to as component (a1)) which is an addition reaction product of a hydroxyl group-containing polyfunctional (hereinafter referred to as component (a1-2)) and / (Meth) acrylate (a2) (hereinafter referred to as component (a2)) is used.

(a1)성분은 분자 중에 복수의 수산기와 (메타)아크릴로일기를 함유하는 공중합체이며, (B)성분과 조합시킴으로써 높은 표면장력과 경도 및 우수한 내찰상성을 구비하는 상기 하드코팅 도포막을 제공한다.The component (a1) is a copolymer containing a plurality of hydroxyl groups and (meth) acryloyl groups in the molecule, and is combined with the component (B) to provide the hard coating film having high surface tension and hardness and excellent scratch resistance .

(a1)성분의 수산기 농도는, (A)성분의 상기 수산기 농도를 충족하는 한 특별하게 한정되지 않지만, 상기 하드코팅 도포막의 표면장력 및 도포막 외관의 관점으로부터, 구체적으로는 보통 0.8ｍｍｏｌ/ｇ 이상, 바람직하게는 1.6∼4.7ｍｍｏｌ/ｇ 정도, 더 바람직하게는 2.0∼4.7ｍｍｏｌ/ｇ 정도가 되는 범위이면 좋다. 또한 (a1)성분의 중량평균분자량도 특별히 제한되지 않지만, 상기 도포막의 경도나 내찰상성의 관점으로부터, 보통 1,000∼100,000 정도, 바람직하게는 10,000∼50,000 정도가 되는 범위이면 좋다. 여기에서 말하는 중량평균분자량은, 겔 퍼미에이션 크로마토그래피(ＧＰＣ)법에 의한 폴리스티렌 환산치이다.The hydroxyl group concentration of the component (a1) is not particularly limited as long as it satisfies the above hydroxyl group concentration of the component (A), but from the viewpoints of the surface tension of the hard coat coating film and the appearance of the coating film, specifically 0.8 mmol / g Or more, preferably about 1.6 to 4.7 mmol / g, and more preferably about 2.0 to 4.7 mmol / g. The weight average molecular weight of the component (a1) is not particularly limited, but it is usually in the range of about 1,000 to about 100,000, preferably about 10,000 to about 50,000 from the viewpoints of hardness and scratch resistance of the coating film. The weight average molecular weight as referred to herein is a polystyrene equivalent value determined by gel permeation chromatography (GPC).

(a1-1)성분의 에폭시기 함유 모노(메타)아크릴레이트란, 분자내에 적어도 1개의 에폭시기와 1개의 중합성 불포화 2중결합을 구비하는 화합물이다. 구체적으로는, 글리시딜(메타)아크릴레이트, β-메틸글리시딜(메타)아크릴레이트, 3,4-에폭시시클로헥실메틸(메타)아크릴레이트, 비닐시클로헥센모노옥사이드(즉, 1,2-에폭시-4-비닐시클로헥산) 등을 들 수 있다. 이들은 각각을 단독으로 또는 2종 이상을 병용해서 배합하여도 좋다. 이들 중에서 입수 용이성과 조달비용의 면으로부터, 글리시딜(메타)아크릴레이트가 바람직하다.The epoxy group-containing mono (meth) acrylate of the component (a1-1) is a compound having at least one epoxy group and one polymerizable unsaturated double bond in the molecule. Specific examples thereof include glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene monoxide -Epoxy-4-vinylcyclohexane). These may be used alone or in combination of two or more. Among these, glycidyl (meth) acrylate is preferable from the viewpoints of availability and procurement cost.

(a1-1)성분을 구성하는 모노머 성분에는, 상기 에폭시기 함유 모노(메타)아크릴레이트의 이외에 공중합 가능한 모노머를 포함해도 좋다. 상기 모노머로서는, 구체적으로는, (메타)아크릴산메틸, (메타)아크릴산에틸 등의 사슬모양 알킬기를 구비하는 (메타)아크릴산에스테르류, (메타)아크릴산이소보닐 등의 지환구조를 구비하는 (메타)아크릴산에스테르류, 에톡시화o-페닐페놀아크릴레이트 등의 방향환을 구비하는 (메타)아크릴산에스테르류, 아크릴로일 모르폴린 등의 질소 함유 아크릴산에스테르류, (메타)아크릴아미드, 아크릴로니트릴, 스티렌, α-메틸스티렌, 비닐톨루엔 등의 방향족계 비닐 화합물, 아세트산비닐, 및 어느 일방의 말단에 불포화 2중결합을 구비하고 에폭시기 및 카르복실기를 함유하지 않는 매크로모노머(macromonomer) 등을 들 수 있다. 이들은 단독으로 또는 2종 이상을 병용해서 배합하여도 좋다.The monomer component constituting the component (a1-1) may include a copolymerizable monomer other than the epoxy group-containing mono (meth) acrylate. Specific examples of the monomer include (meth) acrylic acid esters having a chain alkyl group such as methyl (meth) acrylate and ethyl (meth) acrylate, (meth) acrylic acid esters having an alicyclic structure such as (meth) (Meth) acrylates having an aromatic ring such as ethoxylated o-phenylphenol acrylate, nitrogen-containing acrylates such as acryloylmorpholine, (meth) acrylamides, acrylonitrile, Aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene; vinyl acetate; and macromonomers which have an unsaturated double bond at either end and do not contain an epoxy group and a carboxyl group. These may be used alone or in combination of two or more.

(a1-2)성분으로서는, (a1-1)성분의 에폭시기와 부가반응할 수 있는 α,β-불포화 카르복시산이면, 각종 공지의 것을 특별하게 한정없이 사용할 수 있다. 구체적으로는, (메타)아크릴산 등의 α,β-불포화 모노카르복시산, 말레인산이나 푸마르산 등의 α,β-불포화 디카르복시산 등을 들 수 있다. 이들은 각각을 단독으로 또는 2종 이상을 병용하여도 좋다. 이들 중에서 상기 (a1-1)성분과의 반응성이나 저장안정성의 관점으로부터, (메타)아크릴산이 바람직하다.As the component (a1-2), various known ones can be used without particular limitation, provided that the component is an alpha, beta -unsaturated carboxylic acid capable of addition reaction with the epoxy group of the component (a1-1). Specific examples include?,? - unsaturated monocarboxylic acids such as (meth) acrylic acid, and?,? - unsaturated dicarboxylic acids such as maleic acid and fumaric acid. These may be used alone or in combination of two or more. Among them, (meth) acrylic acid is preferable from the viewpoints of reactivity with the component (a1-1) and storage stability.

(a2)성분은, (a1)성분 이외의 다관능 (메타)아크릴레이트류로서, 1분자 중에 적어도 3개의 (메타)아크릴로일기와 적어도 1개의 수산기를 함유하는 (메타)아크릴레이트를 포함하는 것이면, 각종 공지의 것을 특별하게 한정없이 사용할 수 있다. 구체적으로는, 펜타에리스리톨트리(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트 등의, 분자 중에 1개 이상의 수산기 및 3개 이상의 (메타)아크릴로일기를 포함하는 폴리펜타에리스리톨폴리(메타)아크릴레이트, 디트리메틸올프로판트리(메타)아크릴레이트 등의, 분자 중에 1개 이상의 수산기 및 3개 이상의 (메타)아크릴로일기를 포함하는 폴리트리메틸올프로판폴리(메타)아크릴레이트 등을 들 수 있다. 이들은 각각을 단독으로 또는 2종 이상을 병용해서 배합하여도 좋다. 2종 이상 사용하는 경우의 각 다관능 (메타)아크릴레이트 성분의 사용비율은 특별히 제한되지 않는다.The component (a2) is a polyfunctional (meth) acrylate other than the component (a1), and includes a (meth) acrylate containing at least three (meth) acryloyl groups and at least one hydroxyl group in one molecule , Various known ones can be used without particular limitation. Specifically, a polypentaerythritol poly (metha) acrylate having at least one hydroxyl group and at least three (meth) acryloyl groups in the molecule, such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (Meth) acrylate having at least one hydroxyl group and at least three (meth) acryloyl groups in the molecule, such as trimethylolpropane tri (meth) acrylate and ditrimethylol propane tri (meth) have. These may be used alone or in combination of two or more. The use ratio of each polyfunctional (meth) acrylate component in the case of using two or more kinds is not particularly limited.

(a2)성분은, 수산기를 포함하지 않는 폴리(메타)아크릴레이트류를 포함해도 좋다. 상기 폴리(메타)아크릴레이트류로서는, 구체적으로는, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트 등의, 분자 중에 수산기를 포함하지 않는 폴리펜타에리스리톨폴리(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트 등의, 분자 중에 수산기를 포함하지 않는 폴리트리메틸올프로판폴리(메타)아크릴레이트 등을 들 수 있다. (a2)성분에 있어서의 상기 폴리(메타)아크릴레이트류의 함유량은, 특별하게 한정되지 않지만, 보통 10∼50질량％ 정도이다.The component (a2) may include a poly (meth) acrylate not containing a hydroxyl group. Specific examples of the poly (meth) acrylates include polypentaerythritol poly (meth) acrylate having no hydroxyl group in the molecule such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) Polytrimethylol propane poly (meth) acrylate that does not contain a hydroxyl group in the molecule, such as ditrimethylolpropane tetra (meth) acrylate, and the like. The content of the poly (meth) acrylates in the component (a2) is not particularly limited, but is usually about 10 to 50 mass%.

(a2)성분의 시판품으로서는, 예를 들면 아로닛스Ｍ-303, Ｍ-305, Ｍ-306, Ｍ-400, Ｍ-402, Ｍ-403, Ｍ-404, Ｍ-405, Ｍ-406(모두 동아합성(주)(TOAGOSEI CO., LTD.) 제품), ＮＫ에스테르Ａ-9530, Ａ-9550, Ａ-9550Ｗ, Ａ-9570Ｗ, Ａ-ＴＭＭ-3, Ａ-ＴＭＭ-3Ｌ, Ａ-ＴＭＭ-3ＬＭ-Ｎ(모두 신나카무라화학공업(주)(Shin Nakamura Chemical Co., Ltd.) 제품) 등을 들 수 있고, 이들은 각각을 단독으로 또는 2종 이상을 병용할 수 있다.M-402, M-403, M-404, M-405, and M-406 (all of which are commercially available as Aronites M-303, M-305, M-306, M-400, A-TMM-3L, A-TMM-3L, and A-TMM-3L are commercially available from TOAGOSEI CO., LTD.), NK Ester A-9530, A-9550, A- 3LM-N (all available from Shin Nakamura Chemical Co., Ltd.), and these may be used singly or in combination of two or more kinds.

(a2)성분의 수산기 농도는, (A)성분의 상기 수산기 농도를 충족하는 한 특별하게 한정되지 않지만, 상기 하드코팅 도포막의 표면장력 및 도포막 외관의 관점으로부터, 보통 0.8ｍｍｏｌ/ｇ 이상, 바람직하게는 1.6∼4.7ｍｍｏｌ/ｇ 정도, 더 바람직하게는 2.0∼4.7ｍｍｏｌ/ｇ 정도가 되는 범위이면 좋다.The hydroxyl group concentration of the component (a2) is not particularly limited as long as it satisfies the above hydroxyl group concentration of the component (A), but is preferably 0.8 mmol / g or more, more preferably 0.8 mmol / g or more from the viewpoint of the surface tension of the hard coat coating film and the appearance of the coating film , Preferably about 1.6 to 4.7 mmol / g, and more preferably about 2.0 to 4.7 mmol / g.

(a1)성분과 (a2)성분은, 각각을 단독으로 또는 병용해서 사용할 수 있다. 병용하는 경우에 그들의 질량비는 특별하게 한정되지 않지만, 하드코팅성이나 경화성의 관점으로부터 보통 1/99∼80/20 정도, 바람직하게는 5/95∼50/50 정도가 되는 범위이면 좋다.The component (a1) and the component (a2) may be used alone or in combination. When they are used in combination, their mass ratio is not particularly limited, but it is usually in the range of about 1/99 to 80/20, preferably about 5/95 to 50/50 from the viewpoint of hard coatability and curability.

(B)성분은, 그 표면에 존재하는 실라놀기(silanol group)(이하, 표면 실라놀기)의 농도(이하, 표면 실라놀기 농도)가 특정한 범위인 실리카 미립자이면, 각종 공지의 것을 특별히 제한없이 사용할 수 있다. 당해 표면 실라놀기 농도는, 하드코팅 도포막에 높은 표면장력을 부여할 수 있는 범위인 것이 좋고, 구체적으로는, 보통 60∼200μｍｏｌ/ｇ 정도, 바람직하게는 100∼200μｍｏｌ/ｇ 정도, 더 바람직하게는 120∼200μｍｏｌ/ｇ 정도가 되는 범위이면 좋다. 여기에서 말하는 표면 실라놀기 농도는, 메틸레드 흡착법으로부터 구한 값이다. 메틸레드 흡착법은, 예를 들면 Ｔｈｅ Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ, 72, 776∼782(1950), 공업화학잡지 제68권 제3호 429∼432(1965) 등에 기재되어 있는 방법이다.(B) is a silica fine particle having a specific concentration range (hereinafter referred to as surface silanol group concentration) of a silanol group (hereinafter referred to as a surface silanol group) present on the surface thereof, various known compounds may be used without particular limitation . The surface silanol group concentration is preferably in the range capable of imparting a high surface tension to the hard coat film. Specifically, the surface silanol group concentration is usually about 60 to 200 占 퐉 ol / g, preferably about 100 to 200 占 퐉 ol / g, May be in the range of about 120 to 200 占 퐉 ol / g. Here, the surface silanol group concentration is a value obtained from the methyl red adsorption method. The methyl red adsorption method is a method described in, for example, The Journal of the American Chemical Society, 72, 776-782 (1950), Journal of Industrial Chemistry, Vol. 68, No. 3, 429-432 (1965)

(B)성분에는 표면 실라놀기가 많이 존재하고 있고, 당해 표면 실라놀기는 친수성이기 때문에, (B)성분은 높은 친수성을 구비한다. 본 발명의 하드코팅제에 (B)성분이 포함됨으로써 상기 하드코팅 도포막은 높은 표면장력을 구비한다. 이유는 불분명하지만, 상기 도포막 표면에 표면 실라놀기가 배향함으로써 상기 도포막의 표면장력이 높아지기 때문이라고 추정된다.(B) contains a large amount of surface silanol groups, and since the surface silanol groups are hydrophilic, component (B) has high hydrophilicity. By including the component (B) in the hard coating agent of the present invention, the hard coat coating film has a high surface tension. The reason is unclear, but it is presumed that the surface tension of the coating film is increased by orienting the surface silanol groups on the surface of the coating film.

(B)성분의 입자지름은 특별히 제한되지 않지만, 평균1차입경이 보통 10∼50nm 정도, 바람직하게는 10∼20nm 정도의 범위로 제어된 것이면 좋다. 당해 입경은, ＢＥＴ법에 의해 계측된 평균1차입경이다. 상기 입경이 이 범위이면, 하드코팅 도포막에 높은 표면장력을 부여할 수 있다.The particle diameter of the component (B) is not particularly limited, and may be any value as long as the average primary particle size is controlled to a range of usually about 10 to 50 nm, preferably about 10 to 20 nm. The particle diameter is an average primary inclination measured by the BET method. When the particle diameter is within this range, a high surface tension can be imparted to the hard coat film.

(B)성분으로서는, 표면 실라놀기 농도가 상기 범위이면, 각종 공지의 것을 특별하게 한정없이 사용할 수 있다. 구체적으로는, 습식법으로 제조되는 콜로이달 실리카나, 건식법으로 제조되는 흄드 실리카 등을 들 수 있다. 또한 (B)성분은, 표면 실라놀기 농도가 상기 범위이면, 실리카 표면의 일부가 유기물 등으로 수식(modification)되어 있는 것이라도 좋고, 실리카 표면이 수식되어 있지 않은 것(표면미처리 실리카)이라도 좋다.As the component (B), if the surface silanol group concentration is in the above range, various known ones can be used without any particular limitation. Specifically, colloidal silica produced by a wet process or fumed silica produced by a dry process may be mentioned. The component (B) may be one in which a part of the surface of the silica is modified with an organic substance or the like and the surface of the silica not modified (surface-untreated silica) if the surface silanol group concentration is within the above range.

콜로이달 실리카는, 구체적으로는 물을 분산매로 한 수성 콜로이드, 또는 메틸알코올, 에탄올, 이소프로필알코올, 에틸렌글리콜 혹은 프로필렌글리콜모노메틸에테르 등의 친수성 용매에 콜로이드상으로 분산시킨 오르가노졸(organosol)의 형태인 것(예를 들면 오르가노 실리카졸) 등을 들 수 있다. 흄드 실리카는, 건식법으로 제작된 비정질의 실리카로서, 규소를 포함하는 휘발성 화합물을 기상(氣相)으로 반응시킴으로써 얻을 수 있다. 구체적으로는, 예를 들면 사염화규소(ＳｉＣｌ4) 등의 규소화합물을 산소와 수소의 염(炎) 중에서 가수분해해서 생성된 것 등을 들 수 있다.Specifically, the colloidal silica may be an aqueous colloid in which water is used as a dispersion medium, or an organosol in which a colloid is dispersed in a hydrophilic solvent such as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol or propylene glycol monomethyl ether (For example, organosilica sol), and the like. Fumed silica can be obtained by reacting a volatile compound containing silicon with a gas phase as an amorphous silica produced by a dry process. Specifically, for example, those produced by hydrolyzing a silicon compound such as silicon tetrachloride (SiCl 4 ) in a salt of oxygen and hydrogen.

상기 콜로이달 실리카의 시판품으로서는, 예를 들면 스노우텍스(SNOWTEX), ＭＡ-ＳＴ-Ｍ, ＭＡ-ＳＴ-Ｌ, ＩＰＡ-ＳＴ, ＩＰＡ-ＳＴ-Ｌ, ＩＰＡ-ＳＴ-ＺＬ, ＩＰＡ-ＳＴ-ＵＰ, ＰＧＭ-ＳＴ(모두 닛산화학공업(주)(Nissan Chemical Industries, Ltd.) 제품), 쿼트론(Quartron)(후소화학공업(주)(FUSO CHEMICAL CO., LTD.) 제품), 아에로질(니폰아에로질(주)(NIPPON AEROSIL CO., LTD.) 제품), 실덱스(シルデックス)(아사히가라스(주)(Asahi Glass Co., Ltd.) 제품), 시리시아470(후지시리시아화학(주)(Fuji Silysia Chemical Ltd.) 제품) 등을 들 수 있다.Examples of commercially available products of the colloidal silica include SNOWTEX, MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST- , PGM-ST (all manufactured by Nissan Chemical Industries, Ltd.), Quartron (manufactured by FUSO CHEMICAL CO., LTD.), (Manufactured by NIPPON AEROSIL CO., LTD.), Sildex (manufactured by Asahi Glass Co., Ltd.), Silicia 470 (Manufactured by Fuji Silysia Chemical Ltd.) and the like.

본 발명의 하드코팅제에 있어서, (A)성분 및 (B)성분의 고형분환산으로의 질량비(이하, (A)/(B))는, 하드코팅 도포막에 높은 표면장력을 부여할 수 있고, 상기 도포막의 내구성이 높은 범위이면 좋다. 구체적으로는, (A)/(B)가 보통 20/80∼90/10 정도, 바람직하게는 30/70∼70/30 정도가 되는 범위인 것이 좋다. 20/80 미만에서는 상기 도포막이 약해져서 도포막 표면으로부터 (B)성분의 결락이 나타난다. 90/10을 넘으면 상기 도포막의 표면장력이 낮아진다.In the hard coating agent of the present invention, the mass ratio of the component (A) and the component (B) in terms of solid content (hereinafter referred to as (A) / (B)) can impart a high surface tension to the hard coat film, The durability of the coating film may be high. Specifically, it is preferable that (A) / (B) is in the range of usually about 20/80 to 90/10, preferably about 30/70 to 70/30. When the ratio is less than 20/80, the coating film is weakened and the component (B) is missing from the surface of the coating film. When the ratio exceeds 90/10, the surface tension of the coating film is lowered.

본 발명의 하드코팅제에는 필요에 따라 광중합개시제(C)(이하, (C)성분)를 포함해도 좋다. (C)성분은, 활성에너지선에 의해 분해되어 라디칼이 발생해서 중합을 개시시킬 수 있는 것이면 각종 공지의 것을 특별하게 한정없이 사용할 수 있다. 구체적으로는, 예를 들면 2,2-디메톡시-1,2-디페닐에탄-1-온, 1-시클로헥실페닐케톤, 2-히드록시-2-메틸-1-페닐-프로판-1-온, 1-[4-(2-히드록시에톡시)-페닐]-2-히드록시-2-메틸-1-프로판-1-온, 2-히드록시-1-{4-[4-(2-히드록시-2-메틸-프로피오닐)-벤질]-페닐}-2-메틸-프로판-1-온, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부타논(butanone)-1, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드, 2,4,6-트리메틸벤조일-디페닐-포스핀옥사이드, 4-메틸 벤조페논 등을 들 수 있다. 이들은 1종을 단독으로 혹은 2종 이상을 조합하여 사용할 수 있다.The hard coating agent of the present invention may optionally contain a photopolymerization initiator (C) (hereinafter referred to as component (C)). The component (C) may be any of various known ones as long as it can be decomposed by an active energy ray to generate radicals to initiate polymerization. Specific examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy- 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- ( Methyl-1- [4- (methylthio) phenyl] -2-morpholino-2-methyl-propan- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide , 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, and the like. These may be used singly or in combination of two or more.

(C)성분의 시판품으로서는, 예를 들면 Ｉｒｇａｃｕｒｅ 651, Ｉｒｇａｃｕｒｅ 184, Ｉｒｇａｃｕｒｅ 1173, Ｉｒｇａｃｕｒｅ 2959, Ｉｒｇａｃｕｒｅ 127, Ｉｒｇａｃｕｒｅ 907, Ｉｒｇａｃｕｒｅ 369, Ｉｒｇａｃｕｒｅ 819, Ｉｒｇａｃｕｒｅ ＴＰＯ(모두 ＢＡＳＦ사 제품), Ｏｍｎｉｒａｄ 651, Ｏｍｎｉｒａｄ 184, Ｏｍｎｉｒａｄ 1173, Ｏｍｎｉｒａｄ 2959, Ｏｍｎｉｒａｄ 127, Ｏｍｎｉｒａｄ 907, Ｏｍｎｉｒａｄ 369, Ｏｍｎｉｒａｄ 819, Ｏｍｎｉｒａｄ ＴＰＯ(모두 ＩＧＭ Ｒｅｓｉｎｓ사 제품), Ｓｐｅｅｄｃｕｒｅ ＴＰＯ, Ｓｐｅｅｄｃｕｒｅ ＭＢＰ(모두 Ｌａｍｂｓｏｎ사 제품) 등을 들 수 있고, 이들은 각각을 단독으로 또는 2종 이상을 병용할 수 있다.Examples of commercially available products of the component (C) include Irgacure 651, Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127, Irgacure 907, Irgacure 369, Irgacure 819, Irgacure TPO (all from BASF), Omnirad 651, Omnirad 184, Omnirad TPO (all available from IGM Resins), Speedcure TPO, and Speedcure MBP (both available from Lambson), which may be used alone or in combination, Or two or more of them may be used in combination.

(C)성분의 사용량은 특별하게 한정되지 않지만, 보통 (A)성분 및 (B)성분의 합계 100질량부(고형분환산)에 대하여 0.1∼20질량부(고형분환산) 정도가 되는 범위이면 좋다.The amount of the component (C) to be used is not particularly limited, but may be in the range of about 0.1 to 20 parts by mass (in terms of solid content) relative to 100 parts by mass (in terms of solid content) of the components (A) and (B).

본 발명의 하드코팅제는, 필요에 따라 (A)성분 이외의 다관능 아크릴레이트류(D)(이하, (D)성분)를 더 포함해도 좋다. (D)성분은, 1분자 중에 (메타)아크릴로일기를 적어도 2개 구비하는 (메타)아크릴레이트이면, 각종 공지의 것을 특별하게 한정없이 사용할 수 있다. 구체적으로는, 글리세린프로폭시트리(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 트리메틸올프로판폴리(반복수1∼3)프로폭시트리(메타)아크릴레이트, 트리메틸올프로판폴리(반복수1∼3)에톡시트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 펜타에리스리톨폴리(반복수1∼4)프로폭시테트라(메타)아크릴레이트, 펜타에리스리톨폴리(반복수1∼4)에톡시테트라(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 디펜타에리스리톨폴리(반복수1∼6)프로폭시헥사(메타)아크릴레이트, 디펜타에리스리톨폴리(반복수1∼6)에톡시헥사(메타)아크릴레이트, 비스페놀A폴리(반복수1∼4)프로폭시디(메타)아크릴레이트), 비스페놀A폴리(반복수1∼4)에톡시디(메타)아크릴레이트, 또한 ε-카프로락톤 변성 트리스-(2-(메타)아크릴록시에틸)이소시아누레이트, ε-카프로락톤 변성 디펜타에리스리톨헥사(메타)아크릴레이트, 우레탄(메타)아크릴레이트, 폴리에스테르(메타)아크릴레이트 등을 들 수 있다. 이들은 각각을 단독으로 또는 2종 이상을 병용하여도 좋다. 하드코팅성 및 경화성의 점으로부터 바람직하게는, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 글리세린프로폭시트리(메타)아크릴레이트, ε-카프로락톤 변성 트리스-(2-(메타)아크릴록시에틸)이소시아누레이트, 우레탄(메타)아크릴레이트, 폴리에스테르(메타)아크릴레이트이다.The hard coating agent of the present invention may further contain polyfunctional acrylates (D) (hereinafter referred to as component (D)) other than the component (A), if necessary. As the component (D), various known ones can be used without particular limitation, provided that (meth) acrylate having at least two (meth) acryloyl groups in one molecule is used. Specific examples thereof include glycerin propoxy tri (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane poly (repeating number 1 to 3) propoxy tri (meth) acrylate, trimethylol propane poly Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol poly (repeating number 1 to 4) propoxytetra (meth) acrylate, pentaerythritol poly (repeating number 1 to 3) (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (repeating number 1 to 6) propoxyhexa (meth) acrylate, (Repeating number 1 to 6) ethoxyhexa (meth) acrylate, bisphenol A poly (repeating number 1 to 4) propoxydi (meth) acrylate), bisphenol A poly 4) Ethoxydi ( (Meth) acrylate, ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate, urethane (meth) acrylate, ε-caprolactone- Polyester (meth) acrylate, and the like. These may be used alone or in combination of two or more. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin propoxytri (meth) acrylate, epsilon -caprolactone denatured tris- (2 - (meth) acryloxyethyl) isocyanurate, urethane (meth) acrylate, and polyester (meth) acrylate.

상기 우레탄(메타)아크릴레이트로서는, 다가의 이소시아네이트 화합물과 폴리올을 반응시켜서 얻어지는 말단 이소시아네이트기 함유 화합물에 수산기 함유 (메타)아크릴레이트를 반응시켜서 얻어지고 분자내에 3개 이상의 (메타)아크릴로일기를 구비하는 우레탄(메타)아크릴레이트, 다가 이소시아네이트 화합물과 1개의 수산기를 함유하는 (메타)아크릴레이트 화합물과를 반응시켜서 얻어지고 분자 중에 3개 이상의 (메타)아크릴로일기를 구비하는 우레탄(메타)아크릴레이트 등을 들 수 있다.The urethane (meth) acrylate is obtained by reacting a terminal isocyanate group-containing compound obtained by reacting a polyvalent isocyanate compound with a polyol, and reacting the (meth) acrylate containing a hydroxyl group to obtain three or more (meth) acryloyl groups Urethane (meth) acrylate which is obtained by reacting a urethane (meth) acrylate having a hydroxyl group and a (meth) acrylate compound containing one hydroxyl group and having at least three (meth) acryloyl groups in the molecule, And the like.

상기 폴리올로서는, 2개 이상의 수산기를 구비하는 것이면 특별하게 한정되지 않고, 예를 들면 (폴리)에틸렌글리콜, (폴리)프로필렌글리콜, 부탄디올, 네오펜틸글리콜, 헥산디올, 비스페놀A, S, F 등을 들 수 있다. 또한 폴리(에틸렌-프로필렌)글리콜 등의, 2종 이상의 알킬렌옥시드 골격을 구비하는 2가 알코올이더라도 좋다.(Poly) ethylene glycol, (poly) propylene glycol, butanediol, neopentyl glycol, hexanediol, bisphenol A, S, F and the like can be used as the polyol, . It may be a divalent alcohol having two or more kinds of alkylene oxide skeletons such as poly (ethylene-propylene) glycol.

(D)성분의 사용량은 특별하게 한정되지 않지만, 보통 (A)성분 및 (B)성분의 합계 100질량부(고형분환산)에 대하여 5∼95질량부(고형분환산) 정도가 되는 범위이면 좋다.The amount of the component (D) to be used is not particularly limited, but may be in the range of 5 to 95 parts by mass (in terms of solid content) relative to 100 parts by mass (in terms of solid content) of the components (A) and (B).

본 발명의 하드코팅제는 필요에 따라 첨가제를 더 배합할 수도 있다. 상기 첨가제로서는, 산화방지제, 자외선흡수제, 광안정제, 소포제, 표면조정제, 방오염제, 안료, 대전방지제, 금속산화물 미립자 분산체를 들 수 있다.The hard coating agent of the present invention may further comprise additives as required. Examples of the additives include antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface conditioners, antifouling agents, pigments, antistatic agents and metal oxide fine particle dispersions.

본 발명의 경화도포막(하드코팅 도포막)은, 본 발명의 하드코팅제에 활성에너지선을 조사함으로써 경화시켜서 얻어진다. 활성에너지선으로서는, 광(光)(자외선 등의 광선), 전자선, X선, α선, β선, γ선, 중성자선 등을 들 수 있다.The cured coating film (hard coated film) of the present invention is obtained by curing the hard coating agent of the present invention by irradiating the active energy ray. Examples of the active energy ray include light (light ray such as ultraviolet ray), electron ray, X ray,? Ray,? Ray,? Ray, neutron ray and the like.

본 발명의 하드코팅 도포막은 높은 표면장력 때문에 리코팅성이 양호해서, 각종 코팅제, 도료, 인쇄 잉크 및 점착층과의 밀착성이 높다. 상기 도포막의 표면장력은 특별하게 한정되지 않지만, 상기 리코팅성의 관점으로부터, 구체적으로는 보통 44∼48ｄｙｎ/cm 정도, 바람직하게는 46∼48ｄｙｎ/cm 정도가 되는 범위이면 좋다. 44ｄｙｎ/cm 미만이면 상기 도포막의 리코팅성이 나빠진다. 48ｄｙｎ/cm을 넘으면, 박리 필름·시트나 보호필름·시트에 있어서 점착층과 접하는 측에 상기 도포막을 적층하였을 경우에, 상기 필름·시트의 중박리화(重剝離化)나 점착제로부터의 접착 잔여물이 발생한다. 상기 도포막의 표면장력은 JIS K6768에 준거한 측정치이며, 예를 들면 Ａｒｃｏｔｅｓｔ사 제품의 표면 에너지값 평가용 테스트펜(다인펜)을 사용해서 측정한다.The hard coat coating film of the present invention has good recoatability due to its high surface tension and high adhesion to various coating agents, paints, printing inks and adhesive layers. The surface tension of the coating film is not particularly limited, but is preferably in the range of usually about 44 to 48 dyn / cm, preferably about 46 to 48 dyn / cm from the viewpoint of the recoatability. If it is less than 44 dyn / cm, the coating property of the coating film is deteriorated. When the coating film is overlaid on the side of the release film / sheet or the protective film / sheet in contact with the adhesive layer, if the film / sheet is over 48 dyn / cm, the adhesive residue from the adhesive / Lt; / RTI > The surface tension of the coating film is measured according to JIS K6768, and is measured using, for example, a test pen for evaluating the surface energy value of Arcotest (a die pen).

상기 하드코팅 도포막은 내구성도 우수하여, 상기 도포막을 가열처리 해서 표면을 알코올 등으로 닦아내어도 높은 표면장력이 지속되고, 도포막 표면으로부터 (B)성분의 결락도 없다. 또한 상기 하드코팅 도포막은 도포막 표면이 평활해서, 요철표면(오렌지필), 핀홀 등의 발생이 억제되어 있기 때문에, 도포막 외관이 우수하게 된다.The hard coating film is also excellent in durability, so that even if the surface of the coating film is heat-treated and the surface is wiped with alcohol or the like, a high surface tension is maintained, and no component (B) is lost from the surface of the coating film. In addition, since the surface of the coating film of the hard coat coating film is smooth and the occurrence of irregularities (orange peel), pinholes, and the like are suppressed, the coating film appearance is excellent.

본 발명의 적층필름은, 본 발명의 하드코팅 도포막을 기재에 적층함으로써 얻어진다. 적층필름의 기재로서는 특별히 제한은 없고, 예를 들면 플라스틱(폴리카보네이트, 폴리메틸메타크릴레이트, 폴리스티렌, 폴리에스테르, 폴리올레핀, 에폭시 수지, 멜라민 수지, 트리아세틸셀룰로오스 수지, ABS 수지, AS수지, 노보넨계 수지 등)을 들 수 있다. 상기 기재는 표면처리(코로나 방전 등)가 된 것이어도 좋다. 또한 상기 기재는, 그 편면 혹은 양면에, 본 발명의 하드코팅제 이외의 코팅제, 인쇄 잉크 및 점착제에 의한 층이 형성되어 있더라도 좋다.The laminated film of the present invention is obtained by laminating the hard coat coating film of the present invention on a substrate. The base material of the laminated film is not particularly limited and examples thereof include plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, Resin, etc.). The substrate may be subjected to surface treatment (corona discharge, etc.). The substrate may have a layer formed of a coating agent, a printing ink, and a pressure-sensitive adhesive other than the hard coating agent of the present invention on one side or both sides thereof.

상기 기재에 상기 하드코팅 도포막을 적층시키는 방법으로서는, 공지의 방법으로 본 발명의 하드코팅제를 도포해서 건조시킨 후에, 활성에너지선을 조사해서 경화시킴으로써 한다. 상기 하드코팅제의 도포방법으로서는, 예를 들면 바코터 도포, 메이어 바(meyer bar) 도포, 에어나이프 도포, 그라비아 도포, 리버스 그라비아 도포, 오프셋 인쇄, 플렉소 인쇄, 스크린인쇄법 등을 들 수 있다. 또 도포량은 특별하게 한정되지 않지만, 보통은 건조후의 중량이 0.1∼20g/m2, 바람직하게는 0.5∼10g/m2이 되는 범위이다.As a method for laminating the hard coating film on the base material, a hard coating agent of the present invention is coated by a known method, followed by drying, followed by curing by irradiation with active energy rays. Examples of the application method of the hard coating agent include bar coater application, Meyer bar application, air knife application, gravure application, reverse gravure application, offset printing, flexo printing, screen printing and the like. Also the coating amount is not particularly limited, and usually it is the weight after drying 0.1~20g / m 2, preferably in the range in which the 0.5~10g / m 2.

본 발명의 적층필름은, 하드코팅층 함유 필름에 대하여 하드코팅제, 도료, 인쇄 잉크 및 점착층을 적층하는 용도에 있어서 적합한 필름이 될 수 있다. 특히, 터치패널 등에서 사용되는 ITO 필름의 투명기재에 상기 하드코팅 도포막을 적층하면, ＯＣＡ(광학점착필름) 및 ＯＣＲ(광학점착수지)에 대하여 양호한 밀착성을 나타내는 상기 필름을 제공할 수 있다.The laminated film of the present invention can be a film suitable for use in the lamination of a hard coating agent, a coating material, a printing ink and an adhesive layer to a film containing a hard coating layer. Particularly, when the hard coating film is laminated on a transparent substrate of an ITO film used in a touch panel or the like, the film exhibiting good adhesion to OCA (optical adhesive film) and OCR (optical adhesive resin) can be provided.

[실시예][Example]

이하, 실시예 및 비교예를 통해서 본 발명을 상세하게 설명하지만, 물론 그것에 의해 본 발명의 범위가 한정되는 것은 아니다. 또한 각 실시예 및 비교예에 있어서 부 또는 ％는 질량기준이다.Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto. In each of the examples and comparative examples, parts or% are based on mass.

중량평균분자량(Ｍｗ)은, 하기 조건의 겔 퍼미에이션 크로마토그래피(ＧＰＣ)에 의해 측정했다.The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions.

(ＧＰＣ측정조건)(GPC measurement conditions)

기종 : 제품명 「ＨＬＣ-8120」(도소(주)(Tosoh Corporation) 제품)Model: HLC-8120 (manufactured by Tosoh Corporation)

칼럼 : 제품명 「ＴＳＫｇｅｌ ＳｕｐｅｒＨＭ-L」(도소(주) 제품)×3개Column: " TSKgel SuperHM-L " (product of TOSOH CORPORATION) x 3

전개용매, 유량 : 테트라하이드로퓨란, 0.6ｍＬ/분Developing solvent, flow rate: tetrahydrofuran, 0.6 mL / min

측정온도 : 40℃Measuring temperature: 40 ° C

검출기 : ＲＩDetector: RI

표준 : 단분산 폴리스티렌Standard: Monodisperse polystyrene

시료 ; 수지로부터 고형분환산으로 0.2% 농도의 테트라하이드로퓨란 용액을 조제하고, 상기 용액을 마이크로 필터로 여과한 것(20㎕)sample ; A tetrahydrofuran solution having a concentration of 0.2% in terms of solid content was prepared from the resin, and the solution was filtered with a microfilter (20))

각 실시예 및 비교예에서 사용하는 펜타에리스리톨폴리(메타)아크릴레이트 혼합물, 디펜타에리스리톨폴리(메타)아크릴레이트 혼합물 중의 각 성분의 함유량은, 하기 조건의 고속액체 크로마토그래피(ＨＰＬＣ)를 사용해서 측정되는, 전(全)피크면적 총합계에 대한 각 성분의 피크면적의 비율로부터 산출했다.The content of each component in the mixture of pentaerythritol poly (meth) acrylate and dipentaerythritol poly (meth) acrylate used in each of Examples and Comparative Examples was measured using high performance liquid chromatography (HPLC) under the following conditions Of the peak area of each component relative to the total peak area of the total peak area.

(ＨＰＬＣ측정조건)(HPLC measurement conditions)

측정장치 ; 제품명 「Ｗａｔｅｒｓ2695 Ｓｅｐａｒａｔｉｏｎｓ Ｍｏｄｕｌｅ」(ＷａｔｅｒｓＣｏｒｐｏｒａｔｉｏｎ 제품)Measuring device; Product name "Waters 2695 Separations Module" (Waters Corporation)

칼럼 ; 제품명 「Ｗａｔｅｒｓ Ａｔｌａｎｔｉｓ Ｔ3 5μｍ ＯＤＳ 4.6×250mm」(ＷａｔｅｒｓＣｏｒｐｏｒａｔｉｏｎ 제품) 1개column ; One Waters Atlantis T3 5μm ODS 4.6 x 250mm (Waters Corporation)

검출기 ; 제품명 「Ｗａｔｅｒｓ2998 Ｐｈｏｔｏｄｉｏｄｅ Ａｒｒａｙ(210nm)」(ＷａｔｅｒｓＣｏｒｐｏｒａｔｉｏｎ 제품)Detector; &Quot; Waters2998 Photodiode Array (210nm) " (Waters Corporation)

측정조건 ; 칼럼 오븐 온도 40℃, 주입량 10μL, 유속 0.8ｍＬ/ｍｉｎMeasuring conditions ; Column oven temperature 40 째 C, injection amount 10 袖 L, flow rate 0.8 mL / min

이동상 조성조건 ; 메탄올/물 = 65/35ｗｔ％Mobile phase composition condition; Methanol / water = 65/35 wt%

각 실시예 및 비교예에서 사용하는 오르가노 실리카졸 중의 실리카 미립자의 표면 실라놀기 농도는, 메틸레드 및 분광광도계를 사용하여 하기 방법에 의해 측정했다.The surface silanol group concentration of the fine silica particles in the organosilica sol used in each of the Examples and Comparative Examples was measured by the following method using methyl red and a spectrophotometer.

(표면 실라놀기 농도의 측정방법)(Method for measuring the surface silanol group concentration)

<흡광도 측정용 메틸레드/톨루엔 용액의 조제>&Lt; Preparation of methyl red / toluene solution for absorbance measurement >

메틸레드(와코쥰야쿠공업주식회사(Wako Pure Chemical Industries, Ltd.) 제품) 808mg을 비커에 칭량(稱量)하고, 100ｍＬ의 톨루엔(와코쥰야쿠공업주식회사 제품 와코 1급 톨루엔)에 용해시켰다. 용해액을 1L 메스플라스크(messflask)로 옮기고, 비커 중의 잔액을 동(同)톨루엔으로 씻어 낸 세정액도 메스 플라스크로 옮겨, 농도 3ｍｍｏｌ/L의 메틸레드/톨루엔 용액을 1L 조제하여 흡광도 측정용의 표준시료로 했다.808 mg of methyl red (Wako Pure Chemical Industries, Ltd.) (808 mg) was weighed in a beaker and dissolved in 100 mL of toluene (Wako Junyaku Kogyo KK Toluene). The solution was transferred to a 1 L mess flask. The remaining liquid in the beaker was rinsed with toluene, and the washing liquid was transferred to a measuring flask. 1 L of a methyl red / toluene solution having a concentration of 3 mmol / L was prepared, It was made as a sample.

<표면 실라놀기 농도의 정량용 피험시료의 작성>&Lt; Preparation of test sample for determination of surface silanol group concentration >

오르가노 실리카졸 20g을 원심관에 칭량하고 고속원심기((주)고쿠산(KOKUSAN CO. Ltd.) 제품 Ｈ-201ＦＲ)로 원심분리하여, 실리카 미립자를 침강시켰다. 상등액을 제거한 후에 분리한 실리카 입자를 바람에 쐬어 건조시키고, 그리고 마노유발로 갈아서 으깬 후에 샬레로 이동시키켜, 상압건조기(100℃)로 6시간 건조시켰다. 건조시킨 실리카 입자를 글라스병에 100mg 칭량하고, 상기한 메틸레드/톨루엔 표준시료를 10ｍＬ 첨가하여 진탕기로 1시간 진탕(振蕩)시켰다. 진탕 후에 2시간 정치(靜置)하여 상등액을 피험시료로 했다.20 g of organosilica sol were weighed into a centrifuge tube and centrifuged with a high-speed centrifuge (H-201FR manufactured by KOKUSAN CO. Ltd.) to precipitate the silica fine particles. After removing the supernatant, the separated silica particles were air dried, ground with agate, transferred to a chalet, and dried in an atmospheric pressure dryer (100 ° C) for 6 hours. 100 mg of the dried silica particles were weighed in a glass bottle, and 10 mL of the methyl red / toluene standard sample described above was added, and the mixture was shaken for 1 hour with a shaker. After shaking, it was allowed to stand for 2 hours, and the supernatant was used as a test sample.

<분광광도계에 의한 흡광도 측정과 표면 실라놀기 농도의 정량>&Lt; Measurement of absorbance by spectrophotometer and determination of surface silanol group concentration >

표준시료, 피험시료 각각 1ｍＬ를 톨루엔으로 10배로 희석하고 광로장(光路長) 1mm의 석영셀(지엘사이언스(주)(GL Sciences Inc.) 제품)을 사용하여, 분광광도계(「U-3010」 (주)히타치하이테크사이언스(Hitachi High-Tech Science Corporation) 제품)로 파장 480nm의 최대흡광도를 측정했다. 표준시료의 상기 최대흡광도를 A(ｓｔｄ), 피험시료의 상기 최대흡광도를 A(ｓａｍｐｌｅ)로 하여, 이하의 식으로부터 실리카 미립자의 표면 실라놀기 농도를 산출했다.(U-3010, manufactured by GL Sciences Inc.) was diluted with toluene in an amount of 1 mL each of a standard sample, a test sample, and a quartz cell (GL Sciences Inc.) having an optical path length of 1 mm. (Manufactured by Hitachi High-Tech Science Corporation), and the maximum absorbance at a wavelength of 480 nm was measured. The surface silanol group concentration of the silica fine particles was calculated from the following equation, assuming that the maximum absorbance of the standard sample is A (std) and the maximum absorbance of the test sample is A (sample).

표면 실라놀기 농도(㎛ol/g)={30×(A(ｓｔｄ)-A(ｓａｍｐｌｅ))}/100×1000Surface silanol group concentration (占 퐉 ol / g) = {30 占 (A (std) -A (sample))} / 100 占 1000

(수산기 함유 (메타)아크릴 공중합체 용액(a1)의 제조)(Preparation of hydroxyl group-containing (meth) acrylic copolymer solution (a1)) [

제조예1Production Example 1

교반장치, 냉각관, 적하 깔때기(dropping funnel) 및 질소유입관을 구비한 반응장치에, 글리시딜메타아크릴레이트(이하, ＧＭＡ라고 한다) 272부, 아세트산부틸 947부 및 2,2'-아조비스(2-메틸부티로니트릴)(이하, ＡＢＮＥ라고 한다) 10.8부를 넣은 후, 질소기류하에서 약 1시간에 걸쳐 계(系)내 온도가 약 90℃가 될 때까지 승온시키고 1시간 보온했다. 계속하여 미리 ＧＭＡ 815부, 아세트산부틸 115.0부, ＡＢＮＥ 32.6부로 이루어지는 혼합액을 넣은 적하 깔때기로부터, 질소기류하에서 혼합액을 약 2시간을 들여 계내에 적하하고, 3시간 동(同)온도로 보온한 후에, ＡＢＮＥ 11.0부, 아세트산부틸 20.0부를 넣어 1시간 보온했다. 그 후에 130℃로 승온시키고 2시간 보온했다. 60℃까지 냉각시킨 후에, 질소유입관을 공기유입관으로 바꾸어, 아크릴산(이하, ＡＡ라고 한다) 548부, 메토퀴논 3.1부 및 트리페닐포스핀 6.7부를 넣어 혼합한 후에, 공기 버블링하에서 110℃까지 승온시켰다. 동온도에서 8시간 보온한 후에 메토퀴논 1.6부를 넣어 냉각시키고, 불휘발분이 50%가 되도록 아세트산에틸을 가하여, 수산기 함유 (메타)아크릴 공중합체 용액(이하, (a1)-1성분이라고 한다)을 얻었다. 얻어진 수산기 함유 (메타)아크릴 공중합체는, 수산기 농도 4.67ｍｍｏｌ/g(반복구조 1ｍｏｌ 중에 수산기 1ｍｏｌ, 반복구조의 식량 214.21), 중량평균분자량(ＧＰＣ법에 의한 스티렌 환산치) 30,000이었다.272 parts of glycidyl methacrylate (hereinafter referred to as "GMA"), 947 parts of butyl acetate, and 20 parts of 2,2'-azo (hereinafter referred to as "GMA") were charged in a reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen inlet tube. And 10.8 parts of bis (2-methylbutyronitrile) (hereinafter abbreviated as ABNE) were charged, and then the temperature in the system (system) was raised to about 90 占 폚 for about one hour in a nitrogen stream and then kept warm for one hour. Subsequently, the mixture was dripped into the system over about 2 hours from a dropping funnel containing a mixture of 815 parts of GMA, 115.0 parts of butyl acetate and 32.6 parts of ABNE in advance and kept at the same temperature for 3 hours, 11.0 parts of ABNE and 20.0 parts of butyl acetate were added thereto, and the mixture was kept warm for 1 hour. Thereafter, the temperature was raised to 130 캜 and kept at that temperature for 2 hours. After cooled to 60 DEG C, 548 parts of acrylic acid (hereinafter referred to as AA), 3.1 parts of methoquinone and 6.7 parts of triphenylphosphine were added and mixed by changing the nitrogen inlet tube to an air inlet tube. Thereafter, Lt; / RTI &gt; After maintaining the temperature at the same temperature for 8 hours, 1.6 parts of methoquinone was added and the mixture was cooled. Ethyl acetate was added thereto so that the nonvolatile content became 50% to obtain a solution of a hydroxyl group-containing (meth) acrylic copolymer (hereinafter referred to as component (a1) -1) . The resulting hydroxyl group-containing (meth) acrylic copolymer had a hydroxyl group concentration of 4.67 mmol / g (1 mol of hydroxyl group in 1 mol of the repeating structure, 214.21 of the repeating structure) and a weight average molecular weight (styrene conversion value by GPC method) of 30,000.

(표면의 일부가 유기물로 수식된 친수성 실리카 미립자(B)의 제조)(Preparation of hydrophilic silica fine particles (B) whose surface was partially modified with an organic substance)

제조예2Production Example 2

교반기, 냉각관, 온도계를 구비한 반응장치에, 프로필렌글리콜모노메틸에테르 분산 실리카졸(닛산화학공업(주) 제품 상품명 「ＰＧＭ-ＳＴ」 실리카 고형분 30%, 표면 실라놀기 농도 166μｍｏｌ/g, 평균1차입자지름 10∼20nm)(이하, (B)-1성분이라고 한다) 100부와, 3-메타크릴록시프로필트리메톡시실란 0.9부, 옥틸산주석 0.09부를 가하고, 교반하면서 80℃까지 승온시키고 2시간 가열, 교반함으로써, 표면이 메타크릴록시기로 변성된 실리카졸(이하, (B)-4성분이라고 한다)을 얻었다. 얻어진 (B)-4성분은, 실리카 고형분 31%, 표면 실라놀기 농도 127μｍｏｌ/g 및 평균1차입자지름 10∼20nm이었다.A PGM-ST silica solid content of 30%, a surface silanol group concentration of 166 占 퐉 ol / g, and an average of 1 (1) mole of propylene glycol monomethyl ether dispersed silica sol (Nissan Chemical Industries, Ltd.) was added to a reaction apparatus equipped with a stirrer, Methacryloxypropyltrimethoxysilane (0.9 parts) and tin octylate (0.09 parts) were added, and the mixture was heated to 80 DEG C with stirring, and 2 parts of 2 And heated and stirred for a time to obtain a silica sol (hereinafter referred to as (B) -4 component) whose surface was modified with a methacryloxy group. The obtained component (B) -4 had a silica solid content of 31%, a surface silanol group concentration of 127 占 퐉 ol / g and an average primary particle diameter of 10 to 20 nm.

제조예3Production Example 3

교반기, 냉각관, 온도계를 구비한 반응장치에, (B)-1성분 100부와 3-메타크릴록시프로필트리메톡시실란 3.0부, 옥틸산주석 0.10부를 가하고, 교반하면서 80℃까지 승온시키고 2시간 가열, 교반함으로써, 표면이 메타크릴록시기로 변성된 실리카졸(이하, (B)'-2성분이라고 한다)을 얻었다. 얻어진 (B)'-2성분은, 실리카 고형분 32%, 표면 실라놀기 농도 46μｍｏｌ/g 및 평균1차입자지름 10∼20nm이었다.100 parts of the component (B) -1, 3.0 parts of 3-methacryloxypropyltrimethoxysilane and 0.10 parts of tin octylate were added to a reaction apparatus equipped with a stirrer, a cooling tube and a thermometer, And heated and stirred for a time to obtain a silica sol whose surface was modified with a methacryloxy group (hereinafter referred to as component (B) '- 2). The component (B) '- 2 thus obtained had a silica solid content of 32%, a surface silanol group concentration of 46 μmol / g and an average primary particle diameter of 10 to 20 nm.

(하드코팅제의 제조)(Preparation of hard coating agent)

실시예1Example 1

(a1)-1성분 82.4부에, (B)-1성분 15.3부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.3부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.15.3 parts of the component (B) -1 and 2.3 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 82.4 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether to a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예2Example 2

(a1)-1성분 57.1부에, (B)-1성분 40.8부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.1부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.40.8 parts of the component (B) -1 and 2.1 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 57.1 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예3Example 3

(a1)-1성분 46.5부에, (B)-1성분 51.6부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 1.9부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.51.6 parts of the component (B) -1 and 1.9 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 46.5 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether to a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예4Example 4

(a1)-1성분 36.8부에, (B)-1성분 61.4부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 1.8부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.61.4 parts of the component (B) -1 and 1.8 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 36.8 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예5Example 5

(a1)-1성분 20.1부에, (B)-1성분 78.2부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 1.7부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.78.2 parts of the component (B) -1 and 1.7 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 20.1 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예6Example 6

(a1)-1성분 12.8부에, (B)-1성분 85.6부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 1.6부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.85.6 parts of the component (B) -1 and 1.6 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 12.8 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether to a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예7Example 7

(a1)-1성분 36.8부에, 이소프로필알코올 분산 오르가노 실리카졸(닛산화학공업(주) 제품, 상품명 「ＩＰＡ-ＳＴ」, 실리카 고형분 30%, 표면 실라놀기 농도 170μｍｏｌ/g, 평균1차입자지름 10∼20nm)(이하, (B)-2성분이라고 한다) 61.4부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 1.8부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.(trade name: IPA-ST manufactured by Nissan Chemical Industries, Ltd., silica solid content: 30%, surface silanol group concentration: 170 μmol / g, average primary particle diameter: (Hereinafter referred to as (B) -2 component) (hereinafter referred to as (B) -2 component) and 1.8 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were blended and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예8Example 8

(a1)-1성분 36.8부에, 이소프로필알코올 분산 오르가노 실리카졸(닛산화학공업(주) 제품, 상품명 「ＩＰＡ-ＳＴ-L」, 실리카 고형분 30%, 표면 실라놀기 농도 63μｍｏｌ/g, 평균1차입자지름 40∼50nm)(이하, (B)-3성분이라고 한다) 61.4부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 1.8부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.IPA-ST-L "manufactured by NISSAN CHEMICAL INDUSTRIES CO., LTD., silica solid content 30%, surface silanol group concentration 63 μmol / g, average (average) 61.4 parts of a boron compound (hereinafter, referred to as (B) -3 component) and 1.8 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were blended, and propylene glycol monomethyl ether Diluted and prepared, and uniformly mixed to obtain a hard coating agent.

실시예9Example 9

수산기 농도 3.38ｍｍｏｌ/g의 펜타에리스리톨폴리아크릴레이트 혼합물(펜타에리스리톨디아크릴레이트(1ｍｏｌ 중에 수산기 2ｍｏｌ, 분자량 244.24) 11%, 펜타에리스리톨트리아크릴레이트(1ｍｏｌ 중에 수산기 1ｍｏｌ, 분자량 298.29) 74%, 펜타에리스리톨테트라아크릴레이트(분자 중에 수산기 없음) 15%)(이하, (a2)-1성분이라고 한다) 22.6부에, (B)-1성분 75.2부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.2부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다., A pentaerythritol polyacrylate mixture having a hydroxyl group concentration of 3.38 mmol / g (pentaerythritol diacrylate (2 mol of hydroxyl group in 1 mol, molecular weight 244.24) 11%, pentaerythritol triacrylate (1 mol of hydroxyl group in 1 mol, molecular weight 298.29) 75.2 parts of the component (B) -1 and 2.2 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 22.6 parts of tetraacrylate (no hydroxyl group in the molecule) (hereinafter referred to as component (a2) -1) And diluted with propylene glycol monomethyl ether so as to have a non-volatile content of 30%, and uniformly mixed to obtain a hard coating agent.

실시예10Example 10

수산기 농도 2.08ｍｍｏｌ/g의 펜타에리스리톨폴리아크릴레이트 혼합물(펜타에리스리톨트리아크릴레이트(1ｍｏｌ 중에 수산기 1ｍｏｌ, 분자량 298.29) 62%, 펜타에리스리톨테트라아크릴레이트(분자 중에 수산기 없음) 38%)(이하, (a2)-2성분이라고 한다) 22.6부에, (B)-1성분 75.2부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.2부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.(Pentaerythritol triacrylate (1 mol of hydroxyl group in 1 mol, molecular weight 298.29) 62% and pentaerythritol tetraacrylate (no hydroxyl group in the molecule) 38%) having a hydroxyl group concentration of 2.08 mmol / g ) Component (22.2 parts), 75.2 parts of the component (B) -1 and 2.2 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were blended and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예11Example 11

수산기 농도 1.6ｍｍｏｌ/g의 디펜타에리스리톨폴리아크릴레이트 혼합물(디펜타에리스리톨펜타아크릴레이트(1ｍｏｌ 중에 수산기 1ｍｏｌ, 분자량 524.52) 84%, 디펜타에리스리톨헥사아크릴레이트(분자 중에 수산기 없음) 16%)(이하, (a2)-3성분이라고 한다) 22.6부에, (B)-1성분 75.2부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.2부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.A mixture of dipentaerythritol pentaacrylate (1 mol of hydroxyl group in 1 mol, molecular weight of 524.52) of 84% and dipentaerythritol hexaacrylate (no hydroxyl group in the molecule) of 16%) (hereinafter referred to as &quot; 75.2 parts of the component (B) -1 and 2.2 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 22.6 parts of the component (a2) -3, and propylene glycol monomethyl ether , And uniformly mixed to obtain a hard coating agent.

실시예12Example 12

수산기 농도 0.8ｍｍｏｌ/g의 디펜타에리스리톨폴리아크릴레이트 혼합물(디펜타에리스리톨펜타아크릴레이트(1ｍｏｌ 중에 수산기 1ｍｏｌ, 분자량 524.52) 42%, 디펜타에리스리톨헥사아크릴레이트(분자 중에 수산기 없음) 58%)(이하, (a2)-4성분이라고 한다) 22.6부에, (B)-1성분 75.2부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.2부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.(1 mol of hydroxyl group in 1 mol, molecular weight of 524.52) and 58% of dipentaerythritol hexaacrylate (no hydroxyl group in the molecule)) (hereinafter referred to as &quot; 75.2 parts of the component (B) -1 and 2.2 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 22.6 parts of the component (a2) -4, and propylene glycol monomethyl ether , And uniformly mixed to obtain a hard coating agent.

실시예13Example 13

(a1)-1성분 20.3부에, (a2)-2성분 10.1부, (B)-1성분 67.6부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.0부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.10 parts of the component (a2) -2, 67.6 parts of the component (B) -1) and 2.0 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 20.3 parts of the component (a1) Diluted with propylene glycol monomethyl ether, and uniformly mixed to obtain a hard coating agent.

실시예14Example 14

(a1)-1성분 20.3부에, (a2)-4성분 10.1부, (B)-1성분 67.6부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.0부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.10.1 parts of the component (4) -4, 67.6 parts of the component (B) -1 and 2.0 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 20.3 parts of the component (a1) Diluted with propylene glycol monomethyl ether, and uniformly mixed to obtain a hard coating agent.

실시예15Example 15

(a2)-2성분 11.3부에, (a2)-4성분 11.3부, (B)-1성분 75.2부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.2부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.11.3 parts of (a2) -4 component, 75.2 parts of (B) -1 component and 2.2 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 11.3 parts of the component (a2) Diluted with propylene glycol monomethyl ether, and uniformly mixed to obtain a hard coating agent.

실시예16Example 16

(a1)-1성분 82.9부에, (B)-4성분 14.8부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.3부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.14.8 parts of the component (B) -4 and 2.3 parts of Irgacure 184 (manufactured by BASF) as photopolymerization initiators were added to 82.9 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예17Example 17

(a1)-1성분 57.9부에, (B)-4성분 40.0부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.1부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.40.0 parts of the component (B) -4 and 2.1 parts of Irgacure 184 (manufactured by BASF) as photopolymerization initiators were added to 57.9 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예18Example 18

(a1)-1성분 37.6부에, (B)-4성분 60.6부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 1.8부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.60.6 parts of the component (B) -4 and 1.8 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 37.6 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

실시예19Example 19

(a1)-1성분 20.7부에, (a2)-2성분 10.4부, (B)-4성분 66.8부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.1부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.10 parts of the component (a2) -2, 66.8 parts of the component (B) -4, and 2.1 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 20.7 parts of the component (a1) Diluted with propylene glycol monomethyl ether, and uniformly mixed to obtain a hard coating agent.

실시예20Example 20

(a1)-1성분 13.2부에, (B)-4성분 85.2부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 1.6부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.85.2 parts of the component (B) -4 and 1.6 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 13.2 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

비교예1Comparative Example 1

(a1)-1성분 97.6부에, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.4부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.and 2.4 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 97.6 parts of the component (a1) -1, diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30%, and uniformly mixed to prepare a hard coating agent .

비교예2Comparative Example 2

(a1)-1성분 6.2부에, (B)-1성분 92.3부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 1.5부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.92.3 parts of the component (B) -1 and 1.5 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 6.2 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

비교예3Comparative Example 3

(a1)-1성분 47.3부에, 프로필렌글리콜모노메틸에테르 분산 오르가노 실리카졸(닛산화학공업(주) 제품, 상품명 「ＰＧＭ-ＡＣ-2140Ｙ」, 실리카 고형분 47%, 표면 실라놀기 농도 40μｍｏｌ/g(표면 실라놀기의 일부에 아크릴화 처리), 평균1차입자지름 10∼20nm)(이하, (B)'-1성분이라고 한다) 50.3부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.4부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.propylene glycol monomethyl ether-dispersed organosilica sol (trade name: "PGM-AC-2140Y", product of Nissan Chemical Industries, Ltd., silica solid content: 47%, surface silanol group concentration: 40 μmol / g (Hereinafter, referred to as (B) '- 1 component) and 2.4 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were blended, Diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30%, and uniformly mixed to obtain a hard coating agent.

비교예4Comparative Example 4

수산기 농도 0.17ｍｍｏｌ/g의 펜타에리스리톨폴리아크릴레이트 혼합물(펜타에리스리톨트리아크릴레이트(1ｍｏｌ 중에 수산기 1ｍｏｌ, 분자량 298.29) 5%, 펜타에리스리톨테트라아크릴레이트(분자 중에 수산기 없음) 95%)(이하, (a2）'－1성분이라고 한다) 22.6부에, (B)-1성분 75.2부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.2부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다., 5% of pentaerythritol triacrylate (1 mol of hydroxyl group in 1 mol, molecular weight of 298.29) and 95% of pentaerythritol tetraacrylate (no hydroxyl group in the molecule)) having a hydroxyl group concentration of 0.17 mmol / g (hereinafter referred to as (a2 75.2 parts of the component (B) -1 and 2.2 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 22.6 parts of a polyisocyanate compound And uniformly mixed to obtain a hard coating agent.

비교예5Comparative Example 5

수산기 농도 0.18ｍｍｏｌ/g의 디펜타에리스리톨폴리아크릴레이트 혼합물(디펜타에리스리톨펜타아크릴레이트(1ｍｏｌ 중에 수산기 1ｍｏｌ, 분자량 524.52) 16%, 디펜타에리스리톨헥사아크릴레이트(분자 중에 수산기 없음) 84%)(이하, (a2）'－2성분이라고 한다) 22.6부에, (B)-1성분 75.2부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 2.2부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.(1 mol of hydroxyl group in 1 mol, molecular weight of 524.52) and 84% of dipentaerythritol hexaacrylate (no hydroxyl group in the molecule)) (hereinafter referred to as &quot; 75.2 parts of the component (B) -1 and 2.2 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 22.6 parts of the polyol component (hereinafter referred to as component (a2) '- 2). Propylene glycol monomethyl Diluted with ether, and uniformly mixed to obtain a hard coating agent.

비교예6Comparative Example 6

(a2)-4성분 75.0부에, ＵＶ경화형 친수성 폴리머(대성파인케미컬(주)(Taisei Fine Chemical Co., Ltd.) 제품, 상품명 「아크릿트(アクリット)8ＷＸ-030」, 40% 프로필렌글리콜모노메틸에테르/메탄올 용액) 20.8부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 4.2부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.(trade name: 8 WX-030, manufactured by Taisei Fine Chemical Co., Ltd., trade name: 8 WX-030), 40% propylene glycol mono Methyl ether / methanol solution) and 4.2 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30%, and uniformly mixed to obtain a hard coating agent .

비교예7Comparative Example 7

(a1)-1성분 38.3부에, (B)'-2성분 59.8부, 광중합개시제로서 Ｉｒｇａｃｕｒｅ 184(ＢＡＳＦ사 제품) 1.9부를 배합하고, 불휘발분이 30%가 되도록 프로필렌글리콜모노메틸에테르로 희석하여 조제하고, 균일하게 혼합해서 하드코팅제를 얻었다.59.8 parts of the component (B) '- 2 and 1.9 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were added to 38.3 parts of the component (a1) -1 and diluted with propylene glycol monomethyl ether so as to have a nonvolatile content of 30% And uniformly mixed to obtain a hard coating agent.

(하드코팅 도포막의 평가)(Evaluation of Hard Coat Coating Film)

실시예1∼20 및 비교예1∼7의 하드코팅제를 사용하여 하기의 방법으로 기재 표면에 하드코팅 도포막을 형성시켜서, 도포막 평가를 하였다. 그 결과를 표1에 나타낸다.Using the hard coating agents of Examples 1 to 20 and Comparative Examples 1 to 7, a hard coat coating film was formed on the substrate surface by the following method to evaluate the coating film. The results are shown in Table 1.

<하드코팅 도포막의 형성>&Lt; Formation of hard coating film >

두께 125㎛의 폴리에틸렌테레프탈레이트 필름상에 바코터 #5를 사용해서 각 하드코팅제를 도포하고, 80℃의 순풍건조기(循風乾燥機) 안에서 1분간 건조시켰다. 그 후에 고압수은등(출력 120W/cm)을 사용하여 조사거리 10cm, 벨트 스피드 10m/ｍｉｎ, 적산 조사량 250ｍＪ/cm2의 조건으로 경화시켜서, 하드코팅 도포막을 형성했다.Each hard coating agent was coated on a polyethylene terephthalate film having a thickness of 125 占 퐉 using a bar coater # 5 and dried in a circulating air dryer at 80 占 폚 for 1 minute. Thereafter, a hard coating film was formed by using a high-pressure mercury lamp (output: 120 W / cm) under conditions of irradiation distance of 10 cm, belt speed of 10 m / min, and cumulative dose of 250 mJ / cm 2 .

<하드코팅 도포막의 표면장력 측정>&Lt; Surface tension measurement of hard coating film >

Ａｒｃｏｔｅｓｔ사 제품의 표면 에너지값 평가용 테스트펜(다인펜)을 사용하여 다음과 같이 측정했다. 상기에서 얻어진 하드코팅 도포막에, 각각 소정의 표면장력값(30∼70ｄｙｎ/cm)을 구비하는 다인펜에서 1개를 사용해서 5cm의 선을 긋고, 선의 형상이 5초 이상 유지되어 있으면 젖어 있다고 판정했다. 선의 형상이 5초 이상 유지된 경우에는, 표면장력값이 더 높은 다인펜으로 바꾸어서 선을 긋고 마찬가지로 젖어 있는지 판정했다. 선의 형상이 5초 미만에 붕괴된 경우에는, 표면장력값이 낮은 다인펜으로 바꾸어서 선을 긋고 젖어 있는지 판정했다. 상기 조작을 반복하고, 상기 도포막 표면에서 선의 형상이 5초 이상 유지된 다인펜 중에서 최대의 표면장력값을, 상기 하드코팅 도포막의 표면장력(초기값)으로 했다.A test pen (Dainpen) for evaluating the surface energy value of Arcotest was measured as follows. A 5 cm line was drawn on the hard coat film obtained by using one of the dyne pens each having a predetermined surface tension value (30 to 70 dyn / cm), and when the line shape was maintained for 5 seconds or longer, " When the shape of the line was maintained for 5 seconds or longer, the line was drawn by changing to a multi-in-pen having a higher surface tension value and it was judged whether or not it was wet. When the shape of the line collapsed in less than 5 seconds, the line was drawn by changing to a multi-in-pen having a low surface tension value to determine whether it was wet. The above operation was repeated, and the maximum surface tension value among the dynepens in which the line shape was maintained for 5 seconds or more on the surface of the coating film was regarded as the surface tension (initial value) of the hard coat coating film.

<가열,닦기 시험><Heating and Wiping Test>

상기 하드코팅 도포막을 150℃의 순풍건조기 중에 30분간 보관하고, 그 후에 에탄올을 적신 면봉으로 50왕복 문지른(러빙한) 상기 하드코팅 도포막의 표면장력값을 상기의 방법으로 측정하여, 가열전의 상기 하드코팅 도포막의 표면장력(초기값)과 비교해서 평가했다.The hard coat coating film was stored in a circulating air dryer at 150 캜 for 30 minutes, and then the surface tension value of the hard coating film rubbed (rubbed) through the reciprocating swab 50 times with ethanol was measured by the above-mentioned method, And the surface tension (initial value) of the coated film was evaluated.

○ = 초기값과 변화없음 × = 초기값보다 표면장력값이 저하○ = initial value and no change × = the surface tension value is lower than the initial value

<도포막 외관>&Lt; External appearance of coating film &

상기 하드코팅 도포막의 외관을, 레벨링성(평활성) 및 요철표면, 크롤링(crawling)(핀홀) 등의 불량의 유무에 관해서, 육안으로 평가했다.The outer appearance of the hard coat film was evaluated visually with respect to the leveling property (smoothness), the surface irregularities, the presence of defects such as crawling (pinholes) and the like.

○ = 평활하고, 요철표면, 핀홀 등의 불량이 없다.○ = Smooth, uneven surface, no pinholes, etc.

× = 평활하지 않고, 요철표면, 핀홀 등의 불량이 있다.X: Smooth, uneven surface, pinholes, and the like are defective.

Figure pat00001
Figure pat00001

표1 중의 약어 및 주석은, 아래와 같다.Abbreviations and comments in Table 1 are as follows.

1)실리카 입자가 도포막으로부터 탈락하여, 도포막 평가를 할 수 없었다.1) The silica particles fell off the coating film, and the coating film evaluation could not be performed.

Claims (8)

에폭시기 함유 모노(메타)아크릴레이트를 포함하는 모노머 성분의 라디칼 중합체(a1-1) 및 α,β-불포화 카르복시산(a1-2)의 반응물인 수산기 함유 (메타)아크릴 공중합체(a1), 및/또는 적어도 3개의 (메타)아크릴로일기를 구비하는 수산기 함유 다관능 (메타)아크릴레이트(a2)를 포함하며 수산기 농도가 0.8ｍｍｏｌ/ｇ 이상인 다관능 (메타)아크릴레이트류(A)와,
표면 실라놀기 농도가 60∼200μｍｏｌ/g인 친수성 실리카 미립자(B)를
고형분질량비((A)/(B))로 20/80 ∼ 90/10 포함하는 활성에너지선 경화형 하드코팅제.
(Meth) acrylic copolymer (a1) which is a reactant of a monomer component (a1-1) containing an epoxy group-containing mono (meth) acrylate and an?,? - unsaturated carboxylic acid (a1-2) (Meth) acrylate (A) containing a hydroxyl group-containing polyfunctional (meth) acrylate (a2) having at least three (meth) acryloyl groups and having a hydroxyl group concentration of 0.8 mmol / g or more,
Hydrophilic silica fine particles (B) having a surface silanol group concentration of 60 to 200 占 퐉 ol / g
Active energy ray hardening type hard coating agent containing 20/80 to 90/10 by mass ratio ((A) / (B)).
제1항에 있어서,
(B)성분의 표면 실라놀기 농도가 100∼200μｍｏｌ/g인 활성에너지선 경화형 하드코팅제.
The method according to claim 1,
And the surface silanol group concentration of the component (B) is 100 to 200 占 퐉 ol / g.
제1항 또는 제2항에 있어서,
(A)성분과 (B)성분의 고형분질량비((A)/(B))가 30/70 ∼ 70/30인 활성에너지선 경화형 하드코팅제.
3. The method according to claim 1 or 2,
(A) / (B)) of the component (A) / (B) is in the range of 30/70 to 70/30.
제1항에 있어서,
(B)성분의 평균1차입경이 10∼50nm인 활성에너지선 경화형 하드코팅제.
The method according to claim 1,
(B) having an average primary particle diameter of 10 to 50 nm.
제1항에 있어서,
광중합개시제(C)를 더 함유하는 활성에너지선 경화형 하드코팅제.
The method according to claim 1,
An active energy ray-curable hard coating further comprising a photopolymerization initiator (C).
제1항의 하드코팅제의 경화도포막.
A cured coating of the hard coating of claim 1.
제6항에 있어서,
표면장력이 44∼48ｄｙｎ/cm인 경화도포막.
The method according to claim 6,
A cured film having a surface tension of 44 to 48 dyn / cm.
제6항 또는 제7항의 경화도포막을 구비하는 적층필름.A laminated film comprising the cured coating film of claim 6 or 7.
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