KR20170029655A - Active energy ray-curable resin composition, transfer sheet, decorative board, and method for producing decorative board - Google Patents

Active energy ray-curable resin composition, transfer sheet, decorative board, and method for producing decorative board Download PDF

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KR20170029655A
KR20170029655A KR1020177006388A KR20177006388A KR20170029655A KR 20170029655 A KR20170029655 A KR 20170029655A KR 1020177006388 A KR1020177006388 A KR 1020177006388A KR 20177006388 A KR20177006388 A KR 20177006388A KR 20170029655 A KR20170029655 A KR 20170029655A
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component
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resin
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히로유키 도이
코타로 코데라
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아이카고교 가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
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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
    • C08L33/04—Homopolymers or copolymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/38242—Contact thermal transfer or sublimation processes characterised by the use of different kinds of energy to effect transfer, e.g. heat and light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
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    • 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
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B32B2037/268—Release layers
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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    • B32B2451/00—Decorative or ornamental articles

Abstract

본 발명의 활성 에너지선 경화형 수지 조성물은, (A) 라디칼 반응성기를 2개 포함한 우레탄 아크릴레이트 수지 또는 아크릴 수지와, (B) 라디칼 반응성기를 6개 이상 포함한 우레탄 아크릴레이트 수지 또는 아크릴 수지를 포함하며, 상기 (A) 성분과 상기 (B) 성분의 합계량을 100중량부로 했을 때, 상기 (A) 성분의 양이 30~70중량부인 것을 특징으로 한다.The active energy ray-curable resin composition of the present invention comprises (A) a urethane acrylate resin or an acrylic resin containing two radical reactive groups, (B) a urethane acrylate resin or an acrylic resin containing at least six radical reactive groups, Wherein the amount of the component (A) is 30 to 70 parts by weight based on 100 parts by weight of the total amount of the component (A) and the component (B).

Figure P1020177006388
Figure P1020177006388

Description

활성 에너지선 경화형 수지 조성물, 전사 시트, 화장판 및 화장판의 제조방법{ACTIVE ENERGY RAY-CURABLE RESIN COMPOSITION, TRANSFER SHEET, DECORATIVE BOARD, AND METHOD FOR PRODUCING DECORATIVE BOARD}TECHNICAL FIELD [0001] The present invention relates to an active energy ray-curable resin composition, an active energy ray-curable resin composition, a transfer sheet, a transparent sheet,

본 출원은, 2009년 9월 30일부로 일본 특허청에 출원된 특허 출원 제2009-227539호의 우선권을 주장하는 것으로, 그 모든 내용은, 참조에 의해 본 명세서에 원용된다.This application claims priority of Japanese Patent Application No. 2009-227539, filed with the Japanese Patent Office on Sep. 30, 2009, the entire contents of which are incorporated herein by reference.

본 발명은, 예를 들면, 화장판 용도로 제공되는 활성 에너지선 경화형 수지 조성물, 전사 시트, 화장판 및 그 제조 방법에 관한 것이다.The present invention relates to, for example, an active energy ray-curable resin composition, a transfer sheet, a veneer sheet and a method for producing the same, which are provided for use in a veneer.

종래, 화장판 표면의 내찰상성(耐擦傷性), 내약품성, 내오염성, 내후성(耐候性)을 향상시키는 수단으로서는, 활성 에너지선 경화형 수지나 열경화형 수지를 포함하는 도포액(塗液)을 화장판 표면에 도포하여 경화시키는 방법, 그러한 수지를 포함하는 도포액을 박리성이 있는 기재에 도포하여 경화하고, 전사 시트로 한 후, 전사 시트의 경화 도막(塗膜)을 화장판에 겹치며, 가열 가압 등에 의해, 그 화장판 표면에 경화 도막을 전사하는 방법, 기재 위에 설치한 도막을 반경화 상태로 하여 전사 시트로 하고, 전사 시트의 반경화 상태의 도막을 화장판 표면에 전사한 후에, 다시 경화 처리를 행하여, 화장판 표면에 상기 내성을 가지는 도막을 설치하는 방법이 알려져 있다. 특히, 활성 에너지선에 의해 경화한 도막은, 우수한 도막 특성(내찰상성, 내오염성 등)을 가지기 때문에, 도막을 화장판 표면에 설치하는 방법에 대해서는, 다양하게 제안되고 있다(특허문헌 1~2 참조).Conventionally, as a means for improving the abrasion resistance, chemical resistance, stain resistance and weather resistance of the surface of a veneer, a coating liquid (coating liquid) containing an active energy ray-curable resin or a thermosetting resin A method in which a coating liquid containing such a resin is coated on a releasable substrate and cured to form a transfer sheet, and then the cured coating film (coating film) of the transfer sheet is superimposed on the laminating sheet, A method in which a cured coating film is transferred to the surface of the colored sheet by heating or pressing, or a method in which a coated film provided on a substrate is turned into a semi-cured state to form a transfer sheet, There is known a method in which a hardening treatment is performed again to provide a coating film having the above resistance on the surface of the brightening plate. Particularly, a coating film cured by an active energy ray has excellent coating film properties (scratch resistance, stain resistance, etc.), and therefore various methods for providing a coating film on the surface of a film have been proposed (see Patent Documents 1 to 2 Reference).

일본국 공개특허공보 제2003-137942호Japanese Patent Application Laid-Open No. 2003-137942 일본국 공개특허공보 제2003-183339호Japanese Patent Application Laid-Open No. 2003-183339

그렇지만, 일반적으로 상기 내성을 가지는 도막은, 분자 중에 많은 반응성 관능기를 가지는 재료를 가교시켜 이루어지는 것으로, 높은 가교 밀도를 가지는 경우가 많아, 그 도막을 직접 화장판에 밀착시키고자 한 경우, 도막의 치밀함, 경화 수축 등에 의해, 화장판의 표면에 대한 밀착성이 현저하게 열화하는 경우가 많다. 또한, 전사 시트를 이용하는 경우에는, 전사 시트의 도막측, 혹은 화장판측에 프라이머층이나 접착제층 등을 설치하여, 밀착성을 확보하고 있는 것이 현 상태이다.However, in general, the coating film having the aforementioned resistance is formed by crosslinking a material having a large number of reactive functional groups in the molecule, and often has a high crosslinking density. When the coating film is to be directly adhered to the film, The adherence to the surface of the luster plate is remarkably deteriorated in many cases due to curing, shrinkage or the like. When a transfer sheet is used, a primer layer, an adhesive layer, or the like is provided on the side of the coated film of the transfer sheet or on the side of the transparent sheet to secure adhesion.

본 발명은, 프라이머나 접착제를 반드시 이용하지 않고, 멜라민 수지층 등의 위에 활성 에너지선 경화성 수지 조성물의 경화물을 확실하게 밀착시킬 수 있는 활성 에너지선 경화형 수지 조성물, 전사 시트, 화장판 및 화장판의 제조 방법을 제공하는 것을 목적으로 한다.The present invention relates to an active energy ray-curable resin composition capable of reliably adhering a cured product of an active energy ray-curable resin composition onto a melamine resin layer or the like without necessarily using a primer or an adhesive, a transfer sheet, And a method for producing the same.

본 발명의 활성 에너지선 경화형 수지 조성물은, (A) 라디칼 반응성기를 2개 포함한 우레탄 아크릴레이트 수지(urethane acrylate resin) 또는 아크릴 수지(acrylic resin)와, (B) 라디칼 반응성기를 6개 이상 포함한 우레탄 아크릴레이트 수지 또는 아크릴 수지를 포함하며, 상기 (A) 성분과 상기 (B) 성분의 합계량을 100중량부로 했을 때, 상기 (A) 성분의 양이 30~70중량부인 것을 특징으로 한다.The active energy ray-curable resin composition of the present invention comprises (A) a urethane acrylate resin or an acrylic resin containing two radical reactive groups, (B) a urethane acrylate resin containing at least six radical reactive groups, (A) is 30 to 70 parts by weight based on 100 parts by weight of the total amount of the component (A) and the component (B).

본 발명의 활성 에너지선 경화형 수지 조성물을 이용함으로써, 예를 들면, 전사 시트의 도막측, 혹은 화장판측에 프라이머(primer) 처리를 실시하지 않아도, 활성 에너지선 경화형 수지 조성물로 이루어지는 층(경화물)의 밀착성, 내찰상성, 내약품성이 우수한 화장판을 얻을 수 있다.By using the active energy ray-curable resin composition of the present invention, for example, even when a primer treatment is not performed on the side of the coated film of the transfer sheet or the side of the colored sheet, ), The scratch resistance, and the chemical resistance.

본 발명의 활성 에너지선 경화형 수지 조성물은, 도전성 졸(sol)을 더 포함하는 것이 바람직하다.The active energy ray-curable resin composition of the present invention preferably further comprises a conductive sol (sol).

본 발명의 전사 시트는, 박리성 기재(基材)와, 상기 박리성 기재에 형성된, 상술한 활성 에너지선 경화형 수지 조성물로 이루어지는 층을 구비한다.The transfer sheet of the present invention comprises a releasable base material and a layer formed of the above-mentioned active energy ray-curable resin composition formed on the releasable base material.

본 발명의 화장판은, 멜라민 수지층과, 상기 멜라민 수지층 위에 형성된, 상술한 활성 에너지선 경화형 수지 조성물의 경화물로 이루어지는 층을 구비한다.The colored plate of the present invention comprises a melamine resin layer and a layer formed of the cured product of the above-mentioned active energy ray-curable resin composition formed on the melamine resin layer.

본 발명의 화장판의 제조 방법은, 코어재(core material)와, 화장지에 열경화성 수지를 주(主)성분으로 하는 수지액을 함침(含浸)하며, 건조하여 이루어진 수지 함침 화장지와, 상술한 전사 시트를 적층하고, 열압(熱壓) 성형하며, 상기 열압 성형 후, 상기 박리성 기재를 제거한다.A method of manufacturing a colored sheet according to the present invention comprises a core material, a resin-impregnated toilet paper impregnated with a resin liquid containing a thermosetting resin as a main component and dried, The sheets are laminated and thermoformed, and after the thermoforming, the peelable base material is removed.

도 1은 본 발명의 내약품성 화장판을 얻기 위하여 재료를 적층할 때의 구성 단면도이다.
도 2는 본 발명의 내약품성 화장판의 구성 단면도이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a structural cross-sectional view of a laminated material for obtaining a chemical resistant laminate of the present invention. FIG.
2 is a structural cross-sectional view of the chemical resistant sheet of the present invention.

이하, 본 발명에 대하여 상세하게 설명한다. 본 발명에서 이용하는 (A) 성분 중, 라디칼 반응성기를 2개 포함한 우레탄 아크릴레이트 수지는, 예를 들면, 폴리올(polyol)과 디이소시아네이트(diisocyanate)를 반응시켜 얻어지는 이소시아네이트 화합물(isocyanate compound)과 히드록시에틸아크릴레이트(hydroxyethyl acrylate), 히드록시프로필아크릴레이트(hydroxypropyl acrylate), 히드록시부틸아크릴레이트(hydroxybutyl acrylate) 등의 수산기를 가지는 아크릴레이트 모노머와의 반응 생성물이다. (A) 성분의 중량 평균 분자량은, 500~1500이 바람직하다.Hereinafter, the present invention will be described in detail. Of the component (A) used in the present invention, the urethane acrylate resin containing two radical reactive groups can be obtained by, for example, reacting an isocyanate compound obtained by reacting a polyol with a diisocyanate, Acrylate monomer having a hydroxyl group such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and the like. The weight average molecular weight of the component (A) is preferably 500 to 1500.

또한, 본 발명에서 이용하는 (A) 성분 중, 라디칼 반응성기를 2개 포함한 아크릴 수지로서는, 예를 들면, 아크릴산(acrylic acid), 메타크릴산(methacrylic acid) 또는 이들의 유도체의 중합체로 이루어지는 것으로, 예를 들면, 아크릴산메틸(methyl acrylate), 아크릴산에틸(ethyl acrylate), 아크릴산부틸(butyl acrylate) 등의 아크릴산에스테르(acrylic ester), 메타크릴산메틸(methyl methacrylate), 메타크릴산에틸(ethyl methacrylate), 메타크릴산부틸(butyl methacrylate) 등의 메타크릴산에스테르(methacrylic ester)를 주성분으로 한 중합체를 들 수 있다.Among the components (A) used in the present invention, the acrylic resin containing two radical reactive groups includes, for example, acrylic acid, methacrylic acid or derivatives thereof, For example, acrylic ester such as methyl acrylate, ethyl acrylate and butyl acrylate, methyl methacrylate, ethyl methacrylate, And a polymer mainly composed of a methacrylic ester such as butyl methacrylate.

본 발명에서 이용하는 (B) 성분 중, 라디칼 반응성기를 6개 이상 포함한 우레탄 아크릴레이트 수지는, 예를 들면, 폴리에스테르 폴리올(polyester polyol), 폴리에테르 폴리올(polyether polyol), 폴리카보네이트 폴리올(polycarbonate polyol) 등의 폴리올과 디이소시아네이트를 반응시켜 얻어지는 이소시아네이트 화합물과, 트리메티롤프로판 트리아크릴레이트(trimethylolpropane triacrylate), 펜타에리트리톨 트리아크릴레이트(pentaerythritol triacrylate), 디펜타에리트리톨 트리아크릴레이트(dipentaerythritol triacrylate) 등의 수산기를 가지는 아크릴레이트 모노머와의 반응 생성물이다. (B) 성분의 중량 평균 분자량은 500~6000이 바람직하다.Among the components (B) used in the present invention, the urethane acrylate resin containing at least six radical reactive groups is, for example, a polyester polyol, a polyether polyol, a polycarbonate polyol, Or a mixture of an isocyanate compound obtained by reacting a polyol such as a polyisocyanate with a diisocyanate and a polyisocyanate compound such as trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate, etc. And a reaction product with an acrylate monomer having a hydroxyl group. The weight average molecular weight of the component (B) is preferably from 500 to 6,000.

또한, 본 발명에서 이용하는 (B) 성분 중, 라디칼 반응성기를 6개 이상 포함한 아크릴 수지로서는, 예를 들면, 아크릴산, 메타크릴산 또는 이들의 유도체의 중합체로 이루어지는 것으로, 예를 들면, 아크릴산메틸, 아크릴산에틸, 아크릴산부틸 등의 아크릴산에스테르, 메타크릴산메틸, 메타크릴산에틸, 메타크릴산부틸 등의 메타크릴산에스테르를 주성분으로 한 중합체를 들 수 있다.Among the components (B) used in the present invention, the acrylic resin containing six or more radical reactive groups includes, for example, a polymer of acrylic acid, methacrylic acid or derivatives thereof, and examples thereof include methyl acrylate, Acrylic acid esters such as ethyl and butyl acrylate, and polymers composed mainly of methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate.

(A) 성분과 (B) 성분의 배합 비율은 70:30~30:70중량부(고형분비)로 하는 것이 바람직하고, (B) 성분이 하한에 미치지 못하면, 활성 에너지선 경화형 수지 조성물로 이루어지는 층의 밀착성, 내약품성이 열화하기 쉽고, 상한을 초과하면 밀착성이 열화하기 쉽다.The ratio of the component (A) to the component (B) is preferably from 70:30 to 30:70 parts by weight (solid content ratio). When the amount of the component (B) The adhesion of the layer and the chemical resistance are liable to deteriorate, and when the upper limit is exceeded, the adhesion is likely to deteriorate.

활성 에너지선 경화형 수지 조성물의 전체 고형분에 대한, (A) 성분과 (B) 성분의 합계량의 비율(중량비)은, 90~100%의 범위가 바람직하다.The ratio (weight ratio) of the total amount of the components (A) and (B) to the total solid content of the active energy ray-curable resin composition is preferably in the range of 90 to 100%.

본 발명의 활성 에너지선 경화형 수지 조성물에는, (A) 성분과 (B) 성분 이외에, 도전성 졸을 배합하는 것이 바람직하다. 도전성 졸은, 화장판을 제조할 때, 박리성 기재에 활성 에너지선 경화형 수지 조성물이 도포된 전사 시트의 대전 방지에 효과가 있어, 전사 시트의 취급 중에 정전기 발생에 의한 먼지의 부착을 방지할 수 있다. 특히 안티몬계의 도전성 졸이 바람직하고, 도전성 졸의 사용량은, (A) 성분과 (B) 성분의 합계 100중량부에 대해 8~15중량부의 범위가 바람직하다. 15중량부를 초과하면 착색 및 내약품성이 열화하기 쉽고, 8중량부보다 적으면 충분한 대전 방지 효과를 얻을 수 없는 경우가 있다.In addition to the component (A) and the component (B), a conductive sol is preferably blended in the active energy ray-curable resin composition of the present invention. The conductive sol has an effect of preventing electrification of the transfer sheet coated with the active energy ray-curable resin composition on the releasable substrate when producing the sheet, and it is possible to prevent adhesion of dust due to generation of static electricity during handling of the transfer sheet have. In particular, antimony-based conductive sols are preferred, and the conductive sol is preferably used in an amount of 8 to 15 parts by weight based on 100 parts by weight of the total of the components (A) and (B). If the amount is more than 15 parts by weight, coloring and chemical resistance tend to deteriorate. If less than 8 parts by weight, sufficient antistatic effect may not be obtained.

안티몬계의 도전성 졸로서는, 시판품으로서 닛산 카가쿠 고교 가부시키가이샤 제품의 세르낙스(등록상표) 시리즈(안티몬산아연계)를 들 수 있다. 수(水)분산 졸로서 CX-Z330H, CX-Z330H-F2나, 메탄올분산 졸로서 CX-Z641M, CX-Z603M, CX-Z603M-F2, CX-Z610M-F2, CX-Z653M-F, CX-Z693M-F나, 이소프로판올 분산 졸로서 CX-Z210IP, CX-Z210IP-F2(모두 상품명)가 있으며, (A) 성분, (B) 성분의 종류, 배합 비율에 따라, 적당히 선택하여 이용할 수 있다.As the antimony-based conductive sol, CERAXUS (registered trademark) series (antimony acid anhydride) manufactured by Nissan Kagaku Kogyo Co., Ltd. is commercially available. CX-Z603M-F2, CX-Z653M-F, CX-Z653M-F and CX-Z653M-F as methanol dispersion sols, CX-Z601M, CX- Z693M-F and CX-Z210IP and CX-Z210IP-F2 (all trade names) as an isopropanol dispersed sol and can be appropriately selected depending on the kind of the component (A) and the blending ratio of the component (A).

또한, 자외선 조사하는 경우, 본 발명의 활성 에너지선 경화형 수지 조성물에는, (A) 성분과 (B) 성분 이외에, 광 개시제를 배합하는 것이 바람직하다. 광 개시제는, 예를 들면, 벤질케탈(benzyl ketal),α-히드록시아세토페논(α-hydroxyacetophenone),α-아미노아세토페논(α-aminoacetophenone), 아실포스핀옥사이드(acyl phosphine oxide), 티타노센계 화합물(titanocene-based compound), 옥심에스테르(oxime ester) 등을 이용할 수 있다. 시판품으로서는 IRGACURE 184, 369, 651, 819, DAROCUR 1173(치바·스페셜티·케미칼스 가부시키가이샤 제품, 상품명)등을 들 수 있다. 광 개시제의 사용량은, (A) 성분과 (B) 성분의 합계 100중량부에 대해 1~10중량부인 것이 바람직하다. 10중량부보다 많으면 경화 피막이 착색하기 쉽고, 1중량부보다 적으면 충분한 경화를 얻을 수 없는 경우가 있다.In addition, when irradiated with ultraviolet rays, a photoinitiator is preferably blended with the active energy ray-curable resin composition of the present invention in addition to the components (A) and (B). The photoinitiator may be, for example, benzyl ketal,? -Hydroxyacetophenone,? -Aminoacetophenone, acyl phosphine oxide, A titanocene-based compound, an oxime ester, or the like can be used. Commercially available products include IRGACURE 184, 369, 651, 819, DAROCUR 1173 (trade name, product of Chiba Specialty Chemicals Co., Ltd.) and the like. The amount of the photoinitiator to be used is preferably 1 to 10 parts by weight based on 100 parts by weight of the total of the components (A) and (B). If the amount is more than 10 parts by weight, the cured coating tends to be colored, and if it is less than 1 part by weight, sufficient curing may not be obtained.

본 발명의 전사 시트에서 이용되는(예를 들면, 활성 에너지선 경화형 수지 조성물이 도포되는) 박리성 기재는, 수지 함침 화장지의 표면에 활성 에너지선 경화형 수지 조성물이 열압 성형에 의해 전사된 후, 박리 가능한 것이면 되며, 폴리에스테르 필름(polyester film), 폴리에틸렌 필름(polyethylene film), 폴리프로필렌 필름(polypropylene film), 셀로판(cellophane), 디아세틸셀룰로오스 필름(diacetylcellulose film), 트리아세틸셀룰로오스 필름(triacetylcellulose film), 아세틸셀룰로오스부틸레이트 필름(acetylcellulose butyrate film), 폴리염화비닐 필름(polyvinyl chloride film), 폴리염화비닐리덴 필름(polyvinylidene chloride film), 폴리비닐알코올 필름(polyvinyl alcohol film), 에틸렌비닐알코올 필름(ethylene vinyl alcohol film), 폴리스티렌 필름(polystyrene film), 폴리카보네이트 필름(polycarbonate film), 폴리메틸펜텐 필름(polymethylpentene film), 폴리술폰 필름(polysulfone film), 폴리에테르케톤 필름(polyether ketone film), 폴리에테르술폰 필름(polyether sulfone film), 폴리에테르이미드 필름(polyetherimide film), 폴리이미드 필름(polyimide film), 불소 수지 필름(fluororesin film), 나일론 필름(nylon film), 아크릴 필름(acrylic film) 등의 플라스틱 필름, 알루미늄박, 스테인리스박, 동박 등의 금속박을 사용할 수 있다.The releasable base material used in the transfer sheet of the present invention (for example, to which the active energy ray-curable resin composition is applied) is obtained by transferring the active energy ray-curable resin composition onto the surface of the resin- And may be a polyester film, a polyethylene film, a polypropylene film, a cellophane, a diacetylcellulose film, a triacetylcellulose film, But are not limited to, acetylcellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, film, a polystyrene film, a polycarbonate film, A polyether sulfone film, a polyether sulfone film, a polyether sulfone film, a polyether sulfone film, a polyether sulfone film, a polymethylpentene film, a polysulfone film, a polyether ketone film, a polyether sulfone film, a polyetherimide film, ), A plastic film such as a fluororesin film, a nylon film and an acrylic film, or a metal foil such as an aluminum foil, a stainless steel foil or a copper foil.

상기 박리성 기재의 표면에 상기 활성 에너지선 경화형 수지 조성물을 도포하는 경우는 공지의 방법, 예를 들면, 스프레이(spray) 코팅법, 그라비아(gravure) 코팅법, 바(bar) 코팅법, 나이프(knife) 코팅법, 롤(roll) 코팅법, 블레이드(blade) 코팅법, 다이(die) 코팅법, 커튼(curtain) 코팅법 등을 이용할 수 있다. 건조 후의 도막의 두께는 1~100㎛ 정도인 것이 바람직하다.When the active energy ray-curable resin composition is applied to the surface of the peelable base material, a known method such as a spray coating method, a gravure coating method, a bar coating method, a knife a knife coating method, a roll coating method, a blade coating method, a die coating method, and a curtain coating method may be used. The thickness of the coated film after drying is preferably about 1 to 100 mu m.

박리성 기재의 표면에 활성 에너지선 경화형 수지 조성물을 도포한 후에는, 예를 들면, 전자선, 자외선을 조사할 수 있다. 자외선을 조사하는 경우는, 초고압 수은등, 고압 수은등, 저압 수은등, 카본 아크(carbon arc), 메탈 할라이드 램프(metal halide lamp) 등을 이용하여, 100~400㎚, 바람직하게는 200~400㎚의 파장 영역에서, 100~800mJ/㎝2의 에너지를 가지는 자외선을 조사하는 것이 바람직하다. 이 조건이면 열압 성형 시에 수지 함침 화장지와의 밀착이 강고해진다. 또한, 필요에 따라 질소 분위기 하에서 경화해도 된다.After the active energy ray-curable resin composition is applied to the surface of the peelable base material, it is possible to irradiate, for example, an electron beam or an ultraviolet ray. When irradiating with ultraviolet rays, it is preferable to use a high-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like to emit light of 100 to 400 nm, preferably 200 to 400 nm It is preferable to irradiate ultraviolet rays having an energy of 100 to 800 mJ / cm < 2 >. This condition strengthens adhesion with resin-impregnated toilet paper during hot-pressing. Further, if necessary, it may be cured in a nitrogen atmosphere.

본 발명의 화장판에서 이용되는 수지 함침 화장지로서는, 통상 공지의 화장판용 화장지에 열경화성 수지, 특히 내열성, 내마모성이 우수하 멜라민포름알데히드 수지를 주된 성분으로 하는 수지액을 화장지에 함침하여, 건조한 것이 바람직하게 이용된다.As the resin impregnated toilet paper used in the present invention, it is preferable that a conventional toilet paper is prepared by impregnating a thermosetting resin, particularly a resin liquid having excellent heat resistance and abrasion resistance and containing melamine formaldehyde resin, .

코어재에는, 화장판용 크라프트지(kraft paper), 부직포, 천(cloth) 등에 열경화성 수지를 함침 처리한 수지 함침 코어지나, 합판, MDF(Medium　Density Fiberboard: 중밀도 섬유판), 파티클 보드(particle board) 등의 목질계(木質系) 기재가 이용되며, 적당한 용도, 요구되는 품질에 따라 선택된다.The core material may include a resin impregnated core impregnated with a thermosetting resin for kraft paper, nonwoven fabric, or cloth for a veneer, a plywood, a MDF (Medium Density Fiberboard), a particle board ) Is used, and it is selected according to a suitable use and a required quality.

실시예 1Example 1

(A) 라디칼 반응성기를 2개 포함한 우레탄 아크릴레이트 수지인, UN-2301(상품명 아트레진(Art-Resin), 네가미 고교 가부시키가이샤 제품, 중량 평균 분자량 740) 70중량부, (B) 라디칼 반응성기를 10개 포함한 우레탄 아크릴레이트 수지인, UN-904(상품명 아트레진, 네가미 고교 가부시키가이샤 제품, 중량 평균 분자량 4900) 30중량부, 및 광 개시제인 IRGACURE 184(치바·스페셜티·케미칼즈 가부시키가이샤 제품, 상품명) 3중량부를 메틸에틸케톤(methyl ethyl ketone) 40중량부로 희석하여 자외선 경화형 수지 조성물(활성 에너지선 경화형 수지 조성물)을 얻었다.(A) 70 parts by weight of UN-2301 (trade name: Art-Resin, product of Negami Chemical Industries, Ltd., weight average molecular weight 740), which is a urethane acrylate resin containing two radical reactive groups, (B) 30 parts by weight of UN-904 (trade name: Art resin, product of Negami Kogyo K.K., weight average molecular weight: 4900), which is a urethane acrylate resin containing 10 groups, and IRGACURE 184 (trade name, available from Ciba Specialty Chemicals Co., Ltd.) was diluted with 40 parts by weight of methyl ethyl ketone to obtain an ultraviolet ray curable resin composition (active energy ray curable resin composition).

다음으로, 두께 80㎛의 OPP(Oriented　Polypropylene: 연신 폴리프로필렌) 필름에 건조 막 두께가 30㎛가 되도록 상기 자외선 경화형 수지 조성물을 도포하며, 고압 수은등으로 조사 강도가 400mJ/㎝2가 되도록 자외선을 조사하여 전사 시트를 얻고, 이 전사 시트를 1주간 양생(養生)하였다. 이 전사 시트(3)는, 도 1에 도시한 바와 같이, OPP 필름(1; 박리성 기재)과, 그 OPP 필름(1)에 형성된, 자외선 경화형 수지 조성물로 이루어지는 층(2)를 구비하는 것이다.Next, OPP having a thickness of 80㎛: irradiation of ultraviolet rays, and coating the UV-curable resin composition so that the dry film thickness on 30㎛ (Oriented Polypropylene stretched polypropylene) film, a high-pressure mercury lamp such that the intensity 400mJ / ㎝ 2 To obtain a transfer sheet, and this transfer sheet was cured (cured) for one week. 1, the transfer sheet 3 is provided with an OPP film 1 (releasable substrate) and a layer 2 composed of an ultraviolet curable resin composition formed on the OPP film 1 .

평량(坪量) 100g/m2의 인쇄지에 멜라민포름알데히드 수지(melamine-formaldehyde resin)를 주된 성분으로 하는 수지액을 함침하고, 건조하여 멜라민 수지 함침 화장지를 얻었다.A printing paper having a basis weight of 100 g / m 2 was impregnated with a resin liquid containing melamine-formaldehyde resin as a main component and dried to obtain a tissue paper impregnated with melamine resin.

평량 185g/m2의 크라프트지에 페놀포름알데히드 수지(phenol-formaldehyde resin)를 주된 성분으로 하는 수지액을 함침하고, 건조하여 페놀 수지 함침 코어지를 얻었다.A phenolic resin impregnated core paper was obtained by impregnating a kraft paper having a basis weight of 185 g / m 2 with a resin liquid containing phenol-formaldehyde resin as a main component.

도 1에 도시한 바와 같이, 아래에서부터 순서대로, 페놀 수지 함침 코어지(7)를 5장, 멜라민 수지 함침 화장지(6)를 1장, 전사 시트(3)를 1장 적층하고, 온도 132℃, 압력 70㎏/㎝2의 조건으로 열압 성형하며, 성형 후 OPP(Oriented　Polypropylene: 연신 폴리프로필렌) 필름을 제거하여, 도 2에 도시하는, 내약품성 화장판(9)을 얻었다. 내약품성 화장판(9)에 있어서, 7a는 경화한 수지 함침 코어지이고, 6a는 경화한 수지 함침 화장지이며, 2a는 자외선 경화형 수지 조성물의 경화물이다.1, five phenol resin-impregnated core paper 7, one melamine resin-impregnated toilet paper 6 and one transfer sheet 3 were laminated in this order from the bottom, , And a pressure of 70 kg / cm 2 , and after the molding, the OPP (Oriented Polypropylene) film was removed to obtain a chemical resistant plate 9 shown in FIG. Reference numeral 7a denotes a cured resin impregnated core paper, 6a denotes a cured resin impregnated toilet paper, and 2a denotes a cured product of the ultraviolet curable resin composition.

실시예 2Example 2

(A) 성분으로서 라이트(light) 아크릴레이트 1,6HX-A(쿄에이샤 카가쿠 가부시키가이샤 제품, 분자량 226) 70중량부를 이용하고, (B) 성분으로서 KAYARAD DPHA(니혼 카야쿠 가부시키가이샤 제품, 분자량 878) 30중량부를 이용한 점 이외에는 상기 실시예 1과 동일하게 실시하였다.70 parts by weight of light acrylate 1,6HX-A (manufactured by Kyowa Chemical Co., Ltd., molecular weight 226) was used as the component (A), and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Product, molecular weight 878) were used in place of the above-mentioned components.

여기서, 라이트 아크릴레이트 1,6HX-A는, 라디칼 반응성기를 2개 포함한 아크릴 수지이다. 또한, KAYARAD DPHA는, 라디칼 반응성기를 6개 포함한 아크릴 수지이다.Here, the light acrylate 1,6HX-A is an acrylic resin containing two radical reactive groups. KAYARAD DPHA is an acrylic resin containing six radical reactive groups.

실시예 3Example 3

(A) 성분의 배합량을 50중량부로 하고, (B) 성분의 배합량을 50중량부로 한 점 이외에는 상기 실시예 1과 동일하게 실시하였다.The procedure of Example 1 was repeated except that the amount of the component (A) was changed to 50 parts by weight and the amount of the component (B) was changed to 50 parts by weight.

실시예 4Example 4

(A) 성분으로서 라이트 아크릴레이트 1,6HX-A(쿄에이샤 카가쿠 가부시키가이샤 제품, 분자량 226) 50중량부를 이용하고, (B) 성분으로서 KAYARAD DPHA(니혼 카야쿠 가부시키가이샤 제품, 분자량 878) 50중량부를 이용한 점 이외에는 상기 실시예 1과 동일하게 실시하였다.50 parts by weight of light acrylate 1,6HX-A (manufactured by Kyowa Chemical Co., Ltd., molecular weight 226) was used as the component (A), and KAYARAD DPHA (product of Nippon Kayaku Co., Ltd., 878) were used in place of 50 parts by weight.

실시예 5Example 5

(A) 성분의 배합량을 30중량부로 하고, (B) 성분의 배합량을 70중량부로 한 점 이외에는 상기 실시예 1과 동일하게 실시하였다.The procedure of Example 1 was repeated except that the amount of the component (A) was changed to 30 parts by weight and the amount of the component (B) was changed to 70 parts by weight.

실시예 6Example 6

(A) 라디칼 반응성기를 2개 포함한 우레탄아크릴레이트 수지인, UN-2301(상품명 아트레진, 네가미 고교 가부시키가이샤 제품) 70중량부, (B) 라디칼 반응성기를 10개 포함한 우레탄아크릴레이트 수지인, UN-904(상품명 아트레진, 네가미 고교 가부시키가이샤 제품) 30중량부, 광 개시제인 IRGACURE 184(치바·스페셜티·케미칼즈 가부시키가이샤 제품, 상품명) 5중량부, 광 개시제인 IRGACURE 819(치바·스페셜티·케미칼즈 가부시키가이샤 제품, 상품명) 1중량부, 및 도전성 졸인 안티몬산아연의 이소프로판올 분산 졸(세르낙스 CX-Z210IP-F2, ZnSb2O6: 20%, 닛산 카가쿠 고교 가부시키가이샤 제품, 상품명) 12.5중량부를, 4-메틸-2-펜타논(4-methyl-2-pentanone) 20중량부로 희석하여 자외선 경화형 수지 조성물을 얻었다.(A) 70 parts by weight of UN-2301 (trade name: ARTREX, manufactured by Negami Chemical Industries, Ltd.), which is a urethane acrylate resin containing two radical reactive groups, and (B) a urethane acrylate resin containing 10 radical reactive groups, , 30 parts by weight of UN-904 (trade name: ART resin, available from Negami Chemical Industries Ltd.), 5 parts by weight of IRGACURE 184 (trade name, product of Chiba Specialty Chemicals Co.) as a photoinitiator, IRGACURE 819 , manufactured trade name Specialty, as to whether or Chemical's) 1 part, and conductive sol isopropanol dispersion sol (Sergio Knox CX-Z210IP-F2, ZnSb 2 O 6 of antimony acid zinc: 20%, Nissan car manufactured by Chemical Industries whether or Product, trade name) was diluted with 20 parts by weight of 4-methyl-2-pentanone to obtain an ultraviolet ray curable resin composition.

다음으로, 두께 80㎛의 OPP(Oriented　Polypropylene: 연신 폴리프로필렌) 필름에 건조 막 두께가 30㎛가 되도록 상기 자외선 경화형 수지 조성물을 도포하며, 고압 수은등으로 조사 강도가 400mJ/㎝2가 되도록 자외선을 조사하여 전사 시트를 얻고, 이 전사 시트를 1주간 양생하였다.Next, OPP having a thickness of 80㎛: irradiation of ultraviolet rays, and coating the UV-curable resin composition so that the dry film thickness on 30㎛ (Oriented Polypropylene stretched polypropylene) film, a high-pressure mercury lamp such that the intensity 400mJ / ㎝ 2 To obtain a transfer sheet, and this transfer sheet was cured for one week.

평량 100g/m2의 인쇄지에 멜라민포름알데히드 수지를 주된 성분으로 하는 수지액을 함침하고, 건조하여 멜라민 수지 함침 화장지를 얻었다.A printing paper having a basis weight of 100 g / m 2 was impregnated with a resin liquid containing melamine formaldehyde resin as a main component and dried to obtain a tissue paper impregnated with melamine resin.

평량 185g/m2의 크라프트지에 페놀포름알데히드 수지를 주된 성분으로 하는 수지액을 함침하고, 건조하여 페놀 수지 함침 코어지를 얻었다.Impregnated with a resin solution containing phenol formaldehyde resin as a main component, and dried to obtain a phenolic resin impregnated core paper with a basis weight of 185 g / m 2 .

아래에서부터 순서대로, 페놀 수지 함침 코어지를 5장, 멜라민 수지 함침 화장지를 1장, 전사 시트를 1장 적층하고, 온도 132℃, 압력 70㎏/㎝2의 조건으로 열압 성형하며, 성형 후 OPP(Oriented　Polypropylene: 연신 폴리프로필렌) 필름을 제거하여 내약품성 화장판을 얻었다.Five sheets of phenol resin impregnated core paper, one sheet of melamine resin impregnated toilet paper and one transfer sheet were laminated in this order from the bottom, and subjected to hot pressing under the conditions of a temperature of 132 DEG C and a pressure of 70 kg / cm < 2 & Oriented Polypropylene: stretched polypropylene) film was removed to obtain a chemical resistant sheet.

실시예 7Example 7

(A) 성분으로서 라이트 아크릴레이트 1,6HX-A(쿄에이샤 카가쿠 가부시키가이샤 제품, 분자량 226) 70중량부를 이용하고, (B) 성분으로서 KAYARAD DPHA(니혼 카야쿠 가부시키가이샤 제품, 분자량 878) 30중량부를 이용한 점 이외에는 상기 실시예 6과 동일하게 실시하였다.70 parts by weight of light acrylate 1,6HX-A (manufactured by Kyowa Chemical Co., Ltd., molecular weight 226) was used as the component (A), and KAYARAD DPHA (product of Nippon Kayaku Co., Ltd., molecular weight 878) were used in place of 30 parts by weight.

실시예 8Example 8

(A) 성분의 배합량을 50중량부로 하고, (B) 성분의 배합량을 50중량부로 한 점 이외에는 상기 실시예 6과 동일하게 실시하였다.Except that the amount of the component (A) was 50 parts by weight and the amount of the component (B) was 50 parts by weight.

실시예 9Example 9

(A) 성분으로서 라이트 아크릴레이트 1,6HX-A(쿄에이샤 카가쿠 가부시키가이샤 제품, 분자량 226) 50중량부를 이용하고, (B) 성분으로서 KAYARAD DPHA(니혼 카야쿠 가부시키가이샤 제품, 분자량 878) 50중량부를 이용한 점 이외에는 상기 실시예 6과 동일하게 실시하였다.50 parts by weight of light acrylate 1,6HX-A (manufactured by Kyowa Chemical Co., Ltd., molecular weight 226) was used as the component (A), and KAYARAD DPHA (product of Nippon Kayaku Co., Ltd., 878) were used in place of 50 parts by weight.

실시예 10Example 10

(A) 성분의 배합량을 30중량부로 하고, (B) 성분의 배합량을 70중량부로 한 점 이외에는 상기 실시예 6과 동일하게 실시하였다.The procedure of Example 6 was repeated except that the amount of the component (A) was changed to 30 parts by weight and the amount of the component (B) was changed to 70 parts by weight.

실시예 11Example 11

CX-Z210IP-F2의 배합량을 10중량부로 한 점 이외에는 상기 실시예 8과 동일하게 실시하였다.The procedure of Example 8 was repeated except that the amount of CX-Z210IP-F2 was changed to 10 parts by weight.

실시예 12Example 12

CX-Z210IP-F2의 배합량을 15중량부로 한 점 이외에는 상기 실시예 8과 동일하게 실시하였다.The procedure of Example 8 was repeated except that the amount of CX-Z210IP-F2 was changed to 15 parts by weight.

비교예 1Comparative Example 1

(A) 성분의 배합량을 0중량부로 하고(배합하지 않음), (B) 성분의 배합량을 100중량부로 한 점 이외에는 상기 실시예 1과 동일하게 실시하였다.Except that the amount of the component (A) was changed to 0 parts by weight (no blending), and the amount of the component (B) was changed to 100 parts by weight.

비교예 2Comparative Example 2

(A) 성분의 배합량을 10중량부로 하고, (B) 성분의 배합량을 90중량부로 한 점 이외에는 상기 실시예 1과 동일하게 실시하였다.The procedure of Example 1 was repeated except that the amount of the component (A) was changed to 10 parts by weight and the amount of the component (B) was changed to 90 parts by weight.

비교예 3Comparative Example 3

(A) 성분의 배합량을 20중량부로 하고, (B) 성분의 배합량을 80중량부로 한 점 이외에는 상기 실시예 1과 동일하게 실시하였다.The procedure of Example 1 was repeated except that the amount of the component (A) was changed to 20 parts by weight and the amount of the component (B) was changed to 80 parts by weight.

비교예 4Comparative Example 4

(A) 성분의 배합량을 80중량부로 하고, (B) 성분의 배합량을 20중량부로 한 점 이외에는 상기 실시예 1과 동일하게 실시하였다.The procedure of Example 1 was repeated except that the amount of the component (A) was 80 parts by weight and the amount of the component (B) was 20 parts by weight.

비교예 5Comparative Example 5

(A) 성분의 배합량을 90중량부로 하고, (B) 성분의 배합량을 10중량부로 한 점 이외에는 상기 실시예 1과 동일하게 실시하였다.The procedure of Example 1 was repeated except that the amount of the component (A) was changed to 90 parts by weight and the amount of the component (B) was changed to 10 parts by weight.

비교예 6Comparative Example 6

(A) 성분의 배합량을 100중량부로 하고, (B) 성분의 배합량을 0중량부로 한(배합하지 않음) 점 이외에는 상기 실시예 1과 동일하게 실시하였다.Except that the amount of the component (A) was changed to 100 parts by weight, and the amount of the component (B) was changed to 0 parts by weight (no blending).

각 실시예 및 비교예의 조성을 표 1~표 3에 나타낸다.The compositions of the respective Examples and Comparative Examples are shown in Tables 1 to 3.

[표 1][Table 1]

Figure pat00001
Figure pat00001

[표 2][Table 2]

Figure pat00002
Figure pat00002

[표 3][Table 3]

Figure pat00003
Figure pat00003

다음으로, 각 실시예 및 비교예의 화장판을 시험하였다. 시험 방법은 이하와 같이 하였다. 이하의 (a)~(c)의 시험은 모두, 자외선 경화형 수지 조성물로 이루어지는 층(전사층)의 밀착성을 평가하는 시험이다.Next, the gloss plates of each of the examples and comparative examples were tested. The test method was as follows. The following tests (a) to (c) are all tests for evaluating the adhesion of the layer (transfer layer) comprising the ultraviolet-curable resin composition.

(a) 크로스커트(cross cut) : 화장판의 표면에 커터 나이프(cutter knife)에 의해 크로스커트를 넣어, 셀로판 테이프를 일단 점착하고 나서 박리한 후, 전사층의 박리 상태를 육안으로 판정한다. (JISK5400 도료 일반 시험법　X커트 테이프법 준거). 크로스커트 시험의 평가 기준은 이하와 같이 하였다.(a) Cross-cut: A cross-cut is put on a surface of a colored plate by a cutter knife. After the cellophane tape is once adhered and peeled, the peeled state of the transfer layer is visually determined. (According to JISK5400 Paint General Test Methods X-cut tape method). The evaluation criteria of the cross-cut test were as follows.

○ : 전사 시트를 상온에서 1주간 양생하여 박리가 없음.○: The transfer sheet was cured at room temperature for 1 week, and there was no peeling.

× : 전사 시트를 상온에서 1주간 양생하여 테이프를 붙인 X 커트부의 대부분에 박리가 있음.X: The transfer sheet was cured at room temperature for one week, and most of the X-cut portion with the tape attached thereon was peeled off.

(b) 크로스커트 박리 : 크로스커트 테이프 박리(JISK5400　크로스커트 시험 준거)로 평가하였다. 크로스커트 박리의 평가 기준은 이하와 같이 하였다.(b) Cross-cut peeling: Evaluation was made by peeling the cross-cut tape (according to JIS K5400 cross-cut test standard). The criteria for the peeling of the crochet were as follows.

○ : 전사 시트를 상온에서 1주간 양생한 후에 시험하여 95/100 이상 남음.○: The transfer sheet was cured at room temperature for 1 week and then tested and remained at 95/100 or more.

× : 전사 시트를 상온에서 1주간 양생한 후에 시험하여 84/100 이하.X: The transfer sheet was cured at room temperature for 1 week and then tested under 84/100.

(c) 내수 밀착성 : 화장판을 비등수(沸騰水) 중에서 2시간 자비(煮沸)하고, 100℃의 전기 오븐에서 2시간 더 건조한 후, 표면에 커터 나이프에 의해 크로스커트를 넣어, 셀로판 테이프를 일단 붙이고 나서 박리 한 후, 전사층의 박리 상태를 육안으로 판정한다(JISK5400 도료 일반 시험법　X커트 테이프법 준거). 내수 밀착성의 평가 기준은 이하와 같이 하였다.(c) Adhesion to water resistance: The curled plate was boiled for 2 hours in boiling water and dried in an electric oven at 100 캜 for 2 hours. Then, a croquette was put on the surface by a cutter knife, After peeling, the peeled state of the transfer layer is visually judged (in accordance with JIS K5400 Pigment General Test Method X-cut tape method). The criteria for evaluation of the water resistance were as follows.

○ : 전사 시트를 상온에서 1주간 양생한 후에 시험을 해도 박리가 없음.○: The transfer sheet was cured at room temperature for 1 week and then peeled off even after the test.

× : 전사 시트를 상온에서 1주간 양생한 후에 시험을 하여 테이프를 붙인 X커트부의 대부분에 박리가 있음.X: The transfer sheet was cured at room temperature for 1 week, and then the test was carried out. Most of the X-cut portions with the tape were peeled off.

(d) 내약품성 : JIS　K　6902 : 1998의 내오염성에 준거하여, 각종 약품의 내성을 육안으로 관찰한다. 오염 물질의 접촉 시간은 16~24시간. 내약품성의 평가 기준은 이하와 같이 하였다.(d) Chemical resistance: According to the stain resistance of JIS K 6902: 1998, the resistance of various chemicals is visually observed. Contact time of pollutant is 16 ~ 24 hours. Evaluation criteria of chemical resistance were as follows.

○ : 도막에 외관 변화 없음.○: No appearance change on the coating film.

△ : 도막에 약간 흔적이 남거나 또는 도막이 변색.△: A little traces were left on the coating film or the coating film discolored.

× : 도막에 현저한 변화가 보여짐.X: Significant change was observed in the coating film.

(e) 표면 저항값 : JIS　K　6911-5-13(1995년판)에 근거하여, 디지털 초고(extra-high)저항/미소 전류계 R8340A((주) 아드반테스트)를 사용하여 측정한다.(e) Surface resistance value: Measured using a digital extra-high resistance / microammeter R8340A (Advan test) according to JIS K 6911-5-13 (1995 edition).

각 시험의 평가 결과를, 상기 표 1~표 3에 나타낸다. 표 1~표 3으로부터 분명한 바와 같이, 각 실시예의 화장판은, 비교예의 화장판에 비해, 자외선 경화형 수지 조성물로 이루어지는 층(전사층)의 밀착성, 내약품성의 점에서 현저하게 우수하였다.The evaluation results of the respective tests are shown in Tables 1 to 3 above. As is clear from Tables 1 to 3, the colored plates of the respective Examples were remarkably superior in terms of adhesion and chemical resistance of the layer (transfer layer) comprising the ultraviolet-curable resin composition as compared with the colored plates of the comparative examples.

1 : 박리성 기재
2 : 자외선 경화형 수지 조성물
2a : 자외선 경화형 수지 조성물의 경화물
3 : 전사 시트
6 : 수지 함침 화장지
6a : 경화한 수지 함침 화장지
7 : 수지 함침 코어지
7a : 경화한 수지 함침 코어지
9 : 내약품성 화장판1: peelable substrate
2: UV curable resin composition
2a: Curing of UV curable resin composition
3: transfer sheet
6: resin impregnated toilet paper
6a: Cured resin impregnated toilet paper
7: Resin impregnated core paper
7a: Cured resin impregnated core paper
9: Chemical resistance veneer

Claims (5)

(A) 라디칼 반응성기를 2개 포함한 우레탄 아크릴레이트 수지(urethane acrylate resin) 또는 아크릴 수지(acrylic resin)와,
(B) 라디칼 반응성기를 6개 이상 포함한 우레탄 아크릴레이트 수지 또는 아크릴 수지를 포함하며,
상기 (A) 성분과 상기 (B) 성분의 합계량을 100중량부로 했을 때, 상기 (A) 성분의 양이 30~70중량부인 것을 특징으로 하는 활성 에너지선 경화형 수지 조성물.(A) a urethane acrylate resin or an acrylic resin containing two radical reactive groups,
(B) a urethane acrylate resin or an acrylic resin containing at least six radical reactive groups,
Wherein the amount of the component (A) is 30 to 70 parts by weight based on 100 parts by weight of the total amount of the component (A) and the component (B). 제 1 항에 있어서,
도전성 졸(sol)을 더 포함한, 활성 에너지선 경화형 수지 조성물.The method according to claim 1,
The active energy ray-curable resin composition further comprising a conductive sol (sol). 박리성 기재(基材)와,
상기 박리성 기재에 형성된, 제 1 항 또는 제 2 항에 기재된 활성 에너지선 경화형 수지 조성물로 이루어지는 층을 구비한, 전사 시트.A peelable base material,
A transfer sheet comprising a layer made of the active energy ray-curable resin composition according to any one of claims 1 to 3 formed on the releasable substrate. 멜라민 수지층과,
상기 멜라민 수지층 위에 형성된, 제 1 항 또는 제 2 항에 기재된 활성 에너지선 경화형 수지 조성물의 경화물로 이루어지는 층을 구비한, 화장판.A melamine resin layer,
And a layer comprising a cured product of the active energy ray-curable resin composition according to any one of claims 1 to 3 formed on the melamine resin layer. 코어재(core material)와, 화장지에 열경화성 수지를 주(主)성분으로 하는 수지액을 함침(含浸)하며, 건조하여 이루어진 수지 함침 화장지와, 제 3 항에 기재된 전사 시트를 적층하고, 열압(熱壓) 성형하며, 상기 열압 성형 후, 상기 박리성 기재를 제거하는 것을 특징으로 하는 화장판의 제조 방법.A resin impregnated toilet paper made by impregnating (impregnating) a core material, a resin solution containing a thermosetting resin as a main component to a toilet paper, and drying, and a transfer sheet as described in claim 3 are laminated, And the peelable base material is removed after the hot-pressing.
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