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JP2011094132A - Active energy ray-curable resin composition for decorative board, transfer sheet, decorative board, and method for producing decorative board - Google Patents

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

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JP2011094132A
JP2011094132A JP2010220110A JP2010220110A JP2011094132A JP 2011094132 A JP2011094132 A JP 2011094132A JP 2010220110 A JP2010220110 A JP 2010220110A JP 2010220110 A JP2010220110 A JP 2010220110A JP 2011094132 A JP2011094132 A JP 2011094132A
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decorative board
component
active energy
weight
energy ray
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Hiroyuki Doi
裕之 土井
Kotaro Kodera
恒太郎 小寺
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Aica Kogyo Co Ltd
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Aica Kogyo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • 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
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising 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
    • 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
    • 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
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/10—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
    • 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
    • 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
    • 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
    • B32—LAYERED PRODUCTS
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2451/00—Decorative or ornamental articles

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Optics & Photonics (AREA)
  • Fluid Mechanics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition capable of surely tightly abutting a cured product of an active energy ray-curable resin composition onto a melamine resin layer while not always using a primer or an adhesive; and to provide a transfer sheet, a decorative board, and a method for producing the decorative board. <P>SOLUTION: The active energy ray-curable resin composition includes: (A) an urethane acrylate resin or acrylic resin having two radical reactive groups; and (B) an urethane acrylate resin or acrylic resin having six or more radical reactive groups. The amount of the component (A) is 30-70 pts.wt. when the total amount of the component (A) and the component (B) is 100 pts.wt. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、例えば、化粧板用途に供される活性エネルギー線硬化型樹脂組成物、転写シート、化粧板、及びその製造方法に関する。   The present invention relates to an active energy ray-curable resin composition, a transfer sheet, a decorative board, and a method for producing the same, which are used for decorative board applications, for example.

従来、化粧板表面の耐擦傷性、耐薬品性、耐汚染性、耐候性を向上させる手段としては、活性エネルギー線硬化型樹脂や熱硬化型樹脂を含む塗液を化粧板の表面に塗布して硬化せしめる方法、それらの樹脂を含む塗液を剥離性のある基材に塗布し硬化して、転写シートとした後、転写シートの硬化塗膜を化粧板に重ねて、加熱加圧等により、その化粧板表面に硬化塗膜を転写する方法、基材上に設けた塗膜を半硬化の状態にして転写シートとし、転写シートの半硬化状態の塗膜を化粧板表面に転写後に、再度、硬化処理を行い、化粧板表面に上記耐性を有する塗膜を設ける方法が知られている。特に、活性エネルギー線により硬化した塗膜は、優れた塗膜特性（耐擦傷性、耐汚染性等）を有するため、塗膜を化粧板表面に設ける方法については、種々提案されている（特許文献１〜２参照）。   Conventionally, as a means for improving the scratch resistance, chemical resistance, stain resistance and weather resistance of the decorative board surface, a coating liquid containing an active energy ray-curable resin or a thermosetting resin is applied to the surface of the decorative board. After the coating liquid containing these resins is applied to a peelable substrate and cured to form a transfer sheet, the cured coating film of the transfer sheet is layered on a decorative board, and heated and pressed. , A method of transferring the cured coating film to the decorative board surface, a coating sheet provided on the substrate in a semi-cured state as a transfer sheet, and after transferring the semi-cured coating film of the transfer sheet to the decorative board surface, A method is known in which a curing treatment is performed again and a coating film having the above-mentioned resistance is provided on the decorative board surface. In particular, since a coating film cured by active energy rays has excellent coating properties (scratch resistance, stain resistance, etc.), various methods for providing a coating film on a decorative board surface have been proposed (patents). References 1-2).

特開２００３−１３７９４２号公報JP 2003-137842 A 特開２００３−１８３３３９号公報JP 2003-183339 A

しかしながら、一般的に上記耐性を有するような塗膜は、分子中に多くの反応性官能基を有する材料を架橋させてなるものであって、高い架橋密度を有する場合が多く、その塗膜を直接化粧板に密着させようとした場合、塗膜の緻密さ、硬化収縮等により、化粧板の表面への密着性が著しく劣る場合が多い。また、転写シートを用いる場合には、転写シートの塗膜側、或いは、化粧板側にプライマー層や接着剤層などを設けて、密着性を確保しているのが現状である。   However, in general, the coating film having the above-mentioned resistance is formed by crosslinking a material having many reactive functional groups in the molecule, and often has a high crosslinking density. When trying to adhere directly to the decorative board, the adhesion to the surface of the decorative board is often extremely poor due to the denseness of the coating film, curing shrinkage, and the like. In addition, when a transfer sheet is used, a primer layer or an adhesive layer is provided on the coating film side or the decorative plate side of the transfer sheet to ensure adhesion.

本発明は、プライマーや接着剤を必ずしも用いることなく、メラミン樹脂層等の上に活性エネルギー線硬化性樹脂組成物の硬化物を確実に密着させることができる活性エネルギー線硬化型樹脂組成物、転写シート、化粧板、及び化粧板の製造方法を提供することを目的とする。   The present invention relates to an active energy ray-curable resin composition that can reliably adhere 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, transfer It aims at providing the manufacturing method of a sheet | seat, a decorative board, and a decorative board.

本発明の活性エネルギー線硬化型樹脂組成物は、（Ａ）ラジカル反応性基を２つ含むウレタンアクリレート樹脂又はアクリル樹脂と、（Ｂ）ラジカル反応性基を６つ以上含むウレタンアクリレート樹脂又はアクリル樹脂と、を含み、前記（Ａ）成分と前記（Ｂ）成分との合計量を１００重量部としたとき、前記（Ａ）成分の量が３０〜７０重量部であることを特徴とする。   The active energy ray-curable resin composition of the present invention includes (A) a urethane acrylate resin or acrylic resin containing two radical reactive groups, and (B) a urethane acrylate resin or acrylic resin containing six or more radical reactive groups. And when the total amount of the component (A) and the component (B) is 100 parts by weight, the amount of the component (A) is 30 to 70 parts by weight.

本発明の活性エネルギー線硬化型樹脂組成物を用いることにより、例えば、転写シートの塗膜側、或いは、化粧板側にプライマー処理を施さなくても、活性エネルギー線硬化型樹脂組成物から成る層（硬化物）の密着性、耐擦傷性、耐薬品性に優れる化粧板を得ることができる。   By using the active energy ray-curable resin composition of the present invention, for example, a layer made of an active energy ray-curable resin composition without applying primer treatment to the coating film side or decorative plate side of the transfer sheet. A decorative board having excellent (cured) adhesion, scratch resistance, and chemical resistance can be obtained.

本発明の活性エネルギー線硬化型樹脂組成物は、更に導電性ゾルを含むことが好ましい。
本発明の転写シートは、剥離性基材と、前記剥離性基材に形成された、上述した活性エネルギー線硬化型樹脂組成物から成る層と、を備える。 The active energy ray-curable resin composition of the present invention preferably further contains a conductive sol.
The transfer sheet of the present invention includes a peelable substrate and a layer formed of the above-described active energy ray-curable resin composition formed on the peelable substrate.

本発明の化粧板は、メラミン樹脂層と、前記メラミン樹脂層の上に形成された、上述した活性エネルギー線硬化型樹脂組成物の硬化物から成る層と、を備える。
本発明の化粧板の製造方法は、コア材と、化粧紙に熱硬化性樹脂を主成分とする樹脂液を含浸し、乾燥して成る樹脂含浸化粧紙と、上述した転写シートとを積層し、熱圧成形し、前記熱圧成形後、前記剥離性基材を除去する。 The decorative board of the present invention includes a melamine resin layer and a layer formed on the melamine resin layer and made of a cured product of the above-described active energy ray-curable resin composition.
The method for producing a decorative board of the present invention comprises laminating a core material, a resin-impregnated decorative paper obtained by impregnating a decorative paper with a resin liquid containing a thermosetting resin as a main component, and drying, and the transfer sheet described above. Then, after hot pressing, the peelable substrate is removed.

図１は本発明の耐薬品性化粧板を得るために材料を積層する際の構成断面図である。FIG. 1 is a cross-sectional view showing a structure when materials are laminated to obtain a chemical-resistant decorative board of the present invention. 図２は本発明の耐薬品性化粧板の構成断面図である。FIG. 2 is a sectional view of the chemical resistant decorative board of the present invention.

以下、本発明について詳細に説明する。本発明で用いる（Ａ）成分のうち、ラジカル反応性基を２つ含むウレタンアクリレート樹脂は、例えば、ポリオールとジイソシアネートとを反応させて得られるイソシアネート化合物とヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、ヒドロキシブチルアクリレートなどの水酸基を有するアクリレートモノマーとの反応生成物である。（Ａ）成分の重量平均分子量は、５００〜１５００が好ましい。   Hereinafter, the present invention will be described in detail. Among the component (A) used in the present invention, the urethane acrylate resin containing two radical-reactive groups is, for example, an isocyanate compound obtained by reacting a polyol with diisocyanate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate. It is a reaction product with an acrylate monomer having a hydroxyl group. (A) As for the weight average molecular weight of a component, 500-1500 are preferable.

また、本発明で用いる（Ａ）成分のうち、ラジカル反応性基を２つ含むアクリル樹脂としては、例えば、アクリル酸、メタクリル酸またはこれらの誘導体の重合体からなるもので、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル等のアクリル酸エステル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル等のメタクリル酸エステルを主成分とした重合体が挙げられる。   In addition, among the component (A) used in the present invention, the acrylic resin containing two radical reactive groups is, for example, made of a polymer of acrylic acid, methacrylic acid or a derivative thereof, for example, methyl acrylate. And polymers mainly composed of acrylic acid esters such as ethyl acrylate and butyl acrylate, and methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate.

本発明で用いる（Ｂ）成分のうち、ラジカル反応性基を６つ以上含むウレタンアクリレート樹脂は、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオールなどのポリオールとジイソシアネートとを反応させて得られるイソシアネート化合物と、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールトリアクリレート等の水酸基を有するアクリレートモノマーとの反応生成物である。（Ｂ）成分の重量平均分子量は５００〜６０００が好ましい。   Of the component (B) used in the present invention, the urethane acrylate resin containing 6 or more radical-reactive groups is, for example, an isocyanate compound obtained by reacting a polyol such as polyester polyol, polyether polyol or polycarbonate polyol with diisocyanate. And a reaction product of an acrylate monomer having a hydroxyl group such as trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate and the like. (B) As for the weight average molecular weight of a component, 500-6000 are preferable.

また、本発明で用いる（Ｂ）成分のうち、ラジカル反応性基を６つ以上含むアクリル樹脂としては、例えば、アクリル酸、メタクリル酸またはこれらの誘導体の重合体からなるもので、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル等のアクリル酸エステル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル等のメタクリル酸エステルを主成分とした重合体が挙げられる。   In addition, among the component (B) used in the present invention, the acrylic resin containing six or more radical-reactive groups is made of, for example, acrylic acid, methacrylic acid or a polymer of these derivatives. For example, acrylic acid Examples thereof include polymers mainly composed of acrylic esters such as methyl, ethyl acrylate and butyl acrylate, and methacrylic esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate.

（Ａ）成分と（Ｂ）成分の配合割合は７０：３０〜３０：７０重量部（固形分比）とするのが好ましく、（Ｂ）成分が下限に満たないと、活性エネルギー線硬化型樹脂組成物から成る層の密着性、耐薬品性に劣りやすく、上限を超えると密着性に劣りやすくなる。   The mixing ratio of the component (A) and the component (B) is preferably 70:30 to 30:70 parts by weight (solid content ratio). If the component (B) is less than the lower limit, the active energy ray-curable resin is used. The adhesion and chemical resistance of the layer made of the composition are likely to be inferior, and the adhesion is liable to be inferior when the upper limit is exceeded.

活性エネルギー線硬化型樹脂組成物の全固形分に対する、（Ａ）成分と（Ｂ）成分の合計量の比率（重量比）は、９０〜１００％の範囲が好ましい。
本発明の活性エネルギー線硬化型樹脂組成物には、（Ａ）成分と（Ｂ）成分以外に、導電性ゾルを配合することが好ましい。導電性ゾルは、化粧板を製造する際、剥離性基材に活性エネルギー線硬化型樹脂組成物が塗布された転写シートの帯電防止に効果があり、転写シートの取り扱い中に静電気の発生によるゴミの付着を防止することができる。とりわけアンチモン系の導電性ゾルが好ましく、導電性ゾルの使用量は、（Ａ）成分と（Ｂ）成分との合計１００重量部に対して８〜１５重量部の範囲が好ましい。１５重量部を超えると着色及び耐薬品性能が劣りやすく、８重量部よりも少ないと十分な帯電防止効果が得られないことがある。 The ratio (weight ratio) of the total amount of component (A) and component (B) to the total solid content of the active energy ray-curable resin composition is preferably in the range of 90 to 100%.
In addition to the components (A) and (B), the active energy ray-curable resin composition of the present invention preferably contains a conductive sol. The conductive sol is effective in preventing charging of a transfer sheet in which an active energy ray-curable resin composition is applied to a peelable substrate when manufacturing a decorative board, and dust generated by the generation of static electricity during handling of the transfer sheet. Can be prevented. In particular, an antimony-based conductive sol is preferable, and the amount of the conductive sol used is preferably in the range of 8 to 15 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (B). If it exceeds 15 parts by weight, the coloring and chemical resistance performance tends to be poor, and if it is less than 8 parts by weight, a sufficient antistatic effect may not be obtained.

アンチモン系の導電性ゾルとしては、市販品として日産化学工業株式会社製のセルナックス（登録商標）シリーズ（アンチモン酸亜鉛系）が挙げられる。水分散ゾルとしてＣＸ−Ｚ３３０Ｈ、ＣＸ−Ｚ３３０Ｈ−Ｆ２や、メタノール分散ゾルとしてＣＸ−Ｚ６４１Ｍ、ＣＸ−Ｚ６０３Ｍ、ＣＸ−Ｚ６０３Ｍ−Ｆ２、ＣＸ−Ｚ６１０Ｍ−Ｆ２、ＣＸ−Ｚ６５３Ｍ−Ｆ、ＣＸ−Ｚ６９３Ｍ−Ｆや、イソプロパノール分散ゾルとしてＣＸ−Ｚ２１０ＩＰ、ＣＸ−Ｚ２１０ＩＰ−Ｆ２（いずれも商品名）があり、（Ａ）成分、（Ｂ）成分の種類、配合割合に応じ、適宜選択して用いることができる。   Examples of the antimony-based conductive sol include a commercially available Cellnax (registered trademark) series (zinc antimonate-based) manufactured by Nissan Chemical Industries, Ltd. CX-Z330H, CX-Z330H-F2 as water dispersion sol, CX-Z641M, CX-Z603M, CX-Z603M-F2, CX-Z610M-F2, CX-Z653M-F, CX-Z693M-F as methanol dispersion sol In addition, there are CX-Z210IP and CX-Z210IP-F2 (both are trade names) as isopropanol dispersion sols, which can be appropriately selected and used according to the types and blending ratios of the (A) component and (B) component.

また、紫外線照射する場合、本発明の活性エネルギー線硬化型樹脂組成物には、（Ａ）成分と（Ｂ）成分以外に、光開始剤を配合することが好ましい。光開始剤は、例えば、ベンジルケタール、α−ヒドロキシアセトフェノン、α−アミノアセトフェノン、アシルフォスフィンオキサイド、チタノセン系化合物、オキシムエステルなどを用いることができる。市販品としてはＩＲＧＡＣＵＲＥ１８４、３６９、６５１、８１９、ＤＡＲＯＣＵＲ１１７３（チバ・スペシャルティ・ケミカルズ株式会社製、商品名）などが挙げられる。光開始剤の使用量は、（Ａ）成分と（Ｂ）成分との合計１００重量部に対して１〜１０重量部であることが好ましい。１０重量部よりも多いと硬化被膜が着色しやすく、１重量部よりも少ないと十分な硬化が得られないことがある。   Moreover, when irradiating an ultraviolet-ray, it is preferable to mix | blend a photoinitiator with the active energy ray hardening-type resin composition of this invention other than (A) component and (B) component. As the photoinitiator, for example, benzyl ketal, α-hydroxyacetophenone, α-aminoacetophenone, acylphosphine oxide, titanocene compound, oxime ester and the like can be used. Examples of commercially available products include IRGACURE 184, 369, 651, 819, DAROCUR 1173 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), and the like. It is preferable that the usage-amount of a photoinitiator is 1-10 weight part with respect to a total of 100 weight part of (A) component and (B) component. When the amount is more than 10 parts by weight, the cured film tends to be colored, and when it is less than 1 part by weight, sufficient curing may not be obtained.

本発明の転写シートにおいて用いられる（例えば、活性エネルギー線硬化型樹脂組成物が塗布される）剥離性基材は、樹脂含浸化粧紙の表面に活性エネルギー線硬化型樹脂組成物が熱圧成形により転写された後、剥離可能なものであればよく、ポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレンビニルアルコールフィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルフォンフィルム、ポリエーテルケトンフィルム、ポリエーテルスルフォンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッ素樹脂フィルム、ナイロンフィルム、アクリルフィルム等のプラスチックフィルム、アルミニウム箔、ステンレス箔、銅箔などの金属箔を使用することができる。   The releasable substrate used in the transfer sheet of the present invention (for example, to which the active energy ray curable resin composition is applied) is formed on the surface of the resin-impregnated decorative paper by hot pressing the active energy ray curable resin composition. Any film that can be peeled after being transferred, such as polyester film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, Polyvinyl alcohol film, ethylene vinyl alcohol film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ketone film, polyether sulfone film Lum, polyetherimide film, a polyimide film, fluororesin film, nylon film, it is possible to use plastic films, aluminum foil, such as an acrylic film, a stainless steel foil, a metal foil such as copper foil.

前記剥離性基材の表面に前記の活性エネルギー線硬化型樹脂組成物を塗布する場合は公知の方法、例えば、スプレーコート法、グラビアコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、カーテンコート法などを用いることができる。乾燥後の塗膜の厚みは１〜１００μｍ程度であることが好ましい。   When the active energy ray-curable resin composition is applied to the surface of the peelable substrate, a known method such as spray coating, gravure coating, bar coating, knife coating, roll coating, blade A coating method, a die coating method, a curtain coating method, or the like can be used. The thickness of the coating after drying is preferably about 1 to 100 μm.

剥離性基材の表面に活性エネルギー線硬化型樹脂組成物を塗布した後には、例えば、電子線、紫外線を照射することができる。紫外線を照射する場合は、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク、メタルハライドランプ等を用い、１００〜４００ｎｍ、好ましくは２００〜４００ｎｍの波長領域で、１００〜８００ｍＪ／ｃｍ２のエネルギーを有する紫外線を照射することが好ましい。この条件であると熱圧成形時に樹脂含浸化粧紙との密着が強固なものとなる。また、必要に応じて窒素雰囲気下にて硬化してもよい。 After apply | coating the active energy ray curable resin composition to the surface of a peelable base material, an electron beam and an ultraviolet-ray can be irradiated, for example. When irradiating with ultraviolet rays, use an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp, etc., and have an energy of 100 to 800 mJ / cm 2 in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm. It is preferable to irradiate with ultraviolet rays. Under these conditions, the adhesion with the resin-impregnated decorative paper becomes strong during hot pressing. Moreover, you may harden | cure in nitrogen atmosphere as needed.

本発明の化粧版において用いられる樹脂含浸化粧紙としては、通常公知の化粧板用の化粧紙に熱硬化性樹脂、とりわけ耐熱性、耐摩耗性に優れるメラミン−ホルムアルデヒド樹脂を主な成分とする樹脂液を化粧紙に含浸し、乾燥したものが好適に用いられる。   As the resin-impregnated decorative paper used in the decorative plate of the present invention, a resin mainly composed of a thermosetting resin, particularly a melamine-formaldehyde resin excellent in heat resistance and abrasion resistance, for a well-known decorative paper for a decorative board. A liquid obtained by impregnating the liquid into a decorative paper and drying it is preferably used.

コア材には、化粧板用のクラフト紙、不織布、クロスなどに熱硬化性樹脂を含浸処理した樹脂含浸コア紙や、合板、ＭＤＦ（Medium Density Fiberboard：中密度繊維板）、パーティクルボードなどの木質系基材が用いられ、適宜用途、要求される品質により選択される。   Core materials include decorative paper kraft paper, non-woven fabric, cloth-impregnated core paper impregnated with thermosetting resin, plywood, MDF (Medium Density Fiberboard), particleboard, etc. A base material is used and is appropriately selected depending on the intended use and required quality.

（Ａ）ラジカル反応性基を２つ含むウレタンアクリレート樹脂である、ＵＮ−２３０１（商品名アートレジン、根上工業株式会社製、重量平均分子量７４０）７０重量部、（Ｂ）ラジカル反応性基を１０含むウレタンアクリレート樹脂である、ＵＮ−９０４（商品名アートレジン、根上工業株式会社製、重量平均分子量４９００）３０重量部、及び光開始剤であるＩＲＧＡＣＵＲＥ１８４（チバ・スペシャルティ・ケミカルズ株式会社製、商品名）３重量部をメチルエチルケトン４０重量部で希釈して紫外線硬化型樹脂組成物（活性エネルギー線硬化型樹脂組成物）を得た。   (A) A urethane acrylate resin containing two radical-reactive groups, UN-2301 (trade name Art Resin, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight 740), 70 parts by weight, (B) 10 radical-reactive groups 30 parts by weight of UN-904 (trade name Art Resin, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight 4900), which is a urethane acrylate resin, and IRGACURE 184 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), which is a photoinitiator. 3 parts by weight were diluted with 40 parts by weight of methyl ethyl ketone to obtain an ultraviolet curable resin composition (active energy ray curable resin composition).

次いで、厚み８０μｍのＯＰＰ（Oriented Polypropylene：延伸ポリプロピレン）フィルムに乾燥膜厚が３０μｍとなるように前記の紫外線硬化型樹脂組成物を塗布し、高圧水銀灯で照射強度が４００ｍＪ／ｃｍ２となるように紫外線を照射して転写シートを得、この転写シートを１週間養生した。この転写シート３は、図１に示すように、ＯＰＰフィルム（剥離性基材）１と、そのＯＰＰフィルム１に形成された、紫外線硬化型樹脂組成物から成る層２と、を備えるものである。 Next, the UV curable resin composition is applied to an 80 μm thick OPP (Oriented Polypropylene) film so that the dry film thickness is 30 μm, and the irradiation intensity is 400 mJ / cm 2 with a high-pressure mercury lamp. The transfer sheet was obtained by irradiating ultraviolet rays, and the transfer sheet was cured for one week. As shown in FIG. 1, the transfer sheet 3 includes an OPP film (peelable substrate) 1 and a layer 2 made of an ultraviolet curable resin composition and formed on the OPP film 1. .

坪量１００ｇ／ｍ２の印刷紙にメラミン−ホルムアルデヒド樹脂を主な成分とする樹脂液を含浸し、乾燥してメラミン樹脂含浸化粧紙を得た。
坪量１８５ｇ／ｍ２のクラフト紙にフェノール−ホルムアルデヒド樹脂を主な成分とする樹脂液を含浸し、乾燥してフェノール樹脂含浸コア紙を得た。 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 melamine resin-impregnated decorative paper.
Kraft paper having a basis weight of 185 g / m 2 was impregnated with a resin liquid containing phenol-formaldehyde resin as a main component and dried to obtain a phenol resin-impregnated core paper.

図１に示すように、下から順に、フェノール樹脂含浸コア紙７を５枚、メラミン樹脂含浸化粧紙６を１枚、転写シート３を１枚積層し、温度１３２℃、圧力７０ｋｇ／ｃｍ２の条件で熱圧成形し、成形後ＯＰＰ（Oriented Polypropylene：延伸ポリプロピレン）フィルムを除去して、図２に示すような、耐薬品性化粧板９を得た。耐薬品性化粧板９において、７ａは硬化した樹脂含浸コア紙であり、６ａは硬化した樹脂含浸化粧紙であり、２ａは紫外線硬化型樹脂組成物の硬化物である。 As shown in FIG. 1, in order from the bottom, five sheets of phenol resin-impregnated core paper 7, one sheet of melamine resin-impregnated decorative paper 6, and one sheet of transfer sheet 3 are laminated, and the temperature is 132 ° C. and the pressure is 70 kg / cm 2 . The film was hot-pressed under the conditions, and after molding, the OPP (Oriented Polypropylene: stretched polypropylene) film was removed to obtain a chemical-resistant decorative board 9 as shown in FIG. In the chemical resistant decorative board 9, 7a is a cured resin-impregnated core paper, 6a is a cured resin-impregnated decorative paper, and 2a is a cured product of an ultraviolet curable resin composition.

（Ａ）成分としてライトアクリレート１，６ＨＸ−Ａ（共栄社化学株式会社製、分子量２２６）７０重量部を用い、（Ｂ）成分としてＫＡＹＡＲＡＤＤＰＨＡ（日本化薬株式会社製、分子量８７８）３０重量部を用いた点以外は前記実施例１と同様に実施した。   70 parts by weight of light acrylate 1,6HX-A (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight 226) is used as the component (A), and 30 parts by weight of KAYARDDPHA (manufactured by Nippon Kayaku Co., Ltd., molecular weight 878) is used as the component (B). The same operation as in Example 1 was performed except for the points described above.

ここで、ライトアクリレート１，６ＨＸ−Ａは、ラジカル反応性基を２つ含むアクリル樹脂である。また、ＫＡＹＡＲＡＤＤＰＨＡは、ラジカル反応性基を６つ含むアクリル樹脂である。   Here, the light acrylate 1,6HX-A is an acrylic resin containing two radical reactive groups. KAYARDADDHA is an acrylic resin containing six radical reactive groups.

（Ａ）成分の配合量を５０重量部とし、（Ｂ）成分の配合量を５０重量部とした点以外は前記実施例１と同様に実施した。   The same procedure as in Example 1 was performed except that the amount of component (A) was 50 parts by weight and the amount of component (B) was 50 parts by weight.

（Ａ）成分としてライトアクリレート１，６ＨＸ−Ａ（共栄社化学株式会社製、分子量２２６）５０重量部を用い、（Ｂ）成分としてＫＡＹＡＲＡＤＤＰＨＡ（日本化薬株式会社製、分子量８７８）５０重量部を用いた点以外は前記実施例１と同様に実施した。   (A) 50 parts by weight of light acrylate 1,6HX-A (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight 226) is used as component (A), and 50 parts by weight of KAYARDADDHA (manufactured by Nippon Kayaku Co., Ltd., molecular weight 878) is used as component (B). The same operation as in Example 1 was performed except for the points described above.

（Ａ）成分の配合量を３０重量部とし、（Ｂ）成分の配合量を７０重量部とした点以外は前記実施例１と同様に実施した。   The same procedure as in Example 1 was performed except that the amount of component (A) was 30 parts by weight and the amount of component (B) was 70 parts by weight.

（Ａ）ラジカル反応性基を２つ含むウレタンアクリレート樹脂である、ＵＮ−２３０１（商品名アートレジン、根上工業株式会社製）７０重量部、（Ｂ）ラジカル反応性基を１０含むウレタンアクリレート樹脂である、ＵＮ−９０４（商品名アートレジン、根上工業株式会社製）３０重量部、光開始剤であるＩＲＧＡＣＵＲＥ１８４（チバ・スペシャルティ・ケミカルズ株式会社製、商品名）５重量部、光開始剤であるＩＲＧＡＣＵＲＥ８１９（チバ・スペシャルティ・ケミカルズ株式会社製、商品名）１重量部、及び導電性ゾルであるアンチモン酸亜鉛のイソプロパノール分散ゾル（セルナックスＣＸ−Ｚ２１０ＩＰ−Ｆ２、ＺｎＳｂ２Ｏ６：２０％、日産化学工業株式会社製、商品名)１２．５重量部を、４−メチル−２−ペンタノン４０重量部で希釈して紫外線硬化型樹脂組成物を得た。 (A) urethane acrylate resin containing 2 radical reactive groups, UN-2301 (trade name Art Resin, manufactured by Negami Kogyo Co., Ltd.) 70 parts by weight, (B) urethane acrylate resin containing 10 radical reactive groups There are 30 parts by weight of UN-904 (trade name Art Resin, manufactured by Negami Kogyo Co., Ltd.), 5 parts by weight of IRGACURE 184 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRGACURE 819, which is a photoinitiator. (Product name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1 part by weight, and an isopropanol dispersion sol of zinc antimonate, which is a conductive sol (Selnax CX-Z210IP-F2, ZnSb 2 O 6 : 20%, Nissan Chemical Industries Product name) 12.5 parts by weight of 4-methyl-2-pentanone Diluted with 0 parts by weight to obtain an ultraviolet-curable resin composition.

次いで、厚み８０μｍのＯＰＰ（Oriented Polypropylene：延伸ポリプロピレン）フィルムに乾燥膜厚が３０μｍとなるように前記の紫外線硬化型樹脂組成物を塗布し、高圧水銀灯で照射強度が４００ｍＪ／ｃｍ２となるように紫外線を照射して転写シートを得、この転写シートを１週間養生した。 Next, the UV curable resin composition is applied to an 80 μm thick OPP (Oriented Polypropylene) film so that the dry film thickness is 30 μm, and the irradiation intensity is 400 mJ / cm 2 with a high-pressure mercury lamp. The transfer sheet was obtained by irradiating ultraviolet rays, and the transfer sheet was cured for one week.

坪量１００ｇ／ｍ２の印刷紙にメラミン−ホルムアルデヒド樹脂を主な成分とする樹脂液を含浸し、乾燥してメラミン樹脂含浸化粧紙を得た。
坪量１８５ｇ／ｍ２のクラフト紙にフェノール−ホルムアルデヒド樹脂を主な成分とする樹脂液を含浸し、乾燥してフェノール樹脂含浸コア紙を得た。 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 melamine resin-impregnated decorative paper.
Kraft paper having a basis weight of 185 g / m 2 was impregnated with a resin liquid containing phenol-formaldehyde resin as a main component and dried to obtain a phenol resin-impregnated core paper.

下から順に、フェノール樹脂含浸コア紙を５枚、メラミン樹脂含浸化粧紙を１枚、転写シートを１枚積層し、温度１３２℃、圧力７０ｋｇ／ｃｍ２の条件で熱圧成形し、成形後ＯＰＰ（Oriented Polypropylene：延伸ポリプロピレン）フィルムを除去して耐薬品性化粧板を得た。 In order from the bottom, 5 sheets of core paper impregnated with phenol resin, 1 sheet of decorative paper impregnated with melamine resin, and 1 sheet of transfer sheet are laminated and thermo-press molded under the conditions of a temperature of 132 ° C. and a pressure of 70 kg / cm 2. The (Oriented Polypropylene: stretched polypropylene) film was removed to obtain a chemically resistant decorative board.

（Ａ）成分としてライトアクリレート１，６ＨＸ−Ａ（共栄社化学株式会社製、分子量２２６）７０重量部を用い、（Ｂ）成分としてＫＡＹＡＲＡＤＤＰＨＡ（日本化薬株式会社製、分子量８７８）３０重量部を用いる点以外は前記実施例６と同様に実施した。   70 parts by weight of light acrylate 1,6HX-A (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight 226) is used as the component (A), and 30 parts by weight of KAYARDDPHA (manufactured by Nippon Kayaku Co., Ltd., molecular weight 878) is used as the component (B). Except for the points, the same procedure as in Example 6 was performed.

（Ａ）成分の配合量を５０重量部とし、（Ｂ）成分の配料を５０重量部とした点以外は前記実施例６と同様に実施した。   The same procedure as in Example 6 was performed except that the amount of component (A) was 50 parts by weight and the amount of component (B) was 50 parts by weight.

（Ａ）成分としてライトアクリレート１，６ＨＸ−Ａ（共栄社化学株式会社製、分子量２２６）５０重量部を用い、（Ｂ）成分としてＫＡＹＡＲＡＤＤＰＨＡ（日本化薬株式会社製、分子量８７８）５０重量部を用いた点以外は前記実施例６と同様に実施した。   (A) 50 parts by weight of light acrylate 1,6HX-A (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight 226) is used as component (A), and 50 parts by weight of KAYARDADDHA (manufactured by Nippon Kayaku Co., Ltd., molecular weight 878) is used as component (B). The same operation as in Example 6 was performed except for the points described above.

（Ａ）成分の配合量を３０重量部とし、（Ｂ）成分の配合量を７０重量部とした点以外は前記実施例６と同様に実施した。   The same procedure as in Example 6 was performed except that the amount of component (A) was 30 parts by weight and the amount of component (B) was 70 parts by weight.

ＣＸ−Ｚ２１０ＩＰ−Ｆ２の配合量を１０重量部とした点以外は前記実施例８と同様に実施した。   It implemented similarly to the said Example 8 except the point which made the compounding quantity of CX-Z210IP-F2 into 10 weight part.

ＣＸ−Ｚ２１０ＩＰ−Ｆ２の配合量を１５重量部とした点以外は前記実施例８と同様に実施した。
比較例１
（Ａ）成分の配合量を０重量部とし（配合せず）、（Ｂ）成分の配合量を１００重量部とした点以外は前記実施例１と同様に実施した。 It implemented similarly to the said Example 8 except the point which made the compounding quantity of CX-Z210IP-F2 into 15 weight part.
Comparative Example 1
The same procedure as in Example 1 was performed except that the blending amount of the component (A) was 0 part by weight (not blended) and the blending amount of the component (B) was 100 parts by weight.

比較例２
（Ａ）成分の配合量を１０重量部とし、（Ｂ）成分の配合量を９０重量部とした点以外は前記実施例１と同様に実施した。 Comparative Example 2
The same procedure as in Example 1 was performed except that the amount of component (A) was 10 parts by weight and the amount of component (B) was 90 parts by weight.

比較例３
（Ａ）成分の配合量を２０重量部とし、（Ｂ）成分の配合量を８０重量部とした点以外は前記実施例１と同様に実施した。 Comparative Example 3
The same procedure as in Example 1 was performed except that the amount of component (A) was 20 parts by weight and the amount of component (B) was 80 parts by weight.

比較例４
（Ａ）成分の配合量を８０重量部とし、（Ｂ）成分の配合量を２０重量部とした点以外は前記実施例１と同様に実施した。 Comparative Example 4
The same procedure as in Example 1 was performed except that the amount of component (A) was 80 parts by weight and the amount of component (B) was 20 parts by weight.

比較例５
（Ａ）成分の配合量を９０重量部とし、（Ｂ）成分の配合量を１０重量部とした点以外は前記実施例１と同様に実施した。 Comparative Example 5
The same procedure as in Example 1 was performed except that the amount of component (A) was 90 parts by weight and the amount of component (B) was 10 parts by weight.

比較例６
（Ａ）成分の配合量を１００重量部とし、（Ｂ）成分の配合量を０重量部とした（配合しなかった）点以外は前記実施例１と同様に実施した。 Comparative Example 6
It was carried out in the same manner as in Example 1 except that the amount of component (A) was 100 parts by weight and the amount of component (B) was 0 parts by weight (not blended).

各実施例及び比較例の組成を表１〜表３に示す。   Tables 1 to 3 show the compositions of the examples and comparative examples.

Figure 2011094132
Figure 2011094132

Figure 2011094132
Figure 2011094132

Figure 2011094132
Figure 2011094132

次に、各実施例及び比較例の化粧版を試験した。試験方法は以下の通りとした。以下の（ａ）〜（ｃ）の試験は、いずれも、紫外線硬化型樹脂組成物から成る層（転写層）の密着性を評価する試験である。
（ａ）クロスカット：化粧板の表面にカッターナイフにてクロスカットを入れ、セロハンテープを一旦貼付してから剥離した後、転写層の剥離状態を目視判定する。（ＪＩＳＫ５４００塗料一般試験法 Ｘカットテープ法準拠）。クロスカット試験の評価基準は以下のとおりとした。 Next, decorative plates of each example and comparative example were tested. The test method was as follows. The following tests (a) to (c) are all tests for evaluating the adhesion of a layer (transfer layer) made of an ultraviolet curable resin composition.
(A) Cross cut: A cross cut is made on the surface of the decorative board with a cutter knife, and after the cellophane tape is applied and peeled off, the peeled state of the transfer layer is visually determined. (JISK5400 paint general test method X cut tape method compliant). The evaluation criteria for the crosscut test were as follows.

○：転写シートを常温で１週間養生して剥離が無い。
×：転写シートを常温で１週間養生してテープを貼ったＸカット部の大部分に剥がれが有る。
（ｂ）碁盤目剥離：碁盤目テープ剥離（ＪＩＳＫ５４００ 碁盤目試験準拠）で評価した。碁盤目剥離の評価基準は以下のとおりとした。
○：転写シートを常温で１週間養生した後に試験して９５／１００以上残る。
×：転写シートを常温で１週間養生した後に試験して８４／１００以下。
（ｃ）耐水密着性：化粧板を沸騰水中で２時間煮沸し、更に１００℃の電気オーブンで２時間乾燥した後、表面にカッターナイフにてクロスカットを入れ、セロハンテープを一旦貼付してから剥離した後、転写層の剥離状態を目視判定する（ＪＩＳＫ５４００塗料一般試験法 Ｘカットテープ法準拠）。耐水密着性の評価基準は以下のとおりとした。 ○: The transfer sheet was cured at room temperature for 1 week and there was no peeling.
X: The transfer sheet was cured at room temperature for 1 week, and most of the X-cut portion where the tape was applied was peeled off.
(B) Cross-cut peeling: The cross-cut tape peel (based on JISK5400 cross-cut test) was evaluated. The evaluation criteria for cross-cut peeling were as follows.
○: The transfer sheet is tested after curing for 1 week at room temperature and remains at 95/100 or more.
X: Tested after curing the transfer sheet at room temperature for 1 week, 84/100 or less.
(C) Water-resistant adhesion: After the decorative board is boiled in boiling water for 2 hours and further dried in an electric oven at 100 ° C. for 2 hours, a crosscut is put on the surface with a cutter knife, and a cellophane tape is once applied. After peeling, the peeled state of the transfer layer is visually determined (based on JISK5400 paint general test method X cut tape method). The evaluation criteria for water-resistant adhesion were as follows.

○：転写シートを常温で１週間養生した後に試験をしても剥離が無い。
×：転写シートを常温で１週間養生した後に試験をしてテープを貼ったＸカット部の大部分に剥がれが有る。
（ｄ）耐薬品性：ＪＩＳ Ｋ ６９０２：１９９８の耐汚染性に準拠して、各種薬品の耐性を目視観察する。汚染物質の接触時間は１６〜２４時間。耐薬品性の評価基準は以下のとおりとした。 ○: No peeling even after testing after curing the transfer sheet at room temperature for 1 week.
X: The transfer sheet was cured at room temperature for 1 week, and then the X-cut portion where the tape was applied after the test was peeled off.
(D) Chemical resistance: According to JIS K 6902: 1998, the resistance of various chemicals is visually observed. Contaminant contact time is 16-24 hours. The evaluation criteria for chemical resistance were as follows.

○：塗膜に外観変化なし。
△：塗膜にやや跡が残るまたは塗膜が変色。
×：塗膜に顕著な変化が見られる。
（ｅ）表面抵抗値：：ＪＩＳ Ｋ ６９１１−５−１３（１９９５年版）に基づき、デジタル超高抵抗／微小電流計Ｒ８３４０Ａ（（株）アドバンテスト）を使用して測定する
各試験の評価結果を、上記表１〜表３に示す。表１〜表３から明らかなように、各実施例の化粧板は、比較例の化粧板に比べて、紫外線硬化型樹脂組成物から成る層（転写層）の密着性、耐薬品性の点で顕著に優れていた。 ○: No change in appearance of coating film.
(Triangle | delta): A trace remains in a coating film or a coating film discolors.
X: A remarkable change is seen in the coating film.
(E) Surface resistance value: Based on JIS K 6911-5-13 (1995 edition), the evaluation result of each test measured using a digital ultrahigh resistance / microammeter R8340A (Advantest Co., Ltd.) Shown in Tables 1 to 3 above. As is clear from Tables 1 to 3, the decorative board of each example is more adhesive and chemical resistant than the decorative decorative board of the comparative example. It was remarkably superior.

１・・・剥離性基材
２・・・紫外線硬化型樹脂組成物
２ａ・・・紫外線硬化型樹脂組成物の硬化物
３・・・転写シート
６・・・樹脂含浸化粧紙
６ａ・・・硬化した樹脂含浸化粧紙
７・・・樹脂含浸コア紙
７ａ・・・硬化した樹脂含浸コア紙
９・・・耐薬品性化粧板

DESCRIPTION OF SYMBOLS 1 ... Releasable base material 2 ... Ultraviolet curable resin composition 2a ... Hardened | cured material of ultraviolet curable resin composition 3 ... Transfer sheet 6 ... Resin impregnated decorative paper 6a ... Curing Resin-impregnated decorative paper 7 ... Resin-impregnated core paper 7a ... Cured resin-impregnated core paper 9 ... Chemical resistant decorative board

Claims (5)

（Ａ）ラジカル反応性基を２つ含むウレタンアクリレート樹脂又はアクリル樹脂と、
（Ｂ）ラジカル反応性基を６つ以上含むウレタンアクリレート樹脂又はアクリル樹脂と、
を含み、
前記（Ａ）成分と前記（Ｂ）成分との合計量を１００重量部としたとき、前記（Ａ）成分の量が３０〜７０重量部であることを特徴とする活性エネルギー線硬化型樹脂組成物。 (A) a urethane acrylate resin or an acrylic resin containing two radical reactive groups;
(B) a urethane acrylate resin or an acrylic resin containing 6 or more radical reactive groups;
Including
The active energy ray-curable resin composition, wherein the amount of the component (A) is 30 to 70 parts by weight when the total amount of the component (A) and the component (B) is 100 parts by weight. object. 更に導電性ゾルを含む請求項１記載の活性エネルギー線硬化型樹脂組成物。   The active energy ray-curable resin composition according to claim 1, further comprising a conductive sol. 剥離性基材と、
前記剥離性基材に形成された、請求項１又は２記載の活性エネルギー線硬化型樹脂組成物から成る層と、を備えた転写シート。 A peelable substrate;
A transfer sheet comprising: an active energy ray-curable resin composition according to claim 1 or 2 formed on the peelable substrate. メラミン樹脂層と、
前記メラミン樹脂層の上に形成された、請求項１又は２記載の活性エネルギー線硬化型樹脂組成物の硬化物から成る層と、を備える化粧板。 A melamine resin layer;
A decorative board comprising: a layer made of a cured product of the active energy ray-curable resin composition according to claim 1 or 2 formed on the melamine resin layer. コア材と、化粧紙に熱硬化性樹脂を主成分とする樹脂液を含浸し、乾燥して成る樹脂含浸化粧紙と、請求項３記載の転写シートとを積層し、熱圧成形し、前記熱圧成形後、前記剥離性基材を除去することを特徴とする化粧板の製造方法。   A core material, a resin-impregnated decorative paper obtained by impregnating a decorative paper with a resin liquid containing a thermosetting resin as a main component and drying, and the transfer sheet according to claim 3 are laminated, hot-press molded, A method for producing a decorative board, comprising removing the peelable substrate after hot pressing.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012137828A1 (en) * 2011-04-04 2012-10-11 株式会社ダイセル Photocurable composition, conductive composite film, and manufacturing method for same
JP2020026466A (en) * 2018-08-10 2020-02-20 東洋インキＳｃホールディングス株式会社 Coating agent for decorative material
JP6826242B1 (en) * 2020-01-09 2021-02-03 アイカ工業株式会社 Melamine decorative board and manufacturing method of melamine decorative board
WO2021075435A1 (en) * 2019-10-16 2021-04-22 凸版印刷株式会社 Transfer sheet and method for producing melamine decorative panel
WO2021140687A1 (en) * 2020-01-09 2021-07-15 アイカ工業株式会社 Melamine decorative board and method for manufacturing melamine decorative board

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114030259A (en) * 2014-01-14 2022-02-11 扎伊罗技术股份公司 Layered building panel for indoor and outdoor use
JP7024309B2 (en) * 2017-10-16 2022-02-24 Dic株式会社 Active energy ray-curable composition and film using it
CN111942052B (en) * 2020-08-26 2022-02-18 东莞光群雷射科技有限公司 Heat transfer printing positioning stained paper and production process and application method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61258742A (en) * 1985-04-25 1986-11-17 山陽国策パルプ株式会社 Method of forming surface protective layer and surface protective layer attached sheet used for said method
JPH06256444A (en) * 1993-03-08 1994-09-13 Toli Corp Ltd Light/radiation-curing resin composition and flooring material coated therewith
JPH0752178A (en) * 1993-08-12 1995-02-28 Toppan Printing Co Ltd Manufacture of thermosetting resin decorative laminate
JPH11105437A (en) * 1997-10-02 1999-04-20 Dainippon Printing Co Ltd Thermal transfer sheet and photographic object
JP2002264288A (en) * 2001-03-14 2002-09-18 Aica Kogyo Co Ltd Transfer sheet, manufacturing method therefor, and manufacturing method for decorative sheet using the transfer sheet
JP2004059601A (en) * 2002-07-24 2004-02-26 Mitsubishi Rayon Co Ltd Resin composition for optical three-dimensional molding and three-dimensional molded article
JP2005298619A (en) * 2004-04-09 2005-10-27 Tsutsunaka Plast Ind Co Ltd Uv-curable coating material
JP2007039482A (en) * 2005-08-01 2007-02-15 Nippon Kayaku Co Ltd Resin composition, lens resin composition and its cured product

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3960417B2 (en) 2001-11-06 2007-08-15 アイカ工業株式会社 TRANSFER SHEET USING ACTIVE ENERGY RAY-CURABLE RESIN COMPOSITION, PROCESS FOR PRODUCING THE SAME, AND METHOD FOR PRODUCING DECORATIVE BOARD USING THE TRANSFER SHEET
JP3904448B2 (en) 2001-12-21 2007-04-11 アイカ工業株式会社 Active energy ray-curable resin composition for transfer, transfer sheet using the same, method for producing the same, and method for producing a decorative board using the transfer sheet
JP4318577B2 (en) * 2004-03-30 2009-08-26 株式会社巴川製紙所 Low reflection material
CN100560353C (en) * 2006-03-28 2009-11-18 日东电工株式会社 The manufacture method of hard-coated film, hard-coated film, optical element and image display device

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61258742A (en) * 1985-04-25 1986-11-17 山陽国策パルプ株式会社 Method of forming surface protective layer and surface protective layer attached sheet used for said method
JPH06256444A (en) * 1993-03-08 1994-09-13 Toli Corp Ltd Light/radiation-curing resin composition and flooring material coated therewith
JPH0752178A (en) * 1993-08-12 1995-02-28 Toppan Printing Co Ltd Manufacture of thermosetting resin decorative laminate
JPH11105437A (en) * 1997-10-02 1999-04-20 Dainippon Printing Co Ltd Thermal transfer sheet and photographic object
JP2002264288A (en) * 2001-03-14 2002-09-18 Aica Kogyo Co Ltd Transfer sheet, manufacturing method therefor, and manufacturing method for decorative sheet using the transfer sheet
JP2004059601A (en) * 2002-07-24 2004-02-26 Mitsubishi Rayon Co Ltd Resin composition for optical three-dimensional molding and three-dimensional molded article
JP2005298619A (en) * 2004-04-09 2005-10-27 Tsutsunaka Plast Ind Co Ltd Uv-curable coating material
JP2007039482A (en) * 2005-08-01 2007-02-15 Nippon Kayaku Co Ltd Resin composition, lens resin composition and its cured product

Cited By (8)

* Cited by examiner, † Cited by third party
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WO2012137828A1 (en) * 2011-04-04 2012-10-11 株式会社ダイセル Photocurable composition, conductive composite film, and manufacturing method for same
JP2020026466A (en) * 2018-08-10 2020-02-20 東洋インキＳｃホールディングス株式会社 Coating agent for decorative material
JP7119741B2 (en) 2018-08-10 2022-08-17 東洋インキＳｃホールディングス株式会社 Coating agent for cosmetic materials
WO2021075435A1 (en) * 2019-10-16 2021-04-22 凸版印刷株式会社 Transfer sheet and method for producing melamine decorative panel
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WO2021140687A1 (en) * 2020-01-09 2021-07-15 アイカ工業株式会社 Melamine decorative board and method for manufacturing melamine decorative board

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KR20170029655A (en) 2017-03-15
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TWI481665B (en) 2015-04-21
TW201120139A (en) 2011-06-16

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