JP2006272932A - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet hardly darkened to the same degree as a decorative sheet using a solvent type coating agent in a case that the decorative sheet is produced using an aqueous coating agent. <P>SOLUTION: The decorative sheet is constituted by forming a pattern layer on a base material sheet using an aqueous composition comprising a copper complex type yellow pigment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a decorative sheet and a decorative board using the decorative sheet.

  The decorative sheet is intended for surface protection, decoration, etc. of an adherend such as a wooden board, and is formed by laminating a base sheet, a pattern layer, an adhesive layer, a surface protective layer, and the like. . A decorative sheet is used by sticking on the surface of an adherend. And the decorative board obtained by this is used for various building materials, furniture, etc.

  In such a decorative sheet, conventionally, the pattern layer, the adhesive layer and the like have been formed from a solvent-based coating agent containing an aromatic solvent such as toluene and xylene, an aliphatic solvent such as methyl ethyl ketone and ethyl acetate, and the like. .

  All of the above aromatic solvents and aliphatic solvents are organic volatile substances (VOC). In particular, aromatic solvents such as toluene and xylene are designated chemical substances in the Chemical Substances Emissions Management and Promotion Act and chemical substances in indoor air. It is listed as a guideline value formulation substance. In addition, problems in the working environment due to volatilization of VOC contained in the solvent-based coating agent at the time of manufacturing the decorative sheet, environmental safety problems in which the residual VOC at the time of using the decorative sheet is diffused into a general living space, etc. have been pointed out. Yes. Therefore, a decorative sheet made of a water-based coating agent that reduces the amount of VOC used in the decorative sheet is provided (Patent Document 1).

  However, in the decorative sheet using the aqueous coating agent, although the VOC problem described above has been solved, a new problem has arisen. That is, compared with a decorative sheet using a solvent coating agent, a decorative sheet using a water-based coating agent is duller in color than the case of using a solvent-based coating agent (color vividness and clarity). Is inferior). As a result, the design properties of the decorative sheet are inferior.

Therefore, there is a need for a decorative sheet using a water-based coating agent that is less dull than that using a solvent-based coating agent.
JP 2001-38849 A

  The main object of the present invention is to provide a decorative sheet that is less dull than the one using a solvent-based coating agent when a decorative sheet is produced using an aqueous coating agent.

  In light of the problems of the prior art, the present inventor has found that the above object can be achieved by using a laminate having a specific configuration as a decorative sheet as a result of intensive studies, and has completed the present invention. .

  That is, the present invention relates to the following decorative sheet.

  1. A decorative sheet in which a pattern layer is formed on a base sheet with an aqueous composition containing a copper complex yellow pigment.

2. The copper complex yellow pigment is
The result of measuring the haze value of a dry thin film having a thickness of 1 μm formed from a composition comprising 10 parts by weight of the copper complex yellow pigment, 15 parts by weight of an aqueous urethane resin, 75 parts by weight of water and 40 parts by weight of isopropyl alcohol. Showing 45% or less,
The decorative sheet according to Item 1, wherein

  3. Item 3. The decorative sheet according to Item 1 or 2, wherein a colored masking layer is further formed between the base sheet and the pattern layer.

  4). Item 4. The decorative sheet according to Item 3, wherein the colored hiding layer is formed from an aqueous composition.

  5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein a transparent adhesive layer, a transparent resin layer, and a surface protective layer are sequentially laminated on the pattern layer.

  6). Item 6. The decorative sheet according to Item 5, wherein at least one of the transparent adhesive layer and the surface protective layer is formed from an aqueous composition.

  7). The decorative board formed by sticking the base material sheet side of the decorative sheet according to any one of Items 1 to 6 to an adherend.

  According to the decorative sheet of the present invention, since the pattern layer is highly transparent, it is possible to provide a decorative sheet that is less dull than the case of using a solvent-based coating agent. That is, the decorative sheet of the present invention is vivid in color and clear in color. As a result, a decorative sheet having high design properties can be provided.

  The decorative sheet of the present invention is characterized in that a pattern layer is formed on a base sheet with an aqueous composition containing a copper complex yellow pigment. This will be described in detail below.

Base sheet As the base sheet, for example, paper, non-woven fabric, thermoplastic resin sheet, or a composite material thereof is used.

  Examples of the paper include thin paper, kraft paper, high quality paper, linter paper, baryta paper, sulfate paper, and Japanese paper.

Moreover, as a nonwoven fabric, the nonwoven fabric which consists of fibers, such as a polyester resin, an acrylic resin, nylon, vinylon, glass, is mentioned, for example. The basis weight of paper or non-woven fabric is usually about ²⁰ to 100 g / m ² . In addition, for paper or non-woven fabric, resin such as acrylic resin, styrene butadiene rubber, melamine resin, urethane resin is added to strengthen the interlaminar strength between the fibers and other layers, and to prevent galling. It may be impregnated with resin or embedded during papermaking. Note that a decorative sheet using paper (or non-woven fabric) as a base sheet is decorative paper.

  Examples of the thermoplastic resin sheet include acrylic resin, polyester resin, polyolefin resin, polyvinyl chloride resin, polystyrene, ABS resin, polycarbonate resin, and polyamide resin.

  In the present invention, polyolefin resin is particularly preferable. For example, polypropylene, polyethylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, polyolefin-based thermoplastic elastomer, etc. Is mentioned. Further, among these, polypropylene, polyethylene and the like are particularly preferable.

  A copolymer mainly composed of polypropylene is also preferable, and examples thereof include homopolypropylene resins, random polypropylene resins, block polypropylene resins, and α-olefins having a polypropylene crystal part and having 2 to 20 carbon atoms other than propylene. .

  Moreover, the copolymer which has polyethylene as a main component is also preferable, for example, a block polyethylene, a high density polyethylene, a low density polyethylene, and a linear low density polyethylene is mentioned.

  In addition, a propylene-α-olefin copolymer containing 15 mol% or more of a comonomer of butene-1, 4-methylpentene-1, hexene-1, or octene-1 is also preferable.

  The polyolefin resin may be formed into a film by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.

  The thickness of the base sheet is not particularly limited and can be set according to desired product characteristics, but is usually about 40 to 150 μm, preferably about 50 to 100 μm.

  An additive may be mix | blended with a base material sheet as needed. Examples of the additive include a filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, and a colorant. The blending amount of the additive can be appropriately set according to the product characteristics.

  It does not specifically limit as a coloring agent, Well-known coloring agents, such as a pigment and dye, can be used. The coloring mode of the base sheet includes transparent coloring and opaque coloring (hiding coloring), and these can be arbitrarily selected. For example, when the ground color of the adherend (base material to which the decorative sheet is bonded) is concealed, opaque coloring may be selected. On the other hand, in order to make the ground pattern of the adherend visible, transparent coloring may be selected.

  One or both surfaces of the base sheet may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., as necessary. For example, when the corona discharge treatment is performed, the surface tension of the substrate sheet surface may be 30 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.

  A primer layer (for example, a back primer layer for facilitating adhesion of the adherend) may be provided on one side or both sides of the base sheet as necessary. By providing the primer layer, interlayer adhesion with an adjacent layer (for example, an adherend) can be increased.

  A primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a base material sheet. Examples of the primer agent include a urethane resin primer agent made of acrylic modified urethane resin, a primer agent made of urethane-cellulose resin (for example, a resin made by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton), and the like. Is mentioned.

The application amount of the primer agent is not particularly limited, but is usually about 0.1 to 100 g / m ² , preferably about 0.5 to 15 g / m ² .

A pattern layer is formed on the pattern pattern layer base sheet (opposite to the adherend attachment surface, hereinafter the same side in each layer).

  The design pattern layer imparts design properties with a desired design to the decorative sheet, and the type of design is not particularly limited. Examples thereof include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern.

  The pattern layer of the present invention contains a copper complex yellow pigment as a pigment. The copper complex yellow pigment used in the present invention is not particularly limited as long as it is a compound in which an organic dye and a copper ion are coordinated and has a yellow hue range. For example, P.I. Y. 129, P.I. Y. Suitable examples include copper azomethine yellow such as 117.

The copper complex yellow pigment of the present invention is
The result of measuring the haze value of a dry thin film having a thickness of 1 μm formed from a composition comprising 10 parts by weight of the copper complex yellow pigment, 15 parts by weight of an aqueous urethane resin, 75 parts by weight of water and 40 parts by weight of isopropyl alcohol. Showing 45% or less,
It is preferable that More preferably, the measurement result is 0 to 40%.

That is, the copper complex yellow pigment used in the present invention preferably satisfies the following requirements.
1) A composition comprising 10 parts by weight of a copper complex-based yellow pigment, 15 parts by weight of an aqueous urethane resin, 75 parts by weight of water and 40 parts by weight of isopropyl alcohol was prepared. 2) From the resulting composition, the thickness was 1 μm. Thus, after forming a dry thin film, 3) The result of having measured the haze value of the dry thin film shows 45% or less.
More preferably, in 3) above, the measurement result is 0 to 40%.

  By setting the haze value within this range, it is possible to make the pattern layer and thus the entire decorative sheet less dull. More specifically, the color is not as dull as the pattern layer produced using the solvent-based coating agent or more, and can be made clear. As a result, the decorative sheet of the present invention has improved design properties.

  Here, the haze value (cloudiness value) indicates the ratio of the diffuse transmittance to the total light transmittance when the material to be measured is irradiated with visible light. In addition, transparency is shown, so that this value is low. In the present invention, the haze value is measured in accordance with JIS K 7105.

  If the aqueous composition of this invention contains the said copper complex type | system | group yellow pigment, there will be no restriction | limiting in particular, Water-soluble resin may be used and an aqueous resin emulsion may be sufficient. The “aqueous composition” in the present invention refers to both a water-based ink and a water-based coating agent described later.

  In the present invention, an aqueous resin emulsion is particularly preferable. Examples thereof include water-based urethane resins, water-based polyester resins, water-based acrylic resins, water-based acrylic-urethane resins, cellulose resins, shellac resins, casein resins, mixed resins thereof, and those in which a crosslinking component is introduced. Among these, an aqueous urethane resin is particularly preferable. The aqueous urethane resin can be obtained by making the urethane resin aqueous by dissolution, emulsification, microencapsulation or other methods.

  As the ink for forming the pattern layer at the time of coating, water-based ink containing the copper complex yellow pigment is used.

  The water-based ink is obtained, for example, by dispersing (or dissolving) a copper complex yellow pigment in water or a water-based mixed dispersion medium (or solvent) composed of water and alcohol together with the resin and the like.

  The content of the copper complex yellow pigment in the water-based ink is not particularly limited, but is usually about 1 to 200 parts by weight, preferably about 10 to 100 parts by weight with respect to 100 parts by weight of the resin.

  The content of water or a water-based mixed dispersion medium in the water-based ink is not particularly limited, but is usually about 100 to 1000 parts by weight with respect to 100 parts by weight of the resin.

  Further, the particle size of the copper complex yellow pigment is not particularly limited, but from the viewpoint that the pattern layer can be made more dull, the primary particle size is preferably about 50 to 300 nm, more preferably about 50 to 150 nm. It is.

  In addition to the copper complex yellow pigment, other colorants can be used in combination. Organic or inorganic pigments can be added as other colorants. Examples of red pigments include azo pigments such as monoazo, disazo, and polyazo, organic pigments such as quinacridone, and inorganic pigments such as bengara, vermilion, cadmium red, and chrome vermilion. Examples of the blue pigment include organic pigments such as phthalocyanine blue and indanthrene blue, and inorganic pigments such as bitumen, ultramarine blue, and cobalt blue. Examples of the black pigment include organic pigments such as aniline black and inorganic pigments such as carbon black. Examples of white pigments include inorganic pigments such as titanium dioxide, zinc white, and antimony trioxide. In the coloring pigment, fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like may be added.

  Further, a crosslinking agent may be added. Examples of the crosslinking agent include isocyanate group-containing compounds, epoxy group-containing compounds, carbodiimide group-containing compounds, oxazoline group-containing compounds, silanol group-containing compounds, and the like, but isocyanate group-containing compounds are preferred.

  Water-based inks having a crosslinking component introduced therein, for example, water-based inks containing an aqueous compound having an amino group as a main agent and an aqueous compound having two or more epoxy groups in one molecule as a crosslinking agent, have an active hydrogen group An aqueous ink containing an aqueous compound as a main agent and an aqueous compound having two or more isocyanate groups in one molecule as a crosslinking agent, and an aqueous compound having a carboxyl group as a main agent and having two or more carbodiimide groups in one molecule. Examples thereof include water-based inks containing a water-based compound as a crosslinking agent.

  The solvent (or dispersion medium) consists of water or water and alcohol. Examples of the alcohol include lower alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and normal propyl alcohol. Among these, methyl alcohol, ethyl alcohol, isopropyl alcohol, and normal propyl alcohol are preferable. In the case of a mixed solvent of water and alcohol, the weight ratio of water and alcohol is appropriately determined depending on the resin or the like to be dissolved or dispersed, but is usually 100: 0 to 20:80.

  What is necessary is just to form the formation method of a pattern pattern layer using the water-system coating agent containing the water-based ink containing a copper complex type | system | group yellow pigment.

  Water-based coating agent (water-based ink composition) that forms a pattern layer can be used for water-based inks such as waxes, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, crosslinking agents, etc. Add additives arbitrarily, further dissolve (or disperse) in water or water-based mixed dispersion medium (or solvent) consisting of water and alcohol, etc., and mix well with a mixer etc. to adjust be able to.

  The addition amount of water or an aqueous mixed dispersion medium is not limited, but is usually about 1 to 500 parts by weight with respect to 100 parts by weight of the water-based ink.

  The pattern-like layer may be formed by a known printing method. Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When forming a solid pattern pattern layer, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating Various coating methods such as a coating method may be mentioned. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used or combined with other forming methods. Good.

  The aspect in which the aqueous coating agent is applied to the base sheet, the primer layer, the colored concealing layer, etc. is not particularly limited, and may be applied to the entire surface of the layer or may be a part of the surface of the layer. Good. Since the main purpose of the pattern layer is to form a pattern, it is usually applied partially.

  The thickness of the pattern layer is not particularly limited and can be set as appropriate according to product characteristics. The thickness at the time of coating is about 1 to 15 μm, and the thickness after drying is about 0.1 to 10 μm.

Colored concealment layer In the decorative sheet of the present invention, a color concealment layer may be further formed between the base sheet and the pattern layer.

  The colored concealment layer only needs to conceal the ground color of the adherend when the decorative sheet and the adherend are joined, and is usually formed so as to cover the base sheet.

  As a component for forming a colored hiding layer, a component used for forming a pattern layer can be used as it is. Depending on the application, the coloring may be transparent. Moreover, the coloring concealment layer may contain the copper complex yellow pigment mentioned above.

  The ink for the colored hiding layer is preferably an aqueous composition, particularly an aqueous resin emulsion. Examples of the aqueous resin emulsion include those described above for the pattern layer. Among these aqueous resin emulsions, the above-described aqueous acrylic-urethane resin is most preferable from the viewpoints of adhesion and VOC reduction.

  The water-based coating agent for the coloring hiding layer includes additives such as waxes, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, cross-linking agents, etc. in the above-described ink. It is optionally added and further dispersed (or dissolved) in water or a water-based mixed dispersion medium (or solvent) composed of water and alcohol, and mixed well with a mixer or the like to be adjusted.

  The method for forming the colored masking layer is not particularly limited, and as the coating method, for example, various conventionally known coating means such as gravure coating, roll coating, reverse coating, doctor coating and the like can be used.

Usually, the coating amount is desirably in the range of ² to 30 g / m ² at the time of drying and curing. If the amount is too small, the hiding power may be reduced. Moreover, even if too much, the hiding power is saturated. The thickness of the colored masking layer is usually about 0.1 to 20 μm, preferably about 1 to 10 μm.

If necessary, a transparent resin layer may be formed on the transparent adhesive layer pattern layer. A transparent adhesive layer may be formed between the transparent resin layer and the pattern layer in order to improve the adhesion between the layers. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of transparent and colorless, colored and translucent.

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet.

  Examples of the adhesive known in the field of decorative sheets include thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and curable resins such as thermosetting urethane resin. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  The transparent adhesive layer can be formed, for example, by applying an adhesive on the pattern layer, applying a transparent resin constituting the transparent resin layer, and drying and curing.

  In the decorative sheet of the present invention, the ink forming the adhesive layer is formed from an aqueous composition, preferably an aqueous resin emulsion, from the viewpoints of adhesion to an adjacent layer and reducing the amount of VOC used in the decorative sheet. The

  The aqueous resin emulsion contained in the aqueous coating agent is preferably an aqueous urethane resin, and more preferably a two-component aqueous urethane resin containing a crosslinking agent. The aqueous urethane resin can be obtained by making the urethane resin aqueous by dissolution, emulsification, microencapsulation or other methods. As the crosslinking agent, a water-dispersible isocyanate crosslinking agent can be preferably used.

  Other aqueous resin emulsions include polycarbonate, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative, styrene-maleic anhydride copolymer. Examples include polymer alcohol adducts and cellulosic resins.

  Additives such as colorants, waxes, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, crosslinking agents, etc. are optionally added to the aqueous coating agent for the adhesive layer it can. A water-based coating agent is prepared by using water or a water-based mixed solvent composed of water and alcohol and thoroughly mixing with a mixer or the like.

  Conditions such as the drying temperature and drying time of the coating agent are not particularly limited, and may be set as appropriate according to the type of adhesive. The method of applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, and comma coating. The method can be adopted.

  Although the thickness of a transparent adhesive bond layer is not specifically limited, The thickness after drying is about 0.1-30 micrometers, Preferably it is about 1-20 micrometers.

Transparent resin layer A transparent resin layer may be formed on the transparent adhesive layer as necessary.

  The transparent resin layer is not particularly limited as long as it has transparency. For example, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, polymethylpentene, acrylic acid ester, Examples thereof include methacrylic acid ester, polycarbonate, and cellulose triacetate.

  Preferably, a polyolefin resin typified by polypropylene resin is used. Therefore, when using polyolefin-type resin as a transparent resin layer, the various polyolefin-type resin quoted as what comprises a base material sheet can be used.

  The transparent resin layer may be colored as long as it has transparency, but it is particularly desirable not to add a colorant.

  The forming method of the transparent resin layer is not limited, for example, a method of laminating a preformed sheet or film on an adjacent layer, an adjacent layer by melt-extruding a resin composition capable of forming a transparent resin layer Any of a method of coating on top and a method of laminating together with an adjacent layer can be employed. In the present invention, it is particularly preferable to form the transparent resin layer by melt extrusion. In particular, the transparent resin layer is preferably applied by melt extrusion of a polyolefin resin. Specifically, the transparent resin layer can be suitably formed by forming an adhesive layer on the pattern layer in advance, and melt-extruding and applying a polypropylene-based thermoplastic elastomer onto the adhesive layer. What is necessary is just to implement the method of melt extrusion according to the well-known method using a T die etc., for example. In addition, the above resin can be further improved in adhesiveness by co-extrusion of a polypropylene resin centering on an acid-modified component such as polymaleic anhydride.

  Said extrusion process can also be performed simultaneously with an embossing process. That is, a decorative sheet can be efficiently produced by extruding and laminating a transparent resin on the sheet and simultaneously performing an embossing treatment.

The thickness of the transparent resin layer is usually about 20 to 200 μm, similarly to the base sheet 1, but may exceed the above range depending on the use of the decorative sheet and the like.
Moreover, you may provide the primer layer (The primer layer for making formation of the surface protective layer mentioned later easy) on the surface as needed.

  The primer layer can be formed by applying a known primer agent on the transparent resin layer. Examples of the primer agent include a urethane resin-based primer agent composed of an acrylic-modified urethane resin and the like, and a resin-based primer agent composed of a block copolymer of acrylic and urethane.

The application amount of the primer agent is not particularly limited, but is usually about 0.1 to 100 g / m ² , preferably about 0.5 to 15 g / m ² .

If necessary, a surface protective layer may be formed on the surface protective layer transparent resin layer.
The surface protective layer is provided for imparting surface physical properties such as scratch resistance, abrasion resistance, water resistance and stain resistance required for the decorative sheet for flooring. As the resin for forming this surface protective layer, a curable resin such as a thermosetting resin or an ionizing radiation curable resin is suitable. Examples of the thermosetting resin include unsaturated polyester resins and polyurethane resins (two-component curable type). Polyurethane), epoxy resin, amino alkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine-urea cocondensation resin, silicon resin, polysiloxane resin, and the like. A curing agent such as a cross-linking agent and a polymerization initiator, and a polymerization accelerator can be added to the resin as necessary. For example, as curing agents, isocyanates, organic sulfonates, etc. are added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. are added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. A radical initiator is added to the unsaturated polyester resin.

  Further, from the viewpoint of the VOC problem, the ink for forming the surface protective layer is preferably an aqueous composition, particularly an aqueous resin emulsion. That is, the surface protective layer is preferably formed from an aqueous composition, particularly an aqueous resin emulsion. What was mentioned above is mentioned as an aqueous resin emulsion. More preferably, it is an aqueous urethane resin.

  As a method of forming the surface protective layer with the thermosetting resin, for example, the above-mentioned thermosetting resin is used as a solution, and this solution is applied by a known coating method such as a roll coating method or a gravure coating method, and dried. The method of hardening is mentioned. The coating amount of the above solution is suitably about 5 to 30 μm in solid content, preferably 15 to 25 μm.

  The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a cross-linking polymerization reaction by irradiation with ionizing radiation and changes to a three-dimensional polymer structure. Ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, such as visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-ray, electron beam, ion beam, etc. In particular, it is desirable to use ultraviolet rays, electron beams, and the like. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. As the wavelength of the ultraviolet light, a wavelength range of about 190 to 380 nm can be used. As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. As an electron beam to be used, generally, an electron beam of about 100 to 1000 keV, preferably about 100 to 300 keV can be used. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

  The ionizing radiation curable resin is a monomer, prepolymer or polymer having a radically polymerizable unsaturated group such as (meth) acryloyl group, (meth) acryloyloxy group, or a cationically polymerizable functional group such as epoxy group in the molecule. A polymer (hereinafter collectively referred to as a compound). These monomers, prepolymers, and polymers can be used alone or in combination. In this specification, (meth) acrylate is used in the meaning of acrylate or methacrylate.

Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and polyvinylpyrrolidone. This prepolymer usually has a molecular weight of about 10,000 or less. When the molecular weight exceeds 10,000, the cured resin layer has insufficient surface properties such as scratch resistance, abrasion resistance, chemical resistance, and heat resistance. Although the acrylate and methacrylate can be used in common, the acrylate is more advantageous for the purpose of curing efficiently at a high speed and in a short time because the acrylate is faster in terms of the crosslinking curing rate with ionizing radiation.

  Examples of the prepolymer having a cationically polymerizable functional group include epoxy resins such as bisphenol type epoxy resins, novolac type epoxy resins, and alicyclic epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, urethane vinyl ethers, and ester vinyl ethers. And prepolymers such as vinyl ether resins, cyclic ether compounds, and spiro compounds.

  As the monomer having a radical polymerizable unsaturated group, for example, as a monofunctional monomer of (meth) acrylate compound, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl (meth) ) Acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, 2 ethylhexyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, ethyl carbitol ( Acrylate), phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, Examples include 2- (meth) acryloyloxypropyl hydrogen terephthalate.

  Examples of the polyfunctional monomer having a radical polymerizable unsaturated group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. , Dipropylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate Rate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate, tris (meth) acryloyl Examples thereof include oxyethyl phosphate. As the monomer having a cationic polymerizable functional group, a prepolymer monomer having the cationic polymerizable functional group can be used.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam. However, when cured by irradiation with ultraviolet rays, a photopolymerization initiator is added as a sensitizer. Examples of the photopolymerization initiator in the case of a resin system having a radically polymerizable unsaturated group include acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used alone or in combination. In the case of a resin system having a cationically polymerizable functional group, for example, an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonate ester, a freeloxysulfoxonium diallyl iodosyl salt, etc. alone or as a mixture Can be used.

  Although the addition amount of a photoinitiator is not specifically limited, Generally it should just be about 0.1-10 weight part with respect to 100 weight part of ionizing radiation-curable resins.

  As a method of forming the protective layer with an ionizing radiation curable resin, for example, an ionizing radiation curable resin is used as a solution, and this solution may be applied by a known application method such as a gravure coating method or a roll coating method. In this case, the coating amount of the solution may be about 5 to 30 μm, more preferably 15 to 25 μm as the solid content.

  In addition, an inorganic filler can be blended as necessary when further imparting scratch resistance and abrasion resistance to the surface protective layer formed from the ionizing radiation curable resin. For example, powdered aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, gold sand, glass fiber Etc.

  Although the usage-amount of an inorganic filler is not limited, Usually, what is necessary is just to be about 1-80 weight part with respect to 100 weight part of ionizing radiation curable resins.

  The thickness of the surface protective layer is not particularly limited and can be appropriately set according to the characteristics of the final product, but is usually about 0.1 to 50 μm, preferably about 1 to 20 μm.

  Irregularities may be formed on the front surface (surface exposed to the atmosphere) of the surface protective layer. Usually, an uneven pattern is formed by embossing. The embossing method is not particularly limited. For example, a preferable method is to heat soften the front surface of the transparent acrylic resin layer, pressurize and shape with an embossing plate, and then cool. For embossing, a known single-wafer or rotary embossing machine is used. Examples of the concavo-convex shape include a wood grain plate conduit groove, a stone plate surface unevenness (such as granite cleaved surface), a cloth surface texture, a satin texture, a grain, a hairline, a ridge line, and the like.

Adhering material The adhering material to which the decorative sheet of the present invention is applied is not limited, and the same materials as known decorative sheets can be used. For example, a wood material, a metal, ceramics, plastics, glass, etc. are mentioned. In particular, the decorative sheet of the present invention can be suitably used for a wood material. Specific examples of wood materials include veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. ) And the like.

Lamination on adherend The decorative sheet of the present invention is laminated on various adherends and used as a decorative board. The lamination method is not limited. For example, a method of sticking a decorative sheet to an adherend with an adhesive or the like can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, and natural rubber.

  The decorative board produced in this way is, for example, interior decoration materials for buildings such as walls, ceilings and floors, surface decorative boards for furniture such as window frames, doors and handrails, furniture or light electrical appliances, cabinets such as OA equipment. It can be preferably used for a surface decorative board or the like.

  Next, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to the examples.

Example 1
(1) Preparation of aqueous coating agent A for colored hiding layer 100 parts by weight of water-based urethane-acrylic copolymer white ink (Ode KEX White, manufactured by The Inktec Co., Ltd.), water-dispersible isocyanurate bond-containing isocyanate A coating agent A for a colored hiding layer was prepared by mixing 10 parts by weight of a crosslinking agent (NK assist IS-100N manufactured by Nikka Chemical Co., Ltd.), 20 parts by weight of water and 20 parts by weight of isopropyl alcohol.

(2) Preparation of aqueous coating agent B for picture pattern layer Aqueous composition comprising 10 parts by weight of copper complex yellow pigment (Pigment No. PY129), 15 parts by weight of aqueous urethane resin, 55 parts by weight of water and 20 parts by weight of isopropyl alcohol. The ink was further mixed with 20 parts by weight of water and 20 parts by weight of isopropyl alcohol to prepare an aqueous coating agent B for the pattern layer.

(3) Preparation of water-based coating agent C for transparent adhesive layer 100 parts by weight of water-based urethane resin-containing adhesive (Toyobo Co., Ltd. Bironal MD1480), isocyanate crosslinking agent (manufactured by Nikka Chemical Co., Ltd., NK Assist) IS-100N) 10 parts by weight and 10 parts by weight of water were mixed to prepare a coating agent C for a transparent adhesive layer.

(4) Preparation of water-based coating agent D for surface protective layer 100 parts by weight of water-based urethane resin-based ink (No. 135 manufactured by Showa Ink Industries, Ltd.), 10 parts by weight of water-dispersible isocyanurate bond-containing isocyanate crosslinking agent Then, 10 parts by weight of water and 20 parts by weight of isopropyl alcohol were mixed to prepare a coating agent D for the surface protective layer.

(Production of decorative sheet)
A 60 μm colored sheet mainly composed of polypropylene was used as a base sheet, and both front and back surfaces were subjected to corona discharge treatment. After that, the water-based coating agent A for the colored hiding layer and the water-based coating agent B for the pattern layer are sequentially applied and dried on the entire surface of the sheet by the gravure printing method, respectively, and the color hiding is 3 g / m ² . A layer (thickness 3 μm) and a 1 g / m ² pattern layer (thickness 1 μm) were sequentially formed.
Subsequently, the aqueous coating agent C for adhesive layers was apply | coated and dried on it by the gravure printing method, and the 3 g / m < ² > transparent adhesive layer was formed.
On the adhesive layer, a transparent polypropylene film having a thickness of 80 μm was laminated by a dry laminate method to form a transparent resin layer.
Then, after forming irregularities on the surface of the transparent resin layer by embossing, the aqueous coating agent D for the surface protective layer having the above composition was applied and dried by a gravure printing method, and the surface was 5 g / m ² . A protective layer was formed.

Comparative Example 1
In the preparation of the water-based coating agent B for the pattern layer, an ink comprising 10 parts by weight of condensed azo (Pigment No. PY128), 15 parts by weight of a water-based urethane resin, 55 parts by weight of water and 20 parts by weight of isopropyl alcohol is further added to water. A decorative sheet was prepared in the same manner as in Example 1 except that 20 parts by weight and 20 parts by weight of isopropyl alcohol were mixed to prepare an aqueous coating agent B for the pattern layer.

(Test method)
1. A transparent PET film having a thickness of 75 μm (Teijin DuPont Films, Ltd., “HS74”) was used as a substrate sheet for measuring haze values . On the base sheet, the pattern coating layer aqueous coating agent B in Example 1 and Comparative Example 1 was uniformly applied by gravure printing, dried, and 1 g / m ² pattern pattern layer (thickness 1 μm). Formed.

  The haze value of the obtained pattern / pattern layer forming sheet was measured by a direct reading haze meter (manufactured by Toyo Seiki Seisakusho). The results are shown in Table 1 below.

2. Dullness evaluation The dullness of the decorative sheet produced in Example 1 and Comparative Example 1 was visually observed. “No dullness” was evaluated as “◯”, and “dullness” was evaluated as “x”. The results are shown in Table 1.

Claims (7)

A decorative sheet in which a pattern layer is formed on a base sheet with an aqueous composition containing a copper complex yellow pigment. The copper complex yellow pigment is
The result of measuring the haze value of a dry thin film having a thickness of 1 μm formed from a composition comprising 10 parts by weight of the copper complex yellow pigment, 15 parts by weight of an aqueous urethane resin, 75 parts by weight of water and 40 parts by weight of isopropyl alcohol. Showing 45% or less,
The decorative sheet according to claim 1, wherein The decorative sheet according to claim 1 or 2, wherein a colored concealing layer is further formed between the base sheet and the pattern layer. The decorative sheet according to claim 3, wherein the colored hiding layer is formed from an aqueous composition. The decorative sheet according to any one of claims 1 to 4, wherein a transparent adhesive layer, a transparent resin layer, and a surface protective layer are sequentially laminated on the design pattern layer. The decorative sheet according to claim 5, wherein at least one of the transparent adhesive layer and the surface protective layer is formed from an aqueous composition. The decorative board formed by sticking the base material sheet side of the decorative sheet according to any one of claims 1 to 6 to an adherend.