JP2006110726A - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in environmental safety and enhanced in interlaminar bonding. <P>SOLUTION: The decorative sheet 1 is constituted by laminating an ink layer 11 having a solid ink layer 3 and/or a pattern ink layer 4, an adhesive layer 5 and a transparent resin layer 6 on a base material 2 in this order and at least one of the ink layer 11 and the adhesive layer 5 is formed using an aqueous coating agent containing an aqueous compound having at least two carbodiimide groups in one molecule thereof. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a decorative sheet used for interiors of buildings, surface decorations of fittings, interiors of vehicles, and the like. More specifically, the present invention relates to a decorative sheet having significantly improved environmental safety and excellent interlayer adhesion.

  A decorative sheet in which an ink layer having a base material, a solid ink layer and / or a pattern layer, an adhesive layer, and a transparent resin layer are sequentially laminated as a decorative sheet used for interior decoration of a building, surface decoration of a fitting, or interior decoration of a vehicle. Is generally known. Such a decorative sheet is required to be excellent in interlaminar adhesion after the curing treatment between the substrate and the transparent resin layer (referring to a treatment that is held at a predetermined temperature for a predetermined time in order to sufficiently perform a crosslinking reaction). Has been.

  From the viewpoint of satisfying such requirements, a solvent-based coating agent containing a crosslinking agent has been conventionally used for forming an ink layer and an adhesive layer. As a solvent for such a coating agent, an aromatic solvent such as toluene or xylene or an aliphatic solvent such as methyl ethyl ketone or ethyl acetate is used (for example, see Patent Document 1).

  By the way, in recent years, the number of cases of sick house syndrome caused by volatile organic substances released from building materials has been increasing, and the guideline value for the amount of emission using substances considered to be particularly dangerous by the Ministry of Health, Labor and Welfare as designated substances. And guideline values for emission of total volatile organic substances are being implemented. The above-mentioned aromatic solvents such as toluene and xylene and aliphatic solvents such as methyl isobutyl ketone and butyl acetate are organic volatile substances (hereinafter referred to as VOC). In particular, aromatic solvents such as toluene and xylene are those of the PRTR method. Since it is listed as a guideline for setting designated chemical substances and chemical substances in indoor air, there is a movement to reduce the use of such aromatic solvents and other solvents.

Even in the production of decorative sheets, there are problems in the working environment during the production of decorative sheets due to the volatilization of VOCs contained in solvent-based coating agents, and environmental safety problems in which the VOC remaining on the decorative sheets is supplied to general living spaces. There have been proposed various means for reducing the use of VOCs to solve the above problems. For example, Patent Document 2 describes that the above environmental problem is solved by forming an ink layer, an adhesive layer, or the like with an aqueous coating agent in which the content of VOC is reduced as much as possible.
JP-A-11-198309 JP 2000-62970 A

  However, the decorative sheet in which the ink layer and the adhesive layer are formed of an aqueous coating agent can reduce the volatilization amount and residual amount of VOC, and is effective in solving the environmental problems described above. The base material and the transparent resin layer constituting the material are often inferior to the interlayer adhesion after the water resistance test and the interlayer adhesion after the moisture and heat resistance test, and it can be said that the substrate and the transparent resin layer do not necessarily have sufficient interlayer adhesion. It was not.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a decorative sheet having excellent environmental safety and improved interlayer adhesion.

  The decorative sheet of the present invention for solving the above problems is a decorative sheet in which an ink layer having a solid ink layer and / or a pattern ink layer, an adhesive layer, and a transparent resin layer are laminated in this order on a substrate. In addition, at least one of the ink layer and the adhesive layer is formed of an aqueous coating agent containing an aqueous compound having two or more carbodiimide groups in one molecule.

  According to the present invention, since at least one of the ink layer and the adhesive layer constituting the decorative sheet is formed of the aqueous coating agent, the volatilization amount of VOC from the decorative sheet and the VOC remaining in the decorative sheet The amount can be reduced. As a result, it is possible to improve the safety of the working environment and the environmental safety in the living space when manufacturing the decorative sheet. According to the invention, the aqueous coating agent used for forming at least one of the ink layer and the adhesive layer contains an aqueous compound having two or more carbodiimide groups in one molecule. In addition, at least one of the ink layer and the adhesive layer becomes a strong layer by the action of the aqueous compound having the carbodiimide group, and the interlayer adhesion between the substrate and the transparent resin layer can be improved. Furthermore, according to the present invention, the layer formed of the aqueous coating agent containing the aqueous compound having a carbodiimide group described above is crosslinked even at a curing treatment at room temperature over a normal treatment time. At least one of the ink layer and the adhesive layer becomes a strong layer even during the curing process at a low temperature for a long time, and the interlayer adhesion between the substrate and the transparent resin layer can be improved.

  In the decorative sheet of the present invention, in the above-described decorative sheet, (A) the surface on the ink layer side of the substrate is subjected to an easy adhesion treatment, and the ink layer is formed of the water-based coating agent. (B) It is preferable that the transparent resin layer is formed by a melt extrusion coating method using a resin containing a maleic acid-modified polypropylene resin, and the adhesive layer is formed by the aqueous coating agent. .

  The decorative sheet of the present invention is the above decorative sheet, wherein one of the aqueous coating agent forming the ink layer and the aqueous coating agent forming the adhesive layer is an anionic group. It is preferable that the water-based resin component which has this is contained, and it is further more preferable that the anionic group is at least one of the neutralized carboxyl group and the neutralized sulfonic acid group.

  According to this invention, the aqueous resin having an anionic group is contained in the aqueous coating agent that forms at least one of the ink layer and the adhesive layer, and such an anionic group is a carbodiimide group possessed by the aqueous compound. Therefore, the number of unreacted anionic groups that easily adsorb water in the ink layer and / or the adhesive layer constituting the decorative sheet is reduced. As a result, the water resistance, moist heat resistance and weather resistance of the decorative sheet are improved, so that the adhesion between each layer constituting the decorative sheet and the base material and the transparent resin layer by adsorbing moisture in the air by the anionic group, etc. It can suppress that the interlayer adhesiveness falls with time.

  In the decorative sheet of the present invention, it is preferable that the base material is made of a polyolefin-based elastomer and the transparent resin layer is made of a polyolefin-based resin in the decorative sheet.

  In the decorative sheet of the present invention, it is preferable that a first primer layer is further provided on the surface of the base material side in the decorative sheet.

  In the decorative sheet of the present invention, in the decorative sheet, the first primer layer is formed by an aqueous coating agent for a first primer layer containing an aqueous compound having two or more carbodiimide groups in one molecule. It is preferable that the surface of the base material on the first primer layer side is subjected to an easy adhesion treatment.

  In the decorative sheet of the present invention, in the decorative sheet, the aqueous coating agent forming the first primer layer preferably contains an aqueous resin component having an anionic group, and the anionic property More preferably, the group is at least one of a neutralized carboxyl group and a neutralized sulfonic acid group.

  In the decorative sheet of the present invention, in the above-described decorative sheet, it is preferable that a surface protective layer is further laminated on the transparent resin layer (hereinafter, this decorative sheet may be referred to as “decorative sheet I”).

  The decorative sheet of the present invention is the decorative sheet I described above, wherein the surface protective layer is formed of an aqueous coating agent for a surface protective layer containing an aqueous compound having two or more carbodiimide groups in one molecule. It is more preferable that the surface of the transparent resin layer on the surface protective layer side is subjected to an easy adhesion treatment.

  In the decorative sheet of the present invention, in the decorative sheet described above, the aqueous coating agent forming the surface protective layer preferably contains an aqueous resin component having an anionic atomic group. More preferably, the functional group is at least one of a neutralized carboxyl group and a neutralized sulfonic acid group.

  The decorative sheet of the present invention is the decorative sheet I described above, wherein the surface protective layer is formed of an active energy ray-curable coating agent, and a second primer is provided between the surface protective layer and the transparent resin layer. A layer is further provided, and the second primer layer is preferably formed of an aqueous coating agent, and the second primer layer has an aqueous compound having two or more carbodiimide groups in one molecule. It is preferable to form with the aqueous coating agent for surface protection layers containing this. The active energy ray is preferably an electron beam, and the surface protective layer is formed by applying an active energy ray-curable coating agent and then irradiating the active energy ray.

  In the decorative sheet of the present invention, in the decorative sheet, the aqueous coating agent forming the second primer layer preferably contains an aqueous resin component having an anionic group, and the anionic property More preferably, the group is at least one of a neutralized carboxyl group and a neutralized sulfonic acid group.

  According to the decorative sheet of the present invention, it is easy to suppress the volatilization amount of VOC from the decorative sheet and the remaining amount of VOC in the decorative sheet, thereby improving the safety of the working environment and the environmental safety in the living space when manufacturing the decorative sheet. Can be made.

  Further, according to the decorative sheet of the present invention, the ink layer and / or the adhesive layer becomes a strong layer by the crosslinking action of an aqueous compound having two or more carbodiimide groups in one molecule, so Interlayer adhesion with the resin layer can be improved.

  Furthermore, according to the decorative sheet of the present invention, since the ink layer and / or the adhesive layer becomes a strong layer even in the curing treatment at a low temperature, the interlayer adhesion between the substrate and the transparent resin layer is easily improved. be able to.

  The decorative sheet of the present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of the layer structure of the decorative sheet 1 of the present invention.

  As shown in FIG. 1, the decorative sheet 1 of the present invention has an ink layer 11 composed of a solid ink layer 3 and / or a pattern ink layer 4, an adhesive layer 5, and a transparent resin layer 6 on a substrate 2. The uneven pattern 7, the colored layer 8, and the surface protective layer 9 are sequentially laminated, and the first primer layer 10 is further provided on the back surface of the substrate 2.

(Base material)
The base material 2 is an essential component in the decorative sheet 1 of the present invention, and an olefin resin can be preferably applied, but the type is not limited. For example, (a) the main raw material is composed of either high-density polyethylene or polypropylene as a hard segment, and a mixture obtained by adding an elastomer and an inorganic filler as a soft segment to the base 2 can be used. Also, (b) an ethylene-propylene-butene copolymer described in JP-A-9-1111055, JP-A-5-77371, JP-A-7-316358 and the like can be used for the substrate 2. . Also, (c) a mixture of isotactic polypropylene as a hard segment and atactic polypropylene as a soft segment described in JP-B-6-23278 can be used for the substrate 2.

  The high-density polyethylene as the hard segment in the olefin resin (a) is preferably polyethylene having a specific gravity of 0.94 to 0.96, and has a high degree of crystallinity obtained by the low-pressure method. High-density polyethylene, which is a polymer with few branched structures, is used. As the polypropylene as the hard segment, isotactic polypropylene is preferably used.

  Diene rubber, hydrogenated diene rubber, olefin elastomer, and the like are used as the elastomer (i) as the soft segment. The hydrogenated diene rubber is formed by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule, and suppresses crystallization of the polyolefin resin to improve its flexibility. Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene butadiene rubber. The olefin elastomer is an elastic copolymer to which at least one polyene that can be copolymerized with two or more olefins is added. As the olefin, ethylene, propylene, α-olefin, or the like is used. 1,4 hexadiene, cyclic diene, norbornene and the like are used. Preferred examples of the olefin elastomer include elastic copolymers containing olefin as a main component such as ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene rubber, and ethylene-butadiene copolymer rubber. Note that these elastomers may be overcrosslinked using a crosslinking agent such as an organic peroxide or sulfur as necessary.

  The amount of these elastomers added is 10 to 60% by weight, preferably about 30% by weight. If it is lower than 10% by weight, the change in the constant load elongation becomes too steep, and the elongation at break, impact resistance, and easy adhesion are deteriorated. If it is higher than 60% by weight, the transparency, weather resistance and resistance Decrease in creep properties occurs.

  As the inorganic filler (a), a powder having an average particle size of about 0.1 to 10 microns such as calcium carbonate, barium sulfate, clay, talc and the like is used. The addition amount is about 1 to 60% by weight, preferably about 5 to 30% by weight. If the amount is less than 1% by weight, the creep deformation resistance and the easy adhesion property are lowered, and if it exceeds 60% by weight, the elongation at break and the impact resistance are lowered.

  As the (olefin) olefin resin, a thermoplastic elastomer made of an ethylene / propylene / butene copolymer resin is used. Here, as butene, any of the three structural isomers of 1 butene, 2 butene, and isobutylene can be used. The copolymer is a random copolymer and includes a part of an amorphous part.

  Preferable specific examples of the ethylene / propylene / butene copolymer resin include the following (a) to (c).

  (A) A random copolymer of a terpolymer of ethylene, propylene and butene described in JP-A-9-1111055. The weight ratio of the monomer component is preferably 90% by weight or more for propylene, and the melt flow rate is preferably 1 to 50 g / 10 min under the conditions of 230 ° C. and 2.16 kg. With respect to 100 parts by weight of such a ternary random copolymer, the random copolymer includes 0.01 to 50 parts by weight of a transparent nucleating agent mainly composed of a phosphoric acid aryl ester compound and 12 to 12 carbon atoms. It is obtained by melt-kneading 0.003 to 0.3 parts by weight of 22 fatty acid amides. (B) A terpolymer of ethylene, propylene and butene described in JP-A-5-77371, wherein the propylene weight ratio is 50% by weight or more to an amorphous polymer of 20 to 100% by weight, An ethylene / propylene / butene copolymer obtained by adding 80 to 0% by weight of crystalline polypropylene. (C) A terpolymer of ethylene, propylene and 1-butene described in JP-A-7-316358, wherein the low-crystalline polymer 20 has a propylene and / or 1-butene content of 50% by weight or more. 0.5% by weight of oil gelling agent such as N acylamino acid amine salt, N acylamino acid ester, etc. to a composition in which 80 to 0% by weight of crystalline polyolefin such as isotactic polypropylene is mixed with ˜100% by weight % Ethylene / propylene / butene copolymer.

  The ethylene / propylene / butene copolymer resins of the above (a) to (c) may be used alone or, if necessary, further mixed with other polyolefin resins in the ethylene / propylene / butene copolymer resin. May be used.

  As the olefin-based resin (C), the number average molecular weight Mn is 25000 or more as a soft segment described in Japanese Patent Publication No. 6-23278, and the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn. 10 to 90% by weight of atactic polypropylene soluble in boiling heptane of ≦ 7, and 90 to 10% by weight of (B) boiling heptane-insoluble isotactic polypropylene having a melt index of 0.1 to 4 g / 10 min as a hard segment % And a soft polypropylene which consists of a mixture with%.

  Among the olefin-based thermoplastic elastomers of (c) above, a mixture of isotactic polypropylene and atactic polypropylene and a weight ratio of atactic polypropylene of 5 to 50% by weight is preferable, and a weight ratio of atactic polypropylene Is particularly preferably 20 to 40% by weight. When the weight ratio of the atactic polypropylene is less than 5% by weight, it is embossed or unevenly deformed by necking when it is molded into a three-dimensional or uneven article, resulting in wrinkles and patterns Distortion occurs. On the other hand, when the weight ratio of the atactic polypropylene exceeds 50% by weight, the sheet itself is easily deformed, and the sheet is deformed when the sheet is passed through a printing machine. Defects such as failure to fit easily occur, and the sheet is easily torn during molding.

  A colorant, a heat stabilizer, a flame retardant, an ultraviolet absorber, a radical scavenger, and the like are added to the above-described olefin resin forming the substrate 2 as necessary.

  Coloring agents include titanium white, zinc white, bengara, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, etc. Organic pigments or dyes, metallic pigments made of foil powder such as aluminum and brass, pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic zinc carbonate, and the like are used. In addition, if necessary, inorganic fillers may be added, and powders such as calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), alumina (aluminum oxide), etc. may be mentioned. Usually, it is 5 to 60% by weight. The colorant is added to give the base material 2 the color necessary for the decorative sheet 1 and may be either transparent coloring or opaque (concealing) coloring. In general, in order to conceal the adherend. Opaque coloring is preferred.

  Known heat stabilizers such as phenolic, sulfite-based, phenylalkane-based, physphite-based, and amine-based ones can be used, and are used to improve the prevention of deterioration such as thermal discoloration during heat processing. . A flame retardant is added when imparting flame retardancy, and powders such as aluminum hydroxide and magnesium hydroxide are used. The ultraviolet absorber is for imparting good weather resistance (light resistance) to the resin, and is an organic substance such as benzotriazole, benzophenone, salicylic acid ester, or particulate zinc oxide having a diameter of 0.2 μm or less, Inorganic substances such as cerium oxide and titanium oxide are used. In addition, a reactive ultraviolet absorber in which an acryloyl group or a methacryloyl group is introduced into the benzotriazole skeleton is also used. In addition, the addition amount of these ultraviolet absorbers is about 0.5 to 10 weight% normally. The radical scavenger is for further preventing deterioration due to ultraviolet rays and improving weather resistance, and includes bis- (2,2,6,6-tetramethyl-4-biperidinyl) sebacate and bis- (N-methyl). -2,2,6,6-tetramethyl-4-biperidinyl) sebacate, and other hindered radical scavengers such as compounds disclosed in JP-B-4-82625, biperidinyl radical scavengers, etc. Is done.

  The base material 2 can be obtained by forming a film obtained by arbitrarily selecting and blending the above materials by a conventional method such as calendering. The thickness of the base material 2 is 10-200 micrometers, Preferably it is about 50-100 micrometers.

  In addition to the base material 2 made of the polyolefin resin described above, a woven or non-woven fabric using an organic resin such as polyester or vinylon, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, an ethylene-vinyl acetate copolymer. , Vinyl resins such as ethylene-vinyl alcohol copolymer, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate, polymethyl acrylate and polyethyl methacrylate, polystyrene, acrylonitrile butadiene It is also possible to use a sheet or film made of a resin such as a styrene copolymer (ABS), cellulose triacetate, cellophane, or polycarbonate. In addition, thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, fine paper, coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, etc. A so-called vinyl wallpaper original fabric obtained by sol coating or dry laminating vinyl can be used. It is also possible to use a sheet or film made of inorganic fibers such as glass fibers, asbestos, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers. Moreover, metal foils, such as aluminum, iron, stainless steel, copper, etc. can also be used. Further, a material obtained by laminating a plurality of such base material materials can be used as the base material 2.

  As for the base material 2, it is preferable that the single side | surface or both surfaces carry out an easily bonding process. Preferable examples of the easy adhesion treatment include corona discharge treatment, plasma treatment, ozone treatment, and flame treatment. When such a process is performed on the base material 2, adhesion with the ink layer 11 and the first primer layer 10 to be formed later is improved. In particular, since carboxyl groups are generated on the surface of the substrate 2 subjected to such treatment, the ink layer 11 or the first primer layer 10 is an aqueous coating agent containing an aqueous compound having a carbodiimide group. When formed, the carboxyl group on the substrate 2 reacts with the carbodiimide group in the ink layer 11 or the like, and the adhesion between the substrate 2 and the ink layer 11 or the like tends to become stronger. Moreover, you may form an easily bonding layer (it is also called a primer layer or an anchor layer) on the base material 2 as an easily bonding process. As the easy-adhesion layer, a resin layer formed of a resin in which a carboxyl group or an amino group is introduced into a resin such as an acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, urethane resin, chlorinated polypropylene, or polyethylene chloride. Can be mentioned. When an easy-adhesion layer is formed on the substrate 2, carboxyl groups and amino groups are generated on the surface of the substrate 2, so that the substrate 2, the ink layer 11, and the first layer are the same as described above. The adhesion with the primer layer 10 can be further improved. In addition, it is more preferable that such an easy adhesion process is performed on both surfaces of the base material 2.

(Ink layer)
The ink layer 11 is an essential layer in the decorative sheet 1 of the present invention, and is composed of the solid ink layer 3 and / or the pattern ink layer 4.

  As shown in FIG. 1, the solid ink layer 3 is provided for the purpose of concealing the background of the substrate 2, and is usually formed as a solid ink layer having no pattern. The pattern ink layer 4 generally has a pattern or color consisting of a wood grain pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric pattern, etc., depending on figures, characters, symbols, colors, or combinations thereof. On the layer 3, it is formed as a planar, concavo-convex, or convex (see FIG. 1) layer. In some cases, the pattern ink layer 4 also functions as the solid ink layer 3. In this case, the pattern ink layer 4 becomes the solid ink layer 3.

  The ink layer 11 composed of the solid ink layer 3 and / or the pattern ink layer 4 may be provided on the entire surface of the substrate 2 or may be partially provided. Further, as shown in FIG. 1, the ink layer 11 may be composed of a solid ink layer 3 provided on the entire surface of the substrate 2 and a pattern ink layer 4 partially provided on the surface of the solid ink layer 3. it can.

  In the decorative sheet of the present invention, the ink layer 11 is an aqueous coating agent containing an aqueous compound having two or more carbodiimide groups in one molecule (hereinafter referred to as “aqueous coating agent for ink layer”). "). Since the VOC in the decorative sheet 1 can be reduced by forming the ink layer 11 with the aqueous coating agent for the ink layer, the safety of the working environment of the decorative sheet 1 and the safety of the living space can be improved. Can do. In addition, since the ink layer 11 is a strong layer due to the action of an aqueous compound having a carbodiimide group in the aqueous coating agent for the ink layer, the interlayer adhesion between the substrate 2 and the transparent resin layer 6, the ink layer 11 and it Adhesion with adjacent layers (base material 2 and adhesive layer 5) is likely to be improved.

  When the adhesive layer 5 is formed of an aqueous coating agent containing an aqueous compound having two or more carbodiimide groups in one molecule, the ink layer 11 is other than the aqueous coating agent for ink layers. You may form with the other coating agent. Here, from the viewpoint of improving environmental safety, interlayer adhesion, and the like, an aqueous coating in which both the ink layer 11 and the adhesive layer 5 contain an aqueous compound having two or more carbodiimide groups in one molecule. It is preferable that it is formed with an agent.

  In the present invention, it is preferable that either one or both of the solid ink layer 3 and the pattern ink layer 4 are formed of an aqueous coating agent for an ink layer, and both of them are formed of an aqueous coating agent for an ink layer. It is particularly preferable.

  A water-based coating agent for an ink layer is composed of an aqueous resin as a main agent, an aqueous compound having two or more carbodiimide groups in one molecule, various additives such as a colorant, water or water and alcohol, and the like. A coating agent prepared by dissolving or uniformly dispersing in a mixed solvent comprising: As used herein, the term “aqueous resin” refers to a water-soluble resin, a water-soluble resin, a water-dispersible resin, a water-dispersed resin, or the like. To do.

  The water-based resin that is the main agent is polyurethane resin, polyester resin, acrylic resin, polyvinyl resin, polybutadiene resin, polyvinyl chloride resin, chlorinated polypropylene resin, polyethylene resin, polystyrene resin, styrene-acrylate. A resin in which a hydrophilic atomic group (including an atomic group that can be rendered hydrophilic by neutralization) is introduced into a resin such as an alcohol adduct of a styrene-based copolymer resin, a rosin-based resin, or a styrene-maleic anhydride-based copolymer resin, or cellulose Based resins and the like. Such an aqueous resin may be used alone or in combination.

  It is preferable to use an aqueous urethane resin (referred to as a resin in which a hydrophilic atomic group is introduced into a urethane resin; the same shall apply hereinafter) as an aqueous resin as a main ingredient. When an aqueous urethane-based resin is used as the main agent, the interlayer adhesion between the substrate 2 and the transparent resin layer 6 and the adhesion between the ink layer 11 and the adjacent layer can be further improved. The water-based urethane resin may be used by being mixed with another water-based resin. When the water-based urethane resin is used by being mixed with another water-based resin, the interlayer adhesion between the substrate 2 and the transparent resin layer 6 is improved. From the viewpoint, the urethane resin component is contained in an aqueous resin component of the ink layer 11 formed by applying a water-based coating agent and drying the coating film so as to contain 25% by weight or more, more preferably 50% by weight or more. It is preferable to prepare an aqueous coating agent.

  Examples of the hydrophilic atomic group include an anionic group such as a carboxyl group, a sulfonic acid group, a sulfonate group or a phosphoric acid group, a cationic group such as a tertiary amino group or a quaternary amino group, or ethylene oxide. Nonionic groups such as repeating units can be mentioned, and among them, anionic groups such as carboxyl group, sulfonic acid group and phosphoric acid group, and cationic groups such as amino group are preferable. Since these anionic groups and cationic groups have high reactivity with the carbodiimide group of the aqueous compound as will be described later, the carbodiimide group and these hydrophilic atomic groups undergo a cross-linking reaction to cause water in the ink layer. The number of unreacted hydrophilic atomic groups that are likely to adsorb is reduced. As a result, the water resistance, moist heat resistance and weather resistance of the decorative sheet 1 are improved, and the interlayer adhesion between the base material 2 and the transparent resin layer 6 and the ink layer due to the hydrophilic atomic group adsorbing moisture in the air and the like. It can suppress that the adhesiveness of 11 and the layer adjacent to it falls with time. Since the carbodiimide group is also reactive with the neutralized hydrophilic atomic group, such an effect can be obtained even when the hydrophilic atomic group of the aqueous resin is neutralized as described later.

  In order to introduce a hydrophilic atomic group into the resin exemplified above, a compound having a hydrophilic atomic group may be copolymerized when the above resin is produced by polymerization.

  The hydrophilic atomic group introduced into the resin is preferably neutralized with a neutralizing agent as necessary from the viewpoint of easily dissolving or dispersing the aqueous resin in water. The neutralizing agent is not particularly limited as long as it can neutralize or ionize the hydrophilic atomic group. For example, as the neutralizing agent when the hydrophilic atomic group is an anionic atomic group, a non-volatile base such as sodium hydroxide or potassium hydroxide, or a tertiary amine such as trimethylamine, triethylamine, or triethanolamine Or volatile bases, such as ammonia, are mentioned. Further, as the neutralizing agent when the hydrophilic atomic group is a cationic atomic group, it is possible to use an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as formic acid, acetic acid, lactic acid, citric acid or tartaric acid. it can. In place of the neutralizing agent, methyl chloride, methyl bromide, dimethyl sulfate, diethyl sulfate, benzyl chloride, p-nitrobenzyl chloride, benzyl bromide, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, bromobutane, etc. A quaternizing agent may be used.

  The aqueous resin which is the main component of the aqueous coating agent for the ink layer has a functional group having reactivity with a carbodiimide group because it is crosslinked by an aqueous compound having a carbodiimide group. Examples of such a functional group include an anionic group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, a cationic group such as an amino group, and a nonionic group such as a hydroxyl group. From the viewpoint of reactivity with a carbodiimide group Therefore, an anionic group is preferably mentioned. In addition, as described above, when the hydrophilic atomic group of the aqueous resin in the aqueous coating agent for an ink layer is such a functional group, the carbodiimide group reacts with the hydrophilic atomic group. The aqueous resin is cross-linked.

  An aqueous compound having two or more carbodiimide groups in one molecule includes an isocyanate compound (A) having two or more isocyanate groups bonded to carbon of a methylene group in one molecule, and a fat other than the isocyanate compound of (A). It is produced by bonding a monofunctional water-soluble or water-dispersible organic compound (C) to a terminal isocyanate group of a compound obtained by subjecting a cyclic or aliphatic diisocyanate compound (B) to decarbonization condensation reaction. The main component is a carbodiimide compound.

  The isocyanate compound (A) has two or more isocyanates bonded to carbon of a methylene group in the molecule, and a bifunctional diisocyanate compound is particularly preferably used. Further, as the isocyanate compound (A), an isocyanate compound having three or more isocyanate groups can be used in combination with a diisocyanate compound. This isocyanate compound may be any of an aliphatic isocyanate compound, an alicyclic isocyanate compound, and an aromatic isocyanate compound. Examples of such isocyanate compounds include hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (H6XDI), xylylene diisocyanate (XDI), 2,2,4-trimethylhexamethylene diisocyanate (TMHDI), 1,12- One kind selected from diisocyanate dodecane (DDI), norbornane diisocyanate (NBDI) and 2,4-bis- (8-isocyanate octyl) -1,3-dioctylcyclobutane (OCDI) is used alone or in combination of two or more kinds. be able to.

  The isocyanate compound (B) is an alicyclic isocyanate compound or an aliphatic isocyanate compound other than the isocyanate compound (A), and it is particularly preferable to use a diisocyanate compound having two isocyanate groups in the molecule. As such an isocyanate compound, for example, one kind selected from 4,4′-dicyclohexylmethane diisocyanate (HMDI), tetramethylxylylene diisocyanate (TMXDI), and isophorone diisocyanate (IPDI) may be used alone or in combination of two or more kinds. Can be used.

  The mixing ratio of the isocyanate compound of (A) and the isocyanate compound of (B) is the molar ratio of the isocyanate group possessed by the isocyanate compound of (A) and the isocyanate group possessed by the isocyanate compound of (B) (isocyanate of (A) Compound / (B) isocyanate compound) is preferably 1/20 to 50/1, and more preferably 1/10 to 20/1. When the mixing ratio exceeds 50/1, the pot life of the aqueous coating agent in which the resulting compound having a carbodiimide group is used tends to be short, and handling tends to be difficult. In addition, when the mixing ratio is less than 1/20, the crosslinking reactivity of the obtained aqueous compound having a carbodiimide group may be lowered.

  The monofunctional water-soluble or water-dispersible organic compound (C) reacts with the terminal isocyanate group of the carbodiimide compound derived from the isocyanate compound (A) and the isocyanate compound (B) to make the carbodiimide compound water-soluble. Or for water dispersibility. Such a water-soluble or water-dispersible organic compound has one group (functional group) that reacts with an isocyanate group, such as a hydroxyl group, a carboxyl group, an amino group, or a sulfonic acid group, and is dissolved or dispersed in water. Anything is possible. As such a monofunctional water-soluble or water-dispersible organic compound, for example, it is produced from a bifunctional water-soluble or water-dispersible organic compound having preferably each OH group at the terminal, such as polyethylene glycol and polypropylene glycol. Examples thereof include monoalkyl esters and monoalkyl ethers, or monofunctional organic compounds having a cationic group or an anionic group. Specific examples of the monofunctional water-soluble or water-dispersible organic compound include polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, and the like.

  The mixing ratio of the water-soluble or water-dispersible organic compound (C) and the isocyanate compound (A) and (B) is reactive with the isocyanate group of the water-soluble or water-dispersible organic compound (C). The ratio of the functional group possessed to the total isocyanate groups of the isocyanate compounds (A) and (B) (functional group reactive with the isocyanate group possessed by the water-soluble or water-dispersible organic compound (C) / (A ) And (B) all isocyanate groups), 1.1 / 1 to 16/1 (theoretical carbodiimide polymerization degree is n = 0.1 to 15), preferably 1.5 / 1 to 11/1. (Same polymerization degree n = 0.5 to 10), more preferably 2/1 to 6/1 (same polymerization degree n = 1 to 5). When the mixing ratio is less than 1.1 / 1, the affinity of the aqueous compound having a carbodiimide group for water becomes too high, and the water resistance of the decorative sheet 1 may be lowered. On the other hand, when the mixing ratio exceeds 16/1, an aqueous compound having a carbodiimide group is difficult to dissolve or disperse in water, so that the effect as a crosslinking agent may be lowered.

  The average number of functional groups of the aqueous compound having a carbodiimide group is preferably 2 to 15, and particularly preferably 3 to 8. When the average functional group number of the aqueous compound having a carbodiimide group is less than 2, it is difficult to improve the interlayer adhesion between the substrate 2 and the transparent resin layer 6 because the crosslinkability of the aqueous compound is reduced. It becomes difficult to improve the water resistance and moisture and heat resistance of the decorative sheet 1. When the average number of functional groups of an aqueous compound having a carbodiimide group exceeds 15, the aqueous compound is difficult to disperse or dissolve in water. In order to dissolve this aqueous compound in water, a decorative sheet is used. There is a problem that the water-soluble or water-dispersible organic compound (C) described above must be mixed in such a mixing ratio that lowers the water resistance and humidity resistance.

  The amount of the crosslinking agent component in the aqueous coating agent for the ink layer varies depending on the type of the resin component used, but is generally 0.2 to 200 parts by weight with respect to 100 parts by weight of the resin component. It is preferably 5 to 100 parts by weight.

  As the water that is the solvent of the aqueous coating agent for the ink layer, industrial water of a grade that has been conventionally used for aqueous coating agents is used. A mixed solvent composed of water and alcohol can also be used as a solvent for the aqueous coating agent. Examples of alcohols constituting such a mixed solvent include lower alcohols such as ethanol, isopropyl alcohol and N-propyl alcohol, glycols and esters thereof. These solvents such as lower alcohols, glycols and esters thereof are used for the purpose of improving the fluidity of the aqueous coating agent, improving the wettability of the substrate 2 as an object to be coated, and adjusting the drying property. The type, amount used, etc. are determined according to the purpose. The water-based coating agent used in the present invention does not use high-risk aromatic hydrocarbon organic volatile substances such as benzene, toluene, and xylene, and suppresses the use of other organic solvents. Therefore, the occurrence of VOC can be reduced.

  In a mixed solvent composed of water and alcohol, the mixing ratio of water: alcohol and the like (for example, isopropyl alcohol, methanol, ethanol, n-propyl alcohol, etc.) = 20:80 to 100: 0. Can be adjusted in range.

  The aqueous coating agent used for the solid ink layer 3 and the pattern ink layer 4 is mixed with a colorant such as a color pigment or a dye. As the coloring pigment, a commonly used organic or inorganic pigment can be used. Of these colored pigments, yellow pigments include azo pigments such as monoazo, disazo, polyazo, organic pigments such as quinophthalone and isoindolinone, inorganic materials such as chrome lead, yellow iron oxide, cadmium yellow, titanium yellow, and antimony yellow. Pigments can be used. As the red pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals, vermilion, cadmium red and chrome vermilion can be used. As the blue pigment, organic pigments such as phthalocyanine blue and indanthrene blue, and inorganic pigments such as bitumen, ultramarine blue, and cobalt blue can be used. Moreover, as a black pigment, organic pigments, such as aniline black, and inorganic pigments, such as carbon black, can be used. As the white pigment, inorganic pigments such as titanium dioxide, zinc white, and antimony trioxide can be used. Water-based coating agents for ink layers include fillers such as silica, volume pigments such as organic beads, neutralizers, surfactants, waxes, dispersants, antifoaming agents, leveling agents, stabilizers, and fillers. In addition, additives such as a lubricant, a lubricant, an antioxidant, a light stabilizer, and an ultraviolet absorber may be optionally added.

  The ink layer 11 is formed by coating the base material 2 with an aqueous coating agent for an ink layer prepared by sufficiently mixing the above materials with water or an aqueous mixed solvent composed of water and alcohol with a mixer. Or after printing etc., it forms by drying a coating film. More specifically, the solid ink layer 3 is formed by coating or printing a solid ink layer aqueous coating agent on the substrate 2 and then drying and curing. The pattern ink layer 4 is an aqueous coating agent for the pattern ink layer. Is printed on the solid ink layer 3 and then dried and cured. Here, when the surface of the substrate 2 on which the ink layer 11 is formed is subjected to an easy adhesion treatment, the adhesion between the ink layer 11 and the substrate 2 can be improved as described above. it can. As the coating method, for example, roll coat, curtain flow coat, wire bar coat, reverse coat, gravure coat, gravure reverse coat, air knife coat, kiss coat, blade coat, smooth coat, comma coat, spray coat, pouring coat, A method such as brushing can be used. In addition, as printing methods, various known methods such as relief printing such as gravure, letterpress and flexographic printing, lithographic printing such as lithographic offset and dilitho printing, stencil printing such as silk screen, electrostatic printing and ink jet printing are used. Can do. In addition, the film thickness after drying of a solid ink layer is about 0.1-10 micrometers. The film thickness after drying of the pattern ink layer is about 0 to 10 μm. A film thickness of 0 μm after drying the pattern ink layer means that the pattern ink layer is not formed.

  In order to sufficiently perform the crosslinking reaction of the crosslinking agent in the ink layer 11, a curing treatment is usually performed at the stage where all the layers constituting the decorative sheet are laminated. The ink layer 11 formed with the water-based coating agent for the ink layer is easily crosslinked even when the curing treatment temperature is 5 to 50 ° C. and the curing treatment time is 3 to 7 days. Even in the curing treatment, the interlayer adhesion between the substrate 2 and the transparent resin layer 6 is likely to be improved.

  By forming the ink layer 11 with such an aqueous coating agent for an ink layer, the interlayer adhesion between the substrate 2 and the transparent resin layer 6, the adhesion between the ink layer and the adjacent layer, and the decorative sheet 1 It is easy to improve safety and water resistance. Further, in such an aqueous coating agent for an ink layer, a carbodiimide group is relatively difficult to react with a hydroxyl group, so that a crosslinking agent and water as a solvent hardly react. Therefore, compared with the case where an aqueous compound having an isocyanate group that easily reacts with a hydroxyl group is used as the cross-linking agent, there is an effect that the pot life of the coating agent becomes longer. Therefore, the water-based coating agent for the ink layer is difficult to inhibit the action of the cross-linking agent even if the time from preparation to use is relatively long, and as a result, stable coating work is possible. 2 and the transparent resin layer 6 are easily stabilized. In particular, in the formation of the ink layer 11, conventionally, since the pot life of the water-based coating agent is short, the coating agent cannot be prepared and needs to be re-created sequentially, so that it is difficult to match each color. There was a problem. Although such a problem becomes a factor which reduces the designability of the decorative sheet 1 remarkably, such a problem can be eliminated by prolonging a pot life by this invention.

  Furthermore, since an aqueous compound having a carbodiimide group is low in skin irritation and has a negative mutagenicity, even if an unreacted cross-linking agent remains in the ink layer, the cosmetic sheet 1 is harmful to the human body. Is easily suppressed. In general, when a by-product generated by the reaction between the cross-linking agent and the resin component remains on the decorative sheet 1, it may cause a problem as a harmful effect on the human body, but the carbodiimide group is a by-product during the reaction. Such a problem is unlikely to occur.

  The ink layer 11 may be formed of a coating agent other than the aqueous coating agent for the ink layer as described above. Examples of such a coating agent include an aqueous coating agent containing a crosslinking agent other than an aqueous compound having two or more carbodiimide groups in one molecule. As the crosslinking agent in this case, for example, an aqueous compound having at least two isocyanate groups in one molecule is preferably exemplified. Moreover, the aqueous coating agent which does not contain a crosslinking agent can also be used as such a coating agent.

(Adhesive layer)
As shown in FIG. 1, the adhesive layer 5 is provided between the ink layer 11 and the transparent resin layer 6 to improve the adhesion between the substrate 2 on which the ink layer 11 is formed and the transparent resin layer 6. It has a role as a primer layer or an anchor layer, and has an effect of improving durability and long-term appearance maintenance. Such an action can hold the formed pattern for a long time and is extremely effective.

  In the present invention, like the ink layer 11, the adhesive layer 5 is an aqueous coating agent containing an aqueous compound having two or more carbodiimide groups in one molecule (hereinafter referred to as "adhesive"). It is preferably formed of “water-based coating agent for layer”. By forming the adhesive layer 5 with such an aqueous coating agent for an adhesive layer, the safety of the working environment of the decorative sheet 1 and the safety of the living space can be improved. Moreover, since the adhesive layer 11 formed with such an aqueous coating agent for an adhesive layer becomes a strong layer by the action of an aqueous compound having a carbodiimide group (crosslinking agent), the base material 2 and the transparent resin layer 6 Interlayer adhesion is easy to improve. In addition, when the ink layer 11 is formed with said aqueous coating agent for ink layers, the adhesive layer 5 may be formed with other coating agents other than the aqueous coating agent for adhesive layers. Good. As such a coating agent, for example, an aqueous coating agent containing an aqueous compound having at least two or more isocyanate groups in one molecule is preferably exemplified.

  A water-based coating agent for an adhesive layer is a mixture of a water-based resin as a main agent, a water-based compound having two or more carbodiimide groups in one molecule, various additives, etc. with water or water and alcohol. It is a coating agent prepared by dissolving or uniformly dispersing in a solvent. As the aqueous resin that is the main agent, the same aqueous resin as the aqueous coating agent for the ink layer can be used, and it is preferable to use an aqueous urethane resin or an aqueous polyester resin. Further, like the aqueous coating agent for the ink layer, the hydrophilic atomic group possessed by the aqueous resin is preferably an anionic group such as a carboxyl group or a sulfonic acid group. In that case, the carbodiimide group possessed by the aqueous compound Reacts with the hydrophilic atomic group, thereby improving the water resistance and heat-and-moisture resistance of the decorative sheet 1. As the aqueous compound having a carbodiimide group, an aqueous resin similar to the aqueous coating agent for ink layers can be used, and the blending amount thereof is the same as that of the aqueous coating agent for ink layers.

  The kind of water and the mixed solvent composed of water and alcohol constituting the aqueous coating agent for the adhesive layer, the blending ratio, and the effects are also the same as those of the aqueous coating agent for the ink layer described above, and VOC. Can be suppressed. In consideration of the function as the adhesive layer, the water-based coating agent for the adhesive layer includes colorants, waxes, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, etc. An additive may be added.

  The adhesive layer 5 is formed by coating or printing the above-described aqueous coating agent on the ink layer 11 and then drying the coating film. As the coating method, for example, roll coat, curtain flow coat, wire bar coat, reverse coat, gravure coat, gravure reverse coat, air knife coat, kiss coat, blade coat, smooth coat, comma coat, spray coat, pouring coat, A method such as brushing can be used. The thickness of the adhesive layer 5 after drying is about 0.3 to 30 μm.

  By forming the adhesive layer 5 with such an aqueous coating agent for an adhesive layer, interlayer adhesion between the base material 2 and the transparent resin layer 6, adhesion between the adhesive layer 5 and the adjacent layer, and It is easy to improve the safety and water resistance of the decorative sheet 1. Further, such an aqueous coating agent for an adhesive layer has an effect that the pot life of the coating agent is increased for the same reason as the aqueous coating agent for an ink layer. Therefore, the water-based coating agent for the adhesive layer is hardly hindered by the action of the crosslinking agent even if the time from preparation to use is relatively long, and as a result, stable coating work is possible. Interlayer adhesion between the material 2 and the transparent resin layer 6 is easily stabilized. Furthermore, by forming the adhesive layer 5 with such an aqueous coating agent for an adhesive layer, for the same reason as the ink layer 11 formed with the aqueous coating agent for an ink layer, Evil is easily suppressed.

  In addition, when the transparent resin layer 6 adjacent to the adhesive layer 5 formed by the aqueous coating agent for the adhesive layer is formed by melt-extruding a resin containing maleic acid-modified polypropylene resin, Adhesion between the agent layer 5 and the transparent resin layer 6 is improved. Details thereof will be described in the paragraph of the transparent resin layer 6.

(Transparent resin layer)
The transparent resin layer 6 is also referred to as a top resin layer, and the adhesive layer 5 is used for the purpose of protecting the ink layer 11 from scratches, improving the surface strength of the decorative sheet 1, and imparting a feeling of painting. On the ink layer 11.

  The resin constituting the transparent resin layer 6 is not particularly limited as long as it is a transparent resin that is formed in close contact with the ink layer 11 via the adhesive layer 5 described above. For example, a transparent olefin-based resin such as transparent polypropylene is used. A resin, a transparent acrylic resin, a transparent polycarbonate resin, or the like can be preferably exemplified. In addition, the same constituent materials as those of the base material 2 described above can be used.

  The resin forming the transparent resin layer 6 can be formed by adding known additives such as a colorant, a filler, an ultraviolet absorber, a light stabilizer, and a matting agent, if necessary. It is possible to obtain a transparent resin layer or a transparent resin layer having ultraviolet absorption characteristics.

  As a method for forming the transparent resin layer 6, a transparent resin sheet formed separately can be laminated on the adhesive layer 5, or can be formed by a melt extrusion coating method, or can be laminated by other known methods. .

  Further, as shown in FIG. 2, the transparent resin layer 6 may have a multilayer structure of two or more layers. The transparent resin layer 16 formed by laminating two or more layers is advantageous in that the transparent resin layer 6 ′ on the substrate 2 side and the transparent resin layer 6 ″ on the surface protective layer side can have different functions and effects. Specifically, by forming the transparent resin layer 6 ″ on the surface protective layer side with a resin mainly composed of a fluorine-based resin such as vinylidene fluoride, a surface function such as excellent stain resistance is imparted. The transparent resin layer 6 ′ on the substrate side is formed of a thermoplastic acrylic resin or the like, and can be laminated so that the adhesion between the adhesive layer 5 and the like can be improved. Further, by forming the transparent resin layer 6 ′ on the substrate side with a polypropylene resin containing an elastomer, the transparent resin layer 6 ′ can be laminated so that the weather resistance and the adhesion can be improved.

The two or more transparent resin layers 16 can be formed by a melt coextrusion coating method using a plurality of resin compositions, or by various lamination methods such as dry lamination and thermal lamination. At this time, as shown in FIG. 3, a transparent resin layer 16 composed of two or more layers can be formed via an adhesive layer 12 acting as a primer layer or an anchor layer. In this case, the adhesive layer 12 is formed by melt coextrusion together with the transparent resin layers 6 ′ and 6 ″, or is formed by coating with an aqueous coating agent containing the above-described two-component aqueous urethane resin. In this case, the occurrence of VOC can be further suppressed, and the thickness of the transparent resin layer 6 can be applied at a coating amount of about 15 to 500 g / m ² so as to be about 20 to 400 μm. Work.

  The transparent resin layer 6 is preferably formed by melt-extruding a resin containing a maleic acid-modified polypropylene resin component on the surface of the adhesive layer 5 formed with an aqueous coating agent for an adhesive layer. When the transparent resin layer 6 is formed in this way, the carboxyl group of the maleic acid-modified polypropylene resin in the transparent resin layer 6 and the carbodiimide group of the aqueous compound in the adhesive layer 5 show high reactivity. Therefore, cross-linking can occur at the interface between both layers. As a result, in such a decorative sheet 1, the adhesion at the interface between the transparent resin layer 6 and the adhesive layer 5 tends to become stronger. In the case where the transparent resin layer 6 is formed by melt coextrusion, it is desirable that the resin containing the maleic acid-modified polypropylene resin is formed on the adhesive layer 5 side.

  The surface of the transparent resin layer 6 is preferably subjected to the easy adhesion treatment described in the paragraph of the substrate 2. When such a treatment is performed on the transparent resin layer 6, adhesion with the surface protective layer 9 to be formed later is improved. In particular, since a carboxyl group or an amino group is generated on the surface of the transparent resin layer 6 subjected to such treatment, the surface protective layer 9 is formed of an aqueous coating agent containing an aqueous compound having a carbodiimide group. In the case where the carboxyl group on the transparent resin layer 6 reacts with the carbodiimide group in the surface protective layer 9, the adhesion between the transparent resin layer 6 and the surface protective layer 9 becomes stronger. easy. In addition, when giving the following uneven | corrugated pattern 7 to the transparent resin layer 6, it is preferable to give an easily bonding process after giving an uneven | corrugated pattern.

(Uneven pattern)
The uneven pattern 7 is also referred to as an embossed pattern, and is formed on the surface of the transparent resin layer 6 as necessary, as shown in FIG. In addition, when two or more transparent resin layers 16 are formed as shown in FIGS. 2 and 3, the concavo-convex pattern 7 is formed on the outermost transparent resin layer 6 or the transparent resin layer other than the outermost surface is formed. Each can be formed arbitrarily.

  The uneven pattern 7 is not particularly limited as long as it is a pattern according to the use of the decorative sheet 1. For example, wood grain conduit groove, wood grain annual ring irregularity, floatation annual ring irregularity, wood grain irregularity, sand grain, satin, hairline, line-like groove, granite cleaved surface texture, textured surface texture, skin squeezing, text, geometry You can list patterns such as academic patterns.

  Examples of means for forming the concavo-convex pattern 7 include an embossing method by heat and pressure and a T-die melt extrusion method. The embossing method by heat and pressure is a method in which the surface of the transparent resin layer 6 is heated and softened, the surface is pressed with an embossing plate to form an uneven pattern 7 of the embossing plate, and cooled and fixed. A known single-wafer or rotary embossing machine can be used. When forming by the embossing method, it is embossed in advance on the resin sheet to be the transparent resin layer 6 before being laminated by laminating, or at the same time as the resin sheet to be the transparent resin layer 6 is laminated (so-called doubling embossing method) Can go. When the transparent resin layer 6 is laminated by the T-die melt extrusion method, the concavo-convex pattern 7 is formed simultaneously with the formation and lamination of the transparent resin layer 6 by using a cooling roller that also serves as a shaping roller. You can also The embossed pattern can also be formed by hairline processing, sandblasting, or the like.

(Colored layer)
The colored layer 8 is formed in the recessed portion of the concavo-convex pattern 7 by a wiping method. In the wiping method, the coating agent for the colored layer is applied to the entire surface including the recessed portion by the doctor blade coating method or the knife coating method, and then the coating agent for the colored layer is removed from the surface other than the recessed portion. In this method, the colored layer 8 is formed only in the recessed portion. Examples of coating agents for the colored layer include inks and emulsions composed of colored pigments such as organic pigments, inorganic pigments and glitter pigments, and binder resins such as thermoplastic resins, thermosetting resins and ionizing radiation curable resins. A water-type ink of a mold can be used. Moreover, the above-mentioned aqueous coating agent for an ink layer can also be preferably used, and in such a case, it is more preferable from the viewpoint of environmental safety.

(Surface protective layer)
The surface protective layer 9 is also referred to as a topcoat layer or an overprint layer (OP layer), and covers the surface of the concave portion that forms the concavo-convex pattern 7 or the colored layer 8 that is formed in the concave portion to protect the decorative sheet 1. It is provided for the purpose of doing.

  The surface protective layer 9 is formed of an aqueous coating agent containing an aqueous compound having two or more carbodiimide groups in one molecule (hereinafter, this coating agent is referred to as “aqueous coating agent for surface protective layer”). It is preferred that By forming the surface protective layer 9 with such a water-based coating agent for the surface protective layer, the safety of the working environment of the decorative sheet 1 and the safety of the living space can be improved. Since the surface protective layer 9 formed with such a water-based coating agent for the surface protective layer becomes a strong layer by the action of the crosslinking agent, the surface protective layer 9 and the layer adjacent to the surface protective layer 9 (transparent resin layer 6) are in close contact with each other. Therefore, the scratch resistance of the decorative sheet 1 is easily improved. In addition, when the aqueous coating agent for the surface protective layer has a functional group that easily reacts with a carbodiimide group (such as a carboxyl group or a sulfonic acid group) as a hydrophilic atomic group, the hydrophilic atomic group that easily adsorbs water By the reaction of the carbodiimide group, the durability of the surface protective layer with respect to water such as water resistance and moisture heat resistance can be improved. In particular, since the surface protective layer 9 is the outermost surface of the decorative sheet 1, it is easy to effectively improve the water resistance and moist heat resistance of the decorative sheet 1.

  A water-based coating agent for a surface protective layer is a mixture of water resin, which is a main component, an aqueous compound having two or more carbodiimide groups in one molecule, various additives, and the like with water or water and alcohol. It is a coating agent prepared by dissolving or uniformly dispersing in a solvent. As the aqueous resin that is the main agent, the same aqueous resin as the aqueous coating agent for the ink layer can be used. As the aqueous compound having a carbodiimide group, an aqueous resin similar to the aqueous coating agent for ink layers can be used, and the blending amount thereof is the same as that of the aqueous coating agent for ink layers.

  The kind, the mixture ratio, and the effect of the water and the mixed solvent composed of water and alcohol constituting the water-based coating agent for the surface protective layer are the same as those of the water-based coating agent for the ink layer described above. In consideration of the function as the surface protective layer, the water-based coating agent for the surface protective layer includes colorants, waxes, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, etc. Additives may be added. In addition, a known matting agent such as silica is added to the water-based coating agent for the surface protective layer in order to adjust the gloss of the surface protective layer, or an ultraviolet ray is applied to impart better weather resistance or light resistance. An absorber or a light stabilizer may be added. As the ultraviolet absorber, organic substances such as benzotriazole, benzophenone, and salicylic acid ester, or inorganic substances such as fine particle zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used. As the light stabilizer, hindered amine radical scavengers such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, radical scavengers such as piperidine radical scavengers, and the like can be used. These ultraviolet absorbers and light stabilizers are usually added so as to be about 0.5 to 10% by weight, and it is generally preferable to use an ultraviolet absorber and a light stabilizer in combination. In addition, a flame retardant that is a powder of aluminum hydroxide, magnesium hydroxide, or the like may be added to the aqueous coating agent for the surface protective layer. The amount of the flame retardant added is 100 parts by weight of the aqueous resin component, About 10-150 weight part is preferable.

  The surface protective layer 9 is formed by coating or printing the above-described aqueous coating agent for the surface protective layer on the transparent resin layer 6 and then drying the coating film. As coating methods, various known methods such as roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, comma coating, spray coating. The film can be applied such that the film thickness after drying is, for example, about 0.1 to 40 μm, preferably about 1 to 20 μm.

  By forming the surface protective layer 9 with such a water-based coating agent for the surface protective layer, the adhesion between the surface protective layer 9 and the adjacent layer, and the safety, scratch resistance, water resistance, etc. of the decorative sheet 1 are obtained. Can be improved. In addition, in such a water-based coating agent for the surface protective layer, for the same reason as the water-based coating agent for the ink layer, the coating work is facilitated by increasing the pot life of the coating agent. There exists an advantage that it is easy to obtain the decorative sheet which plays. Furthermore, by forming the surface protective layer 9 with such a water-based coating agent for the surface protective layer, for the same reason as the ink layer 11 formed with the water-based coating agent for the ink layer, Evil is easily suppressed. In particular, since the surface protective layer 9 is the outermost surface of the decorative sheet 1, it is possible to effectively suppress the harmful effects of the decorative sheet 1 on the human body.

  Here, the surface protective layer 9 may be formed of a coating agent other than the aqueous coating agent for a surface protective layer. As such a coating agent, for example, an active energy ray-curable solventless coating agent or an active energy ray-curable aqueous coating agent can be used. Also by using such a coating agent, it becomes easy to suppress the generation of VOC from the decorative sheet 1 and the residual amount of VOC in the decorative sheet 1, and improve the safety of the working environment and the safety of living space. be able to. Hereinafter, the active energy ray-curable solventless coating agent and the active energy ray-curable aqueous coating agent are referred to as “active energy ray-curable coating agent”.

  The active energy ray-curable coating agent contains an active energy ray-curable resin as a resin component. The active energy ray-curable resin is a resin that undergoes a crosslinking polymerization reaction when irradiated with active energy rays and changes to a three-dimensional polymer structure. An active energy ray means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, visible light, ultraviolet light (including near ultraviolet light, vacuum ultraviolet light, etc.), X-ray, electron beam, There are ion beams and the like, and usually ultraviolet rays and electron beams are used.

  As the active energy ray-curable resin, in the molecule, a monomer having a radically polymerizable unsaturated group such as (meth) acryloyl group, (meth) acryloyloxy group, or a cationically polymerizable functional group such as epoxy group, It consists of a prepolymer or a polymer. These monomers, prepolymers, and polymers may be used alone or as a mixture of two or more. In the active energy ray-curable aqueous coating agent, the above monomers, prepolymers and polymers are water-soluble by introducing hydrophilic atomic groups (including atomic groups that can become hydrophilic upon neutralization). Or it is water-dispersible. In the case of curing by irradiation with ultraviolet rays, a photopolymerization initiator is added as a sensitizer to the active energy ray-curable coating agent for the surface protective layer. The addition amount of the photopolymerization initiator is generally about 0.1 to 10 parts by weight with respect to 100 parts by weight of the active energy ray curable resin. In addition, when making it harden | cure by irradiating an electron beam, even if a photoinitiator is not added to the active energy ray-curable coating agent for surface protective layers, it hardens | cures sufficiently.

The surface protective layer 9 is coated with an active energy ray-curable coating agent on the transparent resin layer in the same manner as the coating method of the aqueous coating agent for the surface protective layer, and is irradiated with active energy rays. It can be obtained by curing the coating film. In addition, when the active energy ray-curable aqueous coating agent is used, the active energy ray is irradiated after the coating film is dried after the coating agent is applied. 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 a wavelength of ultraviolet rays, a wavelength range of 1900 to 3800 mm (same as 10 ⁻¹ nm) is mainly used, and as an electron beam source, cockroft Walton type, bande graft type, resonant transformer type, insulation Various electron beam accelerators of a core transformer type, a linear type, a dynamitron type, and a high frequency type lamp are used, and those that irradiate electrons having energy of 50 to 1000 keV, preferably 100 to 300 keV can be used.

  As the coating agent other than the aqueous coating agent for the surface protective layer, an aqueous coating agent containing an aqueous compound having an isocyanate group as a crosslinking agent is used in addition to the active energy ray-curable coating agent. You can also

(First primer layer)
The first primer layer 10 is used for the purpose of facilitating the adhesion of the decorative sheet 1 of the present invention to various adherends, and the back surface of the base material 2 (the surface on which the ink layer of the base material 2 is not formed). Optionally formed.

  In the present invention, like the ink layer 11, the first primer layer 13 is an aqueous coating agent containing an aqueous compound having two or more carbodiimide groups in one molecule (hereinafter referred to as "water-based coating agent" It is preferably formed of “aqueous coating agent for first primer layer”. Since the 1st primer layer 13 formed with such a water-based coating agent turns into a firm layer by the effect | action of a crosslinking agent, adhesiveness with the base material 2 is easy to improve. In addition, the 1st primer layer 10 may be formed with other coating agents other than the aqueous | water-based coating agent for 1st primer layers. Examples of such a coating agent include a one-component aqueous coating agent containing an aqueous resin component and an aqueous coating agent containing an aqueous compound having at least two isocyanate groups in one molecule. Preferably mentioned.

  The first primer layer aqueous coating agent is composed of an aqueous resin as a main component, an aqueous compound having two or more carbodiimide groups in one molecule, various additives, and the like, water or water and alcohol. It is a coating agent prepared by dissolving or uniformly dispersing in a mixed solvent. As the aqueous resin as the main agent, the same aqueous resin as the aqueous coating agent for the ink layer can be used, and an aqueous urethane resin or an aqueous polyester resin is preferably used. Further, like the aqueous coating agent for the ink layer, the hydrophilic atomic group possessed by the aqueous resin is preferably an anionic group such as a carboxyl group or a sulfonic acid group. In that case, the carbodiimide group possessed by the aqueous compound Reacts with the hydrophilic atomic group, thereby improving the water resistance of the decorative sheet 1. As the aqueous compound having a carbodiimide group, an aqueous resin similar to the aqueous coating agent for ink layers can be used, and the blending amount thereof is the same as that of the aqueous coating agent for ink layers.

  About the kind of water and the mixed solvent consisting of water and alcohol constituting the first primer layer aqueous coating agent, the blending ratio, and the action and effect are the same as in the case of the aqueous coating agent for ink layer described above, Generation of VOC can be suppressed. Additives such as colorants, waxes, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, etc. may be added to the aqueous coating agent for the adhesive layer. .

  The first primer layer 10 is formed by applying or printing the above-mentioned first primer layer aqueous coating agent on the substrate 2 and drying the coating film. Here, when the surface of the substrate 2 on which the ink layer 11 is formed is subjected to an easy adhesion treatment, the adhesion between the first primer layer 10 and the substrate 2 is improved as described above. be able to. As coating methods, various known methods such as roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, comma coating, spray coating. A method such as flow coating or brush coating can be used, and the coating is performed so that the film thickness after drying is, for example, about 0.1 to 5 μm.

  By forming the first primer layer 10 with such an aqueous coating agent for the first primer layer, the adhesion between the first primer layer 10 and the adjacent layer (base material 2), and the safety of the decorative sheet 1 are obtained. In addition, water resistance and the like can be improved. In addition, in such an aqueous coating agent for the first primer layer, for the same reason as the aqueous coating agent for the ink layer, the coating work is facilitated by increasing the pot life of the coating agent. There is an advantage that it is easy to obtain a decorative sheet having an effect. Furthermore, by forming the first primer layer 10 with such a water-based coating agent for the first primer layer, the human body affected by the decorative sheet 1 for the same reason as the ink layer 11 formed with the water-based coating agent for the ink layer. It is easy to suppress harmful effects. In particular, since the surface protective layer 9 is the outermost surface on the back surface side of the decorative sheet 1, it is possible to effectively suppress the harmful effects of the decorative sheet 1 on the human body in the working environment.

(Second primer layer)
As shown in FIG. 4, the second primer layer 13 is provided between the transparent resin layer 6 and the surface protective layer 9 and has a role of improving the adhesion between the transparent resin layer 6 and the surface protective layer 9. Is. In particular, it is preferably applied when the surface protective layer 9 is formed of an active energy ray-curable coating agent, and has an effect of absorbing shrinkage (followability) when the surface protective layer 9 is cured with active energy rays. . As a result, it is possible to solve the problem of delamination based on the strain generated when the surface protective layer 9 is cured, and to improve the adhesion between the transparent resin layer 6 and the surface protective layer 9.

  In the present invention, like the ink layer 11, the second primer layer 13 is an aqueous coating agent containing an aqueous compound having two or more carbodiimide groups in one molecule (hereinafter referred to as “aqueous coating agent”). It is preferably formed of “aqueous coating agent for second primer layer”. Since the 2nd primer layer 13 formed with such a water-based coating agent turns into a firm layer by the effect | action of a crosslinking agent, the adhesiveness of the transparent resin layer 6 and the surface protective layer 9 is easy to improve. In addition, the 2nd primer layer 13 may be formed with other coating agents other than the aqueous | water-based coating agent for 2nd primer layers. Examples of such a coating agent include a one-component aqueous coating agent containing an aqueous resin component and an aqueous coating agent containing an aqueous compound having at least two isocyanate groups in one molecule. Preferably mentioned.

  The water-based coating agent for the second primer layer comprises a water-based resin as a main agent, an aqueous compound having two or more carbodiimide groups in one molecule, various additives, and the like, water or water and alcohol. It is a coating agent prepared by dissolving or uniformly dispersing in a mixed solvent. As the aqueous resin that is the main agent, the same aqueous resin as the aqueous coating agent for the ink layer can be used, and it is preferable to use an aqueous urethane resin or an aqueous polyester resin. Further, like the aqueous coating agent for the ink layer, the hydrophilic atomic group possessed by the aqueous resin is preferably an anionic group such as a carboxyl group or a sulfonic acid group. In that case, the carbodiimide group possessed by the aqueous compound Reacts with the hydrophilic atomic group, thereby improving the water resistance of the decorative sheet 1. As the aqueous compound having a carbodiimide group, an aqueous resin similar to the aqueous coating agent for ink layers can be used, and the blending amount thereof is the same as that of the aqueous coating agent for ink layers.

  About the kind of water and the mixed solvent consisting of water and alcohol constituting the second primer layer aqueous coating agent, the blending ratio, and the effects are the same as in the case of the aqueous coating agent for the ink layer described above. Generation of VOC can be suppressed. Additives such as colorants, waxes, dispersants, antifoaming agents, leveling agents, stabilizers, fillers, lubricants, lubricants, etc. may be added to the aqueous coating agent for the adhesive layer. .

  The second primer layer 13 is formed by coating or printing the above-described aqueous primer for second primer layer on the transparent resin layer 6 and drying the coating film. As coating methods, various known methods such as roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, comma coating, spray coating. A method such as flow coating or brush coating can be used, and the coating is performed so that the film thickness after drying is, for example, about 0.1 to 5 μm.

  By forming the second primer layer 13 with such a water-based coating agent for the second primer layer, the adhesion between the transparent resin layer 6 and the surface protective layer 9 and the environmental safety and water resistance of the decorative sheet 1 are improved. Can be improved. Further, in the second primer layer aqueous coating agent, for the same reason as the ink layer aqueous coating agent, the coating work is facilitated by increasing the pot life of the coating agent. There is an advantage that it is easy to obtain a decorative sheet having an effect. Further, by forming the second primer layer 13 with such a water-based coating agent for the second primer layer, the human body exerted by the decorative sheet 1 for the same reason as the ink layer 11 formed with the water-based coating agent for the ink layer. It is easy to suppress harmful effects.

(Decorative sheet)
The decorative sheet 1 of the present invention having the above-described configuration is used by being laminated on another adherend (backing material).

  As the adherend, a three-dimensional article 41 as shown in FIG. 5, an article of various shapes such as a plate 51 and a sheet (or film) such as a flat plate and a curved face as shown in FIG. 6 are targeted. Such adherends include wood boards such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), wood boards such as wood fiber board, metals such as iron and aluminum, acrylic, polyester, polystyrene, polyolefin , ABS resin, phenol resin, polyvinyl chloride resin, cellulose resin, rubber resin, glass, ceramics such as ceramics, non-cement ceramic materials such as gypsum, fine paper, Japanese paper, carbon, asbestos, titanium Nonwoven fabrics or woven fabrics made of fibers of potassium acid, glass, synthetic resin, etc. can be mentioned.

  In the relationship between the decorative sheet 1 and the adherend, if the base sheet 2 or the first primer layer 10 of the decorative sheet 1 can be directly bonded to the adherend by heat fusion or the like, the decorative sheet 1 and the adherend are attached. It can be laminated without using an adhesive, but depending on the type of the base material 2 and the first primer layer 10 of the decorative sheet 1, if it cannot be directly bonded to the adherend by heat fusion, Laminate using a suitable adhesive. Examples of the adhesive include vinyl acetate and urea adhesives.

  As a general lamination method, for example, (a) a method of laminating an adherend with a pressure roller via an adhesive, (b) Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43- As described in Japanese Patent No. 27488, etc., the decorative sheet 1 is inserted between both male and female molds for injection molding, both molds are closed, the molten resin is injected and filled from the gate of the male mold, and then cooled and resin is cooled. An injection molding simultaneous laminating method in which the decorative sheet 1 is bonded and laminated on the surface of the molded article at the same time as molding, (c) Japanese Patent Publication No. 56-45768, Japanese Patent Publication No. 60-58014, etc. A vacuum press laminating method in which the decorative sheet 1 is opposed to the surface of the molded product and the decorative sheet 1 is laminated on the molded product surface by a pressure difference caused by vacuum suction from the molded product side, (d) Japanese Patent Publication No. 61-5895 3-2666 As described in the publication, etc., the columnar adherend is supplied by a plurality of different rollers while supplying the decorative sheet 1 via an adhesive in the longitudinal direction of the columnar adherend such as a cylinder or a polygonal column. Examples include a lapping process method in which the decorative sheet 1 is sequentially pressure-bonded and laminated on a plurality of side surfaces.

  The various adherends on which the decorative sheet 1 of the present invention is laminated can be used as various decorative materials and the like by performing a predetermined molding process or the like. For example, interior decorations for buildings such as walls, ceilings, floors, surface decorations for furniture such as window frames, doors, handrails, surface decorations for furniture or cabinets for light electrical / OA equipment, vehicle interiors such as automobiles and trains, aircraft interiors, windows Uses such as glass for cosmetics are listed.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. Hereinafter, “part” means “part by weight”. The decorative sheets of Examples 1 to 8 and Comparative Examples 1 to 3 were produced.

Example 1
A polypropylene colored sheet (thickness: 60 μm) manufactured by Mitsubishi Chemical MKV Co., Ltd. is used as the base material 2 and subjected to corona discharge treatment on each of the front and back surfaces, and then an aqueous coating agent for the first primer layer having the following composition on one side. A was applied by a gravure printing method using a gravure plate having a line number of 54 lines / inch and a plate depth of 40 μm, and dried to form a first primer layer 10 of about 2 g / m ² .

Further, on the opposite side, a solid ink layer aqueous coating agent B, a pattern ink layer aqueous coating agent C, and an adhesive layer aqueous coating agent D having a line number of 54 lines / inch and a plate depth of 40 μm were blended as follows. coated using a gravure plate by gravure printing method, dried for about 2 g / ^{m 2} of Betainki layer 3, about 1.5 g / ^{m 2} of the pattern ink layer 4 are successively an adhesive layer 5 of about 3 g / ^{m 2} Formed.

Furthermore, on the adhesive layer 5, maleic acid-modified polypropylene resin and random copolymer polypropylene resin (70 μm), phenolic antioxidant 0.2 wt%, hindered amine light stabilizer 0.3 wt%, and antiblocking agent The resin added with 0.2% by weight was melted and coextruded with heat at 220 ° C. in a T-die under ozone irradiation so that the adhesive layer side became a maleic acid-modified polypropylene resin. A transparent resin layer 6 having a film thickness of the acid-modified polypropylene resin layer: 10 μm and a film thickness of the random copolymer polypropylene resin: 70 μm was laminated. The surface of the transparent resin layer 6 is subjected to unevenness 7 by hot embossing at about 160 ° C., and further subjected to corona discharge treatment on the surface where the unevenness 7 has been applied. Using a gravure plate having a number of 48 lines / inch and a plate depth of 60 μm, it was applied and dried by a gravure printing method to form a surface protective layer 9 of about 3 g / m ² . Thereafter, curing treatment (aging) was performed at a temperature of 25 ° C. for 3 days to obtain a decorative sheet of Example 1.

Water-based coating agent A for the first primer layer;
Anionic urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., trade name: F-8585D, carboxyl group neutralized with amine): 100 parts Nonionic water-dispersible carbodiimide crosslinking agent (Nisshinbo Industries, Ltd., Product name: Carbodilite E02): 15 parts Silica powder (Fuji Silysia Chemical Co., Ltd., trade name: Cicilia 380): 2 parts Water: 10 parts Isopropyl alcohol: 10 parts Aqueous coating agent B for solid ink layer;
・ Anionic urethane-based white ink (manufactured by The Inktec Co., Ltd., trade name: White for Ode WEK solid, neutralized with carboxyl group with amine): 100 parts ・ Nonionic water-dispersible carbodiimide crosslinking agent (Nisshinbo Industries, Ltd.) Product name: Carbodilite E04): 15 parts Water: 20 parts Isopropyl alcohol: 20 parts Water-based coating agent C for pattern ink layer;
・ Anionic urethane-based red ink (The Inktec Co., Ltd., trade name: Red for Ode WEK pattern, neutralized with carboxyl group with amine): 100 parts ・ Nonionic water-dispersible carbodiimide crosslinking agent (Nisshinbo Industries, Ltd.) Product name: Carbodilite E03A): 15 parts Water: 20 parts Isopropyl alcohol: 20 parts Aqueous coating agent D for adhesive layer;
-Anionic urethane resin (Nikka Chemical Co., Ltd., trade name: Evaphanol HO10, carboxyl group neutralized with amine): 100 parts-Nonionic water-dispersible carbodiimide cross-linking agent (Nisshinbo Co., Ltd., trade name) : Carbodilite E02): 15 parts Water: 5 parts Isopropyl alcohol: 5 parts Aqueous coating agent E for surface protective layer;
Anionic urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., trade name: F-8582D, carboxyl group neutralized with amine): 100 parts Nonionic water-dispersible carbodiimide crosslinking agent (Nisshinbo Industries, Ltd., Product name: Carbodilite E03A): 10 parts Silica powder (Fuji Silysia Chemical Co., Ltd., trade name: Cicilia 380): 2 parts Silicone oil (Shin-Etsu Chemical Co., Ltd., KF353): 0.5 parts Water: 5 Parts Isopropyl alcohol: 5 parts (Example 2)
In the production of the decorative sheet of Example 1, instead of the first primer layer aqueous coating agent A, the following first primer layer aqueous coating agent F was used instead of the pattern ink layer aqueous coating agent C. In the same manner as in Example 1, except that the aqueous coating agent G for pattern ink layer was replaced with the aqueous coating agent H for surface protective layer described below instead of the aqueous coating agent E for surface protective layer. A decorative sheet was obtained.

Water-based coating agent F for the first primer layer;
-Anionic urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., trade name: F-8583D, neutralized carboxyl group with amine): 100 parts-Nonionic water-dispersible isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.) : Aquanate 100): 7.5 parts Silica powder (Fuji Silysia Chemical Co., Ltd., trade name: Cicilia 380): 2 parts Water: 10 parts Isopropyl alcohol: 10 parts Aqueous coating agent G for pattern ink layer ;
・ Anionic urethane red ink (The Inktec Co., Ltd., trade name: Red for Ode WEK pattern, neutralized with carboxyl group with amine): 100 parts ・ Water: 20 parts ・ Isopropyl alcohol: 20 parts Surface Water-based coating agent H for protective layer;
Anionic urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., trade name: F-8582D, carboxyl group neutralized with amine): 100 parts Nonionic water-dispersible isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.) : Aquanate 100): 7.5 parts Silica powder (Fuji Silysia Chemical Co., Ltd., trade name: Cicilia 380): 2 parts Silicone oil (Shin-Etsu Chemical Co., Ltd., KF353): 0.5 parts Water: 5 parts ・ Isopropyl alcohol: 5 parts

(Example 3)
In the production of the decorative sheet of Example 2, the makeup of Example 3 was performed in the same manner as in Example 2 except that the following aqueous coating solution I for adhesive layer was used instead of the aqueous coating solution D for adhesive layer. A sheet was obtained.

Water-based coating agent I for adhesive layer;
Anionic urethane resin (manufactured by Nikka Chemical Co., Ltd., trade name: Evaphanol HO10, carboxyl group neutralized with amine): 100 parts Nonionic water-dispersible isocyanate crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd .: Aqua Nate 100): 15 parts

Example 4
In the production of the decorative sheet of Example 2, the decorative sheet of Example 4 was prepared in the same manner as in Example 2 except that the following solid layer aqueous coating solution J was used instead of the solid ink layer aqueous coating agent B. Obtained.

Water-based coating agent J for solid ink layer;
・ Anionic urethane-based white ink (The Inktec Co., Ltd., trade name: White for Ode WEK solid, carboxyl group neutralized with amine): 100 parts ・ Nonionic water-dispersible isocyanate crosslinking agent (Nippon Polyurethane) Industrial Co., Ltd .: Aquanate 100): 7.5 parts Water: 20 parts Isopropyl alcohol: 20 parts

(Example 5)
In the production of the decorative sheet of Example 2, the surface of the transparent resin layer 6 with the irregularities 7 is subjected to a corona discharge treatment, and the corona discharge treatment surface of the transparent resin layer 6 has the following water composition for the second primer layer: The coating agent K was applied by a gravure printing method using a gravure plate having a number of lines of 70 lines / inch and a plate depth of 30 μm, and the coating film was dried to give about 0.5 g / m ² of the second primer layer 13. Formed. Next, an electron beam curable solventless coating agent L having the following composition is heated to 60 ° C. and applied by the bar coating method on the second primer layer 13, and then an electron beam irradiation apparatus manufactured by Iwasaki Electric Co., Ltd. Using an electro curtain EC250, an electron beam was irradiated with an acceleration voltage of 150 kV and an irradiation dose of 5 Mrad under a nitrogen purge to form a surface protective layer 9 of about 3 g / m ² . Other than that was carried out similarly to Example 1, and obtained the decorative sheet of Example 5.

Aqueous coating agent K for second primer layer;
-Aqueous urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., trade name: F-8583D): 100 parts-Nonionic water-dispersible carbodiimide crosslinking agent (Nisshinbo Co., Ltd., trade name: Carbodilite E03A): 5 parts-Silica Powder (Fuji Silysia Chemical Co., Ltd., trade name: Cicilia 380): 1 part Water: 10 parts Isopropyl alcohol: 10 parts Electron beam curable solventless coating agent L;
-Polyfunctional urethane acrylate (Shin Nakamura Chemical Co., Ltd., trade name: U-15HA): 25 parts-Pentaerythritol triacrylate (Shin Nakamura Chemical Co., Ltd., trade name: A-TMMA): 20 parts Pentaerythritol monohydroxypentaacrylate (manufactured by Sartomer, trade name: SR399): 5 parts Trimethylolpropane acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: TMPTA): 50 parts Silica powder (manufactured by Fuji Silysia Chemical Ltd., Product name: Cicilia 380): 2 parts Silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF353): 0.5 parts

(Example 6)
In the production of the decorative sheet of Example 5, the UV curable solventless coating agent M having the following composition was heated to 60 ° C. on the second primer layer 13 and applied by the bar coating method, followed by UV irradiation. Using the H bulb light source of the apparatus (Fusion UV Systems Japan), the surface protective layer 9 of about 5.0 g / m ² was formed by irradiating ultraviolet rays at a dose of 500 mJ / cm ² under a nitrogen purge. Later, irregularities 7 were formed on the surface protective layer 9 by hot embossing at about 160 ° C. Otherwise, the decorative sheet of Example 6 was obtained in the same manner as Example 5.

UV curable solventless coating agent M;
Polyfunctional urethane acrylate (Shin Nakamura Chemical Co., Ltd., U-15HA): 25 parts Pentaerythritol triacrylate (Shin Nakamura Chemical Co., A-TMMA): 20 parts Dipentaerythritol monohydroxypentaacrylate (Sartomer) Manufactured by SR399): 5 parts ・ 50 parts of trimethylolpropane acrylate (manufactured by Nippon Kayaku Co., Ltd., TMPTA) ・ silica powder (manufactured by Fuji Silysia Chemical, Cicilia 380): 2 parts ・ Silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.) KF353): 0.5 part Photopolymerization initiator (Ciba Specialty Chemicals, Irgacure 184): 1 part

(Example 7)
In the production of the decorative sheet of Example 5, Example 4 was carried out in the same manner as Example 2 except that the following aqueous primer N for second primer layer was used instead of the aqueous primer K for second primer layer. A decorative sheet was obtained.

Aqueous coating agent N for second primer layer;
Aqueous urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., trade name: F-8585D): 100 parts Nonionic water-dispersible isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd .: Aquanate 100): 7.5 parts Silica powder (Fuji Silysia Chemical Co., Ltd., trade name: Cicilia 380): 1 part Water: 10 parts

(Example 8)
In the production of the decorative sheet of Example 5, instead of the polypropylene colored sheet (thickness 60 μm) manufactured by Mitsubishi Chemical MKV Co., Ltd. as the substrate 2, a polyethylene colored sheet (thickness 80 μm) manufactured by Mitsubishi Chemical MKV Co., Ltd. Was used. Otherwise, the decorative sheet of Example 8 was obtained in the same manner as Example 1.

(Comparative Example 1)
In the decorative sheet of Example 1, the first primer layer aqueous coating agent A, the solid ink layer aqueous coating agent B, the pattern ink layer aqueous coating agent C, the adhesive layer aqueous coating agent D, and the surface protection. Instead of the water-based coating agent E for the layer, the water-based coating agent F for the first primer layer, the water-based coating agent J for the solid ink layer, the water-based coating agent G for the pattern ink layer, and the water-based adhesive layer, respectively. Coating agent I and aqueous coating agent H for surface protective layer were used. Otherwise, the decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1.

(Comparative Example 2)
In the decorative sheet of Comparative Example 1, in place of the solid ink layer aqueous coating liquid J and the adhesive layer aqueous coating liquid I, the solid ink layer aqueous coating liquid O and the adhesive layer aqueous coating liquid P having the following composition were used. A decorative sheet of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that was used.

Aqueous coating solution O for solid ink layer;
・ Anionic urethane-based white ink (The Inktec Co., Ltd .: White for Ode Wek solid, carboxyl group neutralized with amine): 100 parts ・ Nonionic water-soluble epoxy crosslinking agent (Nagase ChemteX Corporation) , Trade name: Denacol EX421): 7.5 parts Water: 20 parts Isopropyl alcohol: 20 parts Aqueous coating solution P for adhesive layer;
Anionic urethane resin (manufactured by Nikka Chemical Co., Ltd., trade name: Evaphanol HO30, carboxyl group neutralized with amine): 100 parts Nonionic water-soluble epoxy crosslinking agent (trade name, manufactured by Nagase ChemteX Corporation) : Denacol EX421): 7.5 parts

(Comparative Example 3)
In the decorative sheet of Comparative Example 1, in place of the solid ink layer aqueous coating solution J and the adhesive layer aqueous coating solution I, the solid ink layer aqueous coating solution Q and the adhesive layer aqueous coating solution R having the following composition were used. A decorative sheet of Comparative Example 3 was obtained in the same manner as in Comparative Example 1 except that was used.

Aqueous coating liquid Q for solid ink layer;
・ Anionic urethane-based white ink (manufactured by The Inktec Co., Ltd .: White for Ode WEK solid, neutralized with carboxyl group with amine): 100 parts ・ Water: 20 parts ・ Isopropyl alcohol: 20 parts

Aqueous coating solution R for adhesive layer;
Anionic urethane resin (manufactured by Nikka Chemical Co., Ltd., trade name: Evaphanol HO30, carboxyl group neutralized with amine): 100 parts

<Characteristic evaluation>
About the decorative sheet of Examples 1-8 and Comparative Examples 1-3, the evaluation test (Adhesion test, interlayer adhesion test, and peeling test) was done. Each test was performed on the decorative sheet immediately after the curing treatment (normal state) and on the decorative sheet after the following water resistance test and after the wet heat resistance test.

(Water resistance test)
The decorative sheet used in the following evaluation test was immersed in tap water for one month, and the following evaluation test was performed on the decorative sheet immediately after being taken out and two days after being taken out.

(Moisture and heat resistance test)
The decorative sheet used in the following evaluation test was stored in a high-temperature and high-humidity layer at 60 ° C. and 90% RH for one month, and the following evaluation test was performed on the decorative sheet immediately after being taken out and two days after being taken out.

(Adhesion evaluation test)
A 50 mm long cellophane adhesive tape (Nichiban Co., Ltd., trade name “Cellotape (registered trademark)”, industrial 24 mm width) is applied to the surface (surface protective layer side) of the decorative sheet 1 and is clothed at room temperature (25 ° C.). Rubbed and crimped. The temperature-rise tape surface was cooled to room temperature (25 ° C.), and the cellophane adhesive tape was peeled off by hand at once. The presence or absence of adhesion of the coating film to the cellophane adhesive tape was visually confirmed. The results are shown in Table 1. A film having no adhesion to the cellophane pressure-sensitive adhesive tape was indicated as “good”, and a film having adhesion or peeling between layers was expressed as “failed”.

(Interlayer adhesion evaluation test)
The decorative sheet 1 was cut into a 1-inch width to produce a test piece, and a tensile tester (manufactured by INSTRON, model number: under the condition of an opening angle of 180 ° between the base material 2 of the decorative sheet 1 and the transparent resin layer 6). 5500), a tensile test was performed under the conditions of 25 ° C. and a tensile speed of 100 mm / min, and the peel strength was measured. The results are shown in Table 1. In the decorative sheet immediately after aging, a peel strength of 20 N or more was evaluated as “good”, and a sheet less than 20 N was expressed as “x” and rejected. In the decorative sheet after the water resistance test and in the heat and humidity resistance test, those having a peel strength of 15 N or more are indicated by “◯”, those having a peel strength of 5 N or more and less than 15 N are indicated by “Δ”, and those having less than 5 N are indicated by “X”.

<Evaluation results>
In Examples 1 to 8, all of the obtained decorative sheets were excellent in adhesion between layers and interlayer adhesion between the substrate and the transparent resin layer. Further, even in the decorative sheet after the water resistance test or the like, these adhesions were good.

  On the other hand, in Comparative Examples 1 and 2, the results were inferior to the adhesion and interlayer adhesion of each layer immediately after the water resistance test and immediately after the moisture and heat resistance test. Further, in Comparative Example 2, a normal decorative sheet was not good. As for Comparative Example 3, not only the adhesion of each layer and the adhesion of the interlayer adhesion immediately after the moisture resistance test and 2 days after the removal were inferior, but also the normal adhesion was inferior.

It is sectional drawing which shows an example of the laminated constitution of the decorative sheet of this invention. It is sectional drawing which shows another example of the laminated constitution of the decorative sheet of this invention. It is sectional drawing which shows another example of the laminated constitution of the decorative sheet of this invention. It is sectional drawing which shows another example of the laminated constitution of the decorative sheet of this invention. It is sectional drawing which shows an example of embodiment of the decorative sheet of this invention. It is sectional drawing which shows another example of embodiment of the decorative sheet of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Base material 3 Solid ink layer 4 Picture ink layer 5 Adhesive layer 6, 6 ', 6 "Transparent resin layer 7 Concavity and convexity 8 Ink layer 9 Surface protective layer 10 First primer layer 11 Ink layer 12 Adhesive layer 13 Second primer layer 16 Multi-layer transparent resin layer 41 Three-dimensional shaped article 51 Plate material

Claims (21)

A decorative sheet in which an ink layer having a solid ink layer and / or a pattern ink layer, an adhesive layer, and a transparent resin layer are laminated in this order on a substrate,
At least one of the ink layer and the adhesive layer is formed of an aqueous coating agent containing an aqueous compound having two or more carbodiimide groups in one molecule.   The decorative sheet according to claim 1, wherein an easy adhesion treatment is performed on the surface of the base material on the ink layer side, and the ink layer is formed of the water-based coating agent.   The decorative sheet according to claim 1 or 2, wherein the transparent resin layer is formed of a resin containing a maleic acid-modified polypropylene resin, and the adhesive layer is formed of the aqueous coating agent.   One of the aqueous coating agent forming the ink layer and the aqueous coating agent forming the adhesive layer contains an aqueous resin component having an anionic group. The decorative sheet according to any one of claims 1 to 3.   The decorative sheet according to claim 4, wherein the anionic group is at least one of a neutralized carboxyl group and a neutralized sulfonic acid group.   The decorative sheet according to any one of claims 1 to 5, wherein the base material is made of a polyolefin-based elastomer, and the transparent resin layer is made of a polyolefin-based resin.   The decorative sheet according to any one of claims 1 to 6, wherein a first primer layer is further provided on the surface on the substrate side.   The makeup according to claim 7, wherein the first primer layer is formed of an aqueous coating agent for a first primer layer containing an aqueous compound having two or more carbodiimide groups in one molecule. Sheet.   The decorative sheet according to claim 7 or 8, wherein an easy adhesion treatment is applied to a surface of the base material on the first primer layer side.   The decorative sheet according to any one of claims 7 to 9, wherein the aqueous coating agent forming the first primer layer contains an aqueous resin component having an anionic group.   The decorative sheet according to claim 10, wherein the anionic group is at least one of a neutralized carboxyl group and a neutralized sulfonic acid group.   The decorative sheet according to any one of claims 1 to 11, wherein a surface protective layer is further laminated on the transparent resin layer.   The decorative sheet according to claim 12, wherein the surface protective layer is formed of an aqueous coating agent for a surface protective layer containing an aqueous compound having two or more carbodiimide groups in one molecule.   The decorative sheet according to claim 13, wherein an easy adhesion treatment is applied to a surface of the transparent resin layer on the surface protective layer side.   The decorative sheet according to claim 13 or 14, wherein the aqueous coating agent forming the surface protective layer contains an aqueous resin component having an anionic atomic group.   The decorative sheet according to claim 15, wherein the anionic group is at least one of a neutralized carboxyl group and a neutralized sulfonic acid group.   The surface protective layer is formed of an active energy ray-curable coating agent, a second primer layer is further provided between the surface protective layer and the transparent resin layer, and the second primer layer is an aqueous coating agent. The decorative sheet according to claim 12, wherein the decorative sheet is formed of.   The decorative sheet according to claim 17, wherein the second primer layer is formed of an aqueous coating agent for a surface protective layer containing an aqueous compound having two or more carbodiimide groups in one molecule. .   The decorative sheet according to claim 17 or 18, wherein the active energy ray is an electron beam.   The said water-based coating agent which forms a said 2nd primer layer contains the water-based resin component which has an anionic group, The decorative sheet of any one of Claims 17-19 characterized by the above-mentioned. The decorative sheet according to claim 20, wherein the anionic group is at least one of a neutralized carboxyl group and a neutralized sulfonic acid group.

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