JP2015085686A - Decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative material that can achieve a strong adhesion, a good durability, and a good designability.SOLUTION: Provided is a decorative material obtained by at least laminating a decorative material including on the surface thereof a melamine-containing layer, a primer layer formed on the surface of the melamine-containing layer included by the decorative material, and an ink layer formed on a part or the whole of the surface of the primer layer, and in which the primer layer is formed of a reaction product between a curative agent having at least one functional group selected from an isocyanate group and a carbodiimide group, and a main agent having a plurality of functional groups capable of cross-link reacting with the curative agent, and in which the ink layer is formed of a coloring ink at least comprising a coloring material and an acrylic compound having polymerizable unsaturated group, and of a transparent ink comprising no coloring material and at least comprising an acrylic compound having polymerizable unsaturated group, and in which the transparent ink is applied on a part or the whole of the region where the coloring ink is not applied.

Description

  The present invention relates to a decorating material, and more particularly to a decorating material used in a watering device in which a surface of a melamine-containing layer of a decorative material is decorated with an ink layer.

  Low-pressure melamine decorative materials are used in various products such as wall materials, floor materials, tables, and furniture. In addition, a decorative material obtained by painting a low-pressure melamine decorative material is also used in watering devices such as kitchens, toilets, bathrooms, and toilets.

  On the other hand, a technique is known in which ultraviolet curable ink is ejected onto a certain type of substrate by inkjet printing, and the substrate is decorated by ultraviolet irradiation. Further, acrylic compounds having a polymerizable unsaturated group are known as polymerizable compounds used in such ultraviolet curable inks.

  Also, a method using white ink is known when white or light color decoration is to be performed by ink jet printing.

  Japanese Patent Application Laid-Open No. 2005-238035 (Patent Document 1) discloses an undercoat paint having a resin component of an active hydrogen-containing compound such as acrylic polyol and a polyisocyanate compound as a base material having irregularities on the surface of an asbestos slate plate or the like. A colored ink containing a resin having good adhesion to the undercoat using an ink jet printer is applied on the undercoat with a reaction rate of 20 to 80% applied to the uneven surface. A method for producing a decorative board having irregularities on its surface is described, wherein a pattern coating film is formed by coating on the surface of the pattern coating film and a clear paint is applied to the entire surface of the pattern coating film. According to this document, there is provided a method for producing a decorative board which can easily and efficiently draw a pattern coating layer having excellent design on the surface of a substrate having irregularities on the surface, and which has excellent durability. It is said.

Japanese Patent Laid-Open No. 2005-238035

  Low-pressure melamine cosmetics have the property of swelling due to moisture and moisture. For this reason, low-pressure melamine makeup due to moisture and moisture is used for decorative materials for water-related devices that are coated on low-pressure melamine cosmetics. There was a problem that the decorative material was peeled off due to the volume change of the material, and cracks occurred.

  In addition, even when UV curable ink containing an acrylic compound having a polymerizable unsaturated group is printed on the low-pressure melamine decorative material, the polymerizable property contained in the melamine resin and UV curable ink contained on the surface of the low-pressure melamine decorative material. Since it is impossible to act chemically or physically with an acrylic compound having an unsaturated group, adhesion between the ultraviolet curable ink and the low-pressure melamine decorative material cannot be obtained, and the printed matter There was a problem of peeling off. To solve this problem, we developed special UV curable ink that can adhere to low-pressure melamine cosmetics, and improved commercially available low-pressure melamine cosmetics so that UV curable inks can adhere. Although it is conceivable to do so, it is not practical due to cost.

  In addition, the present inventors use a white member under the ink layer without using a white ink when attempting to decorate white or light colors by inkjet printing, and make use of the white color to obtain a desired white color. When trying to express light colors, such a decorative part has a problem that the clear layer cannot be sufficiently adhered to the primer layer because the colored ink layer is little or almost absent.

  The present inventors have now provided a primer layer formed by curing a specific primer composition on the surface of a melamine-containing layer provided on the surface of a cosmetic material, preferably a low-pressure melamine cosmetic material, and this primer layer Furthermore, the following knowledge was obtained by providing an ink layer formed by applying a specific ink at a predetermined time on the surface.

  Here, the specific primer composition has at least one functional group selected from a functional group that can be chemically bonded to an amino group in the melamine resin contained in the melamine-containing layer, preferably an isocyanate group and a carbodiimide group. And a main agent having a plurality of functional groups capable of crosslinking reaction with the curing agent. Moreover, the predetermined time is an appropriate time during the cross-linking reaction in which the curing agent contained in the primer composition and the main agent react to form a reaction product (cross-linked product), that is, the primer layer. It is an appropriate time while curing is incomplete. Further, the specific ink contains a compound having a polymerizable unsaturated group capable of acting on the reaction product, preferably an acrylic compound having a polymerizable unsaturated group.

  First, it was found that (i) the melamine-containing layer and the primer layer provided on the surface of the melamine decorative material can be firmly adhered by a specific chemical bond. The specific chemical bond refers to a chemical reaction between an amino group in the melamine resin contained in the melamine-containing layer and at least one functional group selected from an isocyanate group and a carbodiimide group contained in the curing agent included in the primer composition. It is at least one chemical bond selected from a urea bond and an amide bond generated at the interface between the two layers.

  In addition, (ii) the knowledge that the primer layer and the ink layer can be firmly adhered by a dense (condensed) structural entanglement generated at the interface between these two layers by a specific mechanism. It was. The specific mechanism is that the acrylic compound having a polymerizable unsaturated group contained in the ink penetrates and diffuses into the reaction product produced by the reaction between the curing agent and the main agent contained in the primer composition, and thereafter When the ink is cured, the reaction product and the polymer of the acrylic compound having a polymerizable unsaturated group act structurally densely (for example, intertwined).

  As a result, (iii) it was found that a decorative material in which the melamine decorative material and the ink layer were firmly adhered as an integral unit of these three layers was obtained via the primer layer.

  Further, the present inventors have found the following configuration in view of the fact that the color tone of the decorative material is determined by the color tone of a single color or a plurality of colored inks and the color tone of a member under the ink layer. . That is, as the ink, both a colored ink containing at least a coloring material and an acrylic compound having a polymerizable unsaturated group and a transparent ink containing at least an acrylic compound having no polymerizable material and having a polymerizable unsaturated group are used. Further, the present inventors have found a configuration in which the ink layer is formed by applying a transparent ink to a part or all of a region to which the colored ink is not applied. With this configuration, second, a clear layer that is difficult to adhere to a white or light-colored decorative portion to which a colored ink layer is not applied is adhered to the transparent ink layer in the same manner as the region where the colored ink layer is formed. It was found that it is possible to make it. In other words, even when the whiteness of the target decorative material is high, the adhesion between the primer layer and the clear layer can be achieved easily and inexpensively without requiring a special paint to form the clear layer. The knowledge that a possible decorating material was obtained was acquired.

  Third, even when the melamine cosmetic material undergoes a volume change due to moisture, the primer layer with excellent flexibility that firmly adheres to the stress caused by this volume change with the melamine cosmetic material is dispersed and absorbed. The knowledge that it is possible to do. In addition, the primer layer and the ink layer can be peeled off by allowing the ink layer having a high layer strength firmly adhered to the primer layer to reliably exert the stress dispersion / absorption ability of the primer layer, The knowledge that the decorating material excellent in durability which does not produce a crack was obtained.

  Fourthly, the inventors have found that a decorative material having high color developability and excellent design properties can be obtained.

  In addition, the present inventors recently provided a clear layer formed of a specific clear paint on the surface of the ink layer, and fifthly, the ink layer and the clear layer have a specific chemical bond. As a result, it has been found that it is possible to firmly adhere. As a result, it was found that a decorative material in which the four layers of the melamine decorative material, the primer layer, the ink layer, and the clear layer were integrated and firmly adhered was obtained.

  Here, the specific clear paint is a compound having a polymerizable unsaturated group having the same polymerization reaction mechanism as the compound having a polymerizable unsaturated group contained in the ink, preferably an acrylic compound having a polymerizable unsaturated group. including. Further, the specific chemical bond has a polymer of an acrylic compound having a polymerizable unsaturated group contained in the ink forming the ink layer and a polymerizable unsaturated group contained in the clear paint forming the clear layer. This is a chemical bond generated at the interface between these two layers because the polymer of the acrylic compound is produced by the same polymerization reaction mechanism.

  Sixth, in addition to the ink layer, the above-described primer layer has the ability to disperse and absorb the stress caused by the volume change of the melamine decorative material. The knowledge that it was possible to make sure it was demonstrated was obtained. Thereby, the knowledge that the decorating material excellent in durability which does not peel a primer layer, an ink layer, and a clear layer, or produce a crack was obtained.

  Seventh, the present inventors have found that a decorative material that protects the ink layer from external stress and is excellent in glossiness and image clarity can be obtained. The present invention is based on the above findings.

  Accordingly, an object of the present invention is to provide a decorating material capable of realizing strong adhesion, excellent durability, and excellent design.

And the decorating material by this invention is
A cosmetic material comprising a melamine-containing layer on its surface;
A primer layer formed on the surface of the melamine-containing layer provided in the decorative material;
A decorative material formed by laminating at least an ink layer formed on a part or all of the surface of the primer layer,
The primer layer is formed from a reaction product of a curing agent having at least one functional group selected from an isocyanate group and a carbodiimide group and a main agent having a plurality of functional groups capable of crosslinking reaction with the curing agent. ,
The ink layer is formed from a colored ink containing at least a coloring material and an acrylic compound having a polymerizable unsaturated group, and a transparent ink containing at least an acrylic compound having no polymerizable material and having a polymerizable unsaturated group. Thus, the transparent ink is applied to a part or all of the region where the colored ink is not applied.

According to one aspect of the present invention, the decorative material according to the present invention comprises:
The melamine-containing layer and the primer layer are chemically bonded to the amino group in the melamine resin contained in the melamine-containing layer and the amino group in the melamine resin contained in the melamine-containing layer that the curing agent has. The primer layer and the ink layer are attached by chemical bonds generated at the interface between these two layers due to chemical reaction with possible functional groups, and the reaction product generated at the interface between these two layers And adhering by structural entanglement with a compound having a polymerizable unsaturated group capable of acting on the reaction product or a polymer thereof.

  According to another aspect of the present invention, the decorating material according to the present invention further comprises a clear layer laminated on the surface of the ink layer, and the clear layer contains a polymerizable unsaturated group contained in the ink. It is formed from the clear coating material containing the compound which has a polymerizable unsaturated group which has the same polymerization reaction mechanism as the compound which has.

  According to still another aspect of the present invention, the ink layer and the clear layer form the clear layer with a polymer of a compound having a polymerizable unsaturated group contained in the ink forming the ink layer. The polymer of the compound having a polymerizable unsaturated group contained in the clear paint is produced by the same polymerization reaction mechanism, and is attached by a chemical bond generated at the interface between these two layers. And

  According to still another aspect of the present invention, the decorative material according to the present invention is characterized in that an edge material is provided on at least the side surface of the base material portion of the decorative material among the side surfaces of the decorative material. And

It is a schematic block diagram of the decorating material by this invention. One mode of the ink layer formed in the primer layer surface of the decorating material by this invention is shown. It is a schematic block diagram of the serial type inkjet printing apparatus used in the manufacturing method of the decorating material by this invention. It is a schematic block diagram of the nozzle head and ultraviolet irradiation means of the serial type inkjet printer used in the manufacturing method of the decorating material by this invention.

Decorating material The decorating material 10 according to the present invention is generally formed by laminating at least a decorative material 11, a primer layer 14, and an ink layer 15, and in some cases, a clear layer 16 is further laminated in this order. It becomes. The decorative material is formed by laminating a base material 12 and a melamine-containing layer 13 on the base material. The schematic block diagram of the decorating material by this invention is shown in FIG.

Cosmetic Material The cosmetic material constituting the decorative material according to the present invention includes a base material and a melamine-containing layer on the surface of the base material. In this invention, a well-known thing can be used as such a cosmetic material, for example, a high-pressure melamine cosmetic material and a low-pressure melamine cosmetic material can be used. These melamine decorative materials are generally manufactured by using a so-called melamine resin-impregnated paper in which paper is impregnated with melamine resin as a decorative base paper, and by heating and compressing this and various base materials. It is divided into a melamine decorative material (for example, 70 to 120 kgf / cm 2) and a low-pressure melamine decorative material (for example, 10 to 40 kgf / cm 2). As a specific example of high-pressure melamine decorative material, one sheet of melamine resin impregnated paper for each of the upper and lower layers and five core papers impregnated with phenolic resin for the middle layer are laminated, and one overlay paper impregnated with melamine for the outermost layer. The thing laminated | stacked one by one is mentioned. When the high-pressure melamine decorative material is used as a decorative material constituting the decorative material according to the present invention, the high-pressure melamine decorative material is used by adhering it to a suitable base material.

Low Pressure Melamine Cosmetic Material According to a preferred embodiment of the present invention, the decorative material constituting the decorative material according to the present invention is preferably a low pressure melamine cosmetic material. In this invention, a well-known thing can be used as such a low-pressure melamine cosmetic material. As the low-pressure melamine decorative material, for example, a melamine resin-impregnated paper that is integrally formed with heat and pressure at a pressure of 10 to 40 kgf / cm ² can be used on the surface of a base material to be described later. Since the surface of the low-pressure melamine decorative material is white, various decorations are possible. Moreover, the white of the ground color can be used as it is as the color of the decorating material. In addition, low-pressure melamine decorative materials are currently widely used in system kitchen cabinets and the like, and the price is relatively low.

The base material (core material) used for the low-pressure melamine decorative material is mainly wood. Concretely, veneer of various materials such as cedar, firewood, firewood, pine, lawan, teak, melapy, wood veneer, wood plywood, particle board, medium density fiber board (MDF), oriented strand board (OSD), etc. Wood material. According to a preferred embodiment of the present invention, the base material is particle board or MDF from the viewpoint that it has a track record in kitchens and vanities, has sufficient mechanical strength, is relatively inexpensive, and is easily available. It is preferable.

Primer layer The primer layer contained in the decorating material according to the present invention comprises a curing agent having a functional group that can be chemically bonded to an amino group in the melamine resin contained in the melamine-containing layer provided in the decorative material, and the curing agent. It is formed from a reaction product with a main agent having a plurality of functional groups capable of crosslinking reaction.

Curing agent The curing agent contained in the primer composition forming the primer layer of the decorating material according to the present invention has a functional group capable of chemically bonding with an amino group in the melamine resin contained in the melamine-containing layer provided in the decorative material. A compound. According to a preferred embodiment of the present invention, the functional group that can be chemically bonded to the amino group in the melamine resin of the curing agent is at least one functional group selected from an isocyanate group or a carbodiimide group. preferable. These functional groups chemically react with amino groups in the melamine resin contained in the melamine-containing layer of the melamine cosmetic material, so that the melamine-containing layer and the primer layer have urea bonds and amides generated at the interface between these two layers. The attachment is possible by at least one chemical bond selected from the bonds. Here, the interface between the melamine-containing layer and the primer layer includes the boundary between these two layers, and as long as it is a region where the above chemical bond occurs, a partial region on the surface side of the melamine-containing layer and the bottom surface side of the primer layer Means a region having a predetermined thickness including a part of the region.

  Isocyanate groups from these oxygen atoms or nitrogen atoms in the melamine-containing layer of the melamine cosmetic material (the melamine and methylol melamine components are also included in the melamine resin). Pulling out and forming a urea bond (-NH-CO-NH-), which makes it possible for the melamine-containing layer and the primer layer of the melamine cosmetic material to be chemically and firmly adhered via the interface between these two layers. Become. In addition, the carbodiimide group draws out hydrogen next to the oxygen atom and nitrogen atom in the melamine resin from these to form an amide bond (—NH—CO—), thereby forming a melamine-containing layer and a primer layer of the melamine cosmetic material. Can be chemically and firmly adhered through the interface between these two layers.

  According to the preferable aspect of this invention, it is preferable that the functional group which can be couple | bonded chemically with the amino group in the melamine resin contained in the melamine content layer with which a cosmetic material is provided is an isocyanate group. There are many types of compounds having an isocyanate group, and it is advantageous in that the reactivity with an amino group and the physical properties of the reaction product can be adjusted by selecting specific compounds from various compounds. As the compound having an isocyanate group, a compound having a urethane resin two-component isocyanate group can be preferably used. More preferably, a compound having a urethane resin two-component diisocyanate group can be used. Examples of the compound having a urethane resin type two-component diisocyanate group include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate (XDI), isophorone diisocyanate, hexamethylene diisocyanate (HDI), 4 Various diisocyanate monomers such as 4,4'-diphenylmethane diisocyanate and hydrogenated products thereof can be preferably used. In addition, adduct type obtained by reacting these diisocyanate monomers with trifunctional active hydrogen-containing compounds such as trimethylolpropane and glycerol, burette type reacted with water, trimer utilizing isocyanurate self-polymerization (isocyanurate) A trifunctional or higher functional derivative such as a type can also be preferably used.

  The above-mentioned compound having a urethane resin two-component isocyanate group can react with the main agent described later at a relatively low temperature (normal temperature to 80 ° C.). Therefore, it is not necessary to treat the melamine decorative material mainly made of wood at a high temperature, and as a result, it is possible to prevent defects such as thermal deformation of the melamine decorative material and peeling, swelling and cracking of the primer layer due to outgassing. . In addition, since it is necessary to heat block type isocyanate at comparatively high temperature, since a melamine cosmetics will deform | transform, it is unsuitable.

  Examples of the compound having a carbodiimide group include di-p-toluyl carbodiimide, poly 4,4'-diphenylmethane carbodiimide, poly 4,4'-dicyclohexyl methane carbodiimide, poly 4,4'-diphenyl ether carbodiimide, poly 3,3'-dimethoxy. -4,4'-biphenylcarbodiimide, poly p-phenylene carbodiimide, polynaphthylene-1,5-carbodiimide, poly m-xylylene carbodiimide, polyhydrogenated xylylene carbodiimide, di-p-toluyl carbodiimide, poly 2,4-tolu Irene carbodiimide, poly 2,6-toluylene carbodiimide, poly o-tolidine carbodiimide; poly tert-butyl carbodiimide, polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide Imides; di C3~10 cycloalkyl carbodiimide, poly tetramethylxylylenecarbodiimide can be suitably used poly isophoronecarbodiimide.

  Also suitable are aromatic, aliphatic and alicyclic polycarbodiimide compounds having two or more carbodiimide groups in the molecule of C2-12 or more (excluding C in -N = C = N- group). Can be used. Specific examples of the aromatic polycarbodiimide compound include xylylene dicarbodiimide, triisopropylbenzene polycarbodiimide, triisopropylbenzene polycarbodiimide and the like; specific examples of the aliphatic polycarbodiimide compound include alkylene (C2-12) dicarbodiimide, alkylene ( C2-12) Polycarbodiimide, dialkylcarbodiimide (diC1-10 alkylcarbodiimide such as diethylcarbodiimide, dipropylcarbodiimide), etc .; Specific examples of alicyclic-containing polycarbodiimide compounds include bicycloheptanetricarbodiimide, dicyclohexylmethane dicarbodiimide, and the like. Can be mentioned.

  According to a preferred embodiment of the present invention, the curing agent contained in the primer composition preferably does not contain an unsaturated bond in the structure from the viewpoint of preventing yellowing. Further, from the viewpoint of the “structural entanglement”, the curing agent is structurally highly similar to the acrylic compound having a polymerizable unsaturated group contained in the ink in a portion other than the reactive functional group, or It is preferably a linear compound that does not contain a cyclic structure (for example, an alicyclic ring, an aromatic ring, or a heterocyclic ring structure). A more preferred curing agent is HDI and its derivatives (for example, isocyanurate type HDI).

Main agent The main agent contained in the primer composition used in the production of the decorating material according to the present invention is a compound having a plurality of functional groups capable of crosslinking reaction with the curing agent. According to a preferred embodiment of the present invention, the main agent is preferably a polymer compound having an OH group and / or an NH group (preferably an NH group derived from an amine). The polymer compound having a plurality of OH groups and / or NH groups is polymerized with the curing agent having the isocyanate group or carbodiimide group to form a urethane bond, an amide bond, or a urea bond. The reaction product (crosslinked product) having these chemical bonds as a skeleton can form a flexible primer layer. That is, in this case, the primer composition contains a so-called two-component urethane resin film-forming component.

Polymer Polyol According to a preferred embodiment of the present invention, as the polymer compound having a plurality of OH groups and / or NH groups, a polymer polyol optionally having a plurality of NH groups can be preferably used. Thereby, a primer layer having excellent stability can be obtained. Furthermore, it becomes possible to realize adhesion between the primer layer and the ink layer formed on a part or all of the surface thereof. Specific examples of the polymer polyol include polyether polyol, polyester polyol, acrylic polyol, polyurethane polyol, and polycarbonate polyol. According to a more preferred aspect of the present invention, water resistance of the coating is required for the watering device, so that acrylic polyol can be more preferably used.

  When a colored ink and a transparent ink, which will be described later, are applied to the primer layer formed from the reaction product while the primer layer is incompletely cured, the following phenomenon occurs: it is conceivable that. That is, it is considered that an acrylic compound having a polymerizable unsaturated group preferably contained in these inks can appropriately permeate and diffuse into the urethane resin during the crosslinking reaction that forms the primer layer. In particular, when the main agent is an acrylic polyol, the acrylic polyol and the acrylic compound having a polymerizable unsaturated group contained in the ink are common in that they are acrylic. Therefore, it is considered that the acrylic compound having a polymerizable unsaturated group contained in these inks can be penetrated and diffused with affinity to the crosslinked body forming the primer layer.

  And in such a state, the colored ink and the transparent ink are cured (for example, by irradiating active energy rays and polymerizing an acrylic compound having a polymerizable unsaturated group contained in these inks), The reaction product forming the primer layer and the acrylic polymer contained in these inks can form a tightly intertwined state. As a result, the primer layer and the ink layer can be firmly adhered by the structural entanglement generated at the interface between these two layers. That is, the ink layer formed on the surface of the primer layer can have excellent layer strength.

  As described above, according to the present invention, the melamine-containing layer of the melamine cosmetic material and the primer layer can be chemically tightly adhered, and further, the primer layer and the ink layer can be structurally intertwined firmly. It becomes. As a result, it is possible to obtain a decorative material in which the three layers of the melamine decorative material, the primer layer, and the ink layer are firmly adhered as a unit. Furthermore, even when the melamine decorative material undergoes a volume change due to moisture, the flexible primer layer can relieve the stress applied to the ink layer due to the volume change, and the ink layer is further affected by this stress. Since it becomes possible to generate a drag against the primer layer, the primer layer can reliably absorb this stress. Therefore, it becomes possible to ensure the protection of the ink layer, and it is possible to obtain a decorative material with excellent durability that does not cause the primer layer or the ink layer to peel off or crack from the melamine decorative material. it can.

  Examples of the polyether polyol include polyalkylene glycol (eg, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol) or alkylene oxide (eg, ethylene oxide, propylene oxide, tetrahydrofuran) and polyol (eg, ethylene glycol). , Diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,2,6-hexanetriol, pentaerythritol, sorbitol , Sorbitan, sucrose, etc.) can be preferably used.

  Examples of the polyester polyol include polybasic acids (for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, hexahydrophthalic acid, highmic acid, het acid, succinic acid, Maleic acid, fumaric acid, adipic acid, sebacic acid, dodecenyl succinic acid, trimellitic acid, pyromellitic acid) or anhydrides thereof and polyhydric alcohols (eg, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, triglyceride) Methylolpropane, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,2,6-hexanetriol, pentaerythritol, sorbitol, bisphenol A Polyester polyol obtained by a condensation reaction with the above, a polyol obtained by reacting the above polyhydric alcohol with an epoxy compound (for example, n-butyl glycidyl ether, allyl glycidyl ether) and the above polybasic acid, the above epoxy compound and the above poly A polyester polyol obtained by reaction with a basic acid, a higher fatty acid (for example, soybean oil, linseed oil, safflower oil, coconut oil, dehydrated castor oil, tung oil, rosin), the polybasic acid and the polyhydric alcohol. An alkyd-type polyol obtained by the reaction, a polymerized polyester polyol obtained by ring-opening polymerization of ε-caprolactam and the above polyhydric alcohol can be preferably used.

  As the acrylic polyol, for example, an ethylenically unsaturated monomer having a hydroxyl group (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate) is an essential monomer. And other monomers (for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, ethylhexyl (meth) acrylate), styrene, α- It is preferable to use those obtained by polymerization reaction using methylstyrene, vinyltoluene, t-butylstyrene, ethylene, propylene, vinyl acetate, vinyl propionate, (meth) acrylonitrile, dimethylaminoethyl (meth) acrylate) in combination. Can.

  Examples of the polyurethane polyol include isocyanate compounds (for example, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1-methyl-2,4-diisocyanate cyclohexane, 1-methyl-2,6-diisocyanate cyclohexane, ω, ω′-diisocyanate diethylbenzene, ω, ω′-diisocyanate methylaminotoluene, ω, ω′-diisocyanate dimethylxylene, ω, ω′-diisocyanate diethylxylene, lysine diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 4, 4′-ethylenebis (cyclohexyl isocyanate), ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′- Isocyanate-1,4-dimethylbenzene, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4-methylenebis (phenyl isocyanate), triphenylmethane tri Isocyanate) or a multimer thereof, and an excessive amount of a low molecular polyol (for example, ethylene glycol, propylene glycol, 1,3-butyl glycol, neopentyl glycol, 2,2,4-trimethyl-1,3- By addition reaction with pentanediol, hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin, sorbitol, sorbitan, sucrose, pentaerythritol) Polyurethane obtained by addition reaction of a polyol compound having a relatively low molecular weight among the polyether polyol, polyester polyol, polymerized polyester polyol and acrylic polyol and an isocyanate compound such as monoisocyanate, diisocyanate and triisocyanate. A polyol or the like can be preferably used.

  According to a preferred embodiment of the present invention, the polymer polyol described above preferably does not contain an unsaturated bond such as a conjugated double bond or an aromatic ring in the structure from the viewpoint of preventing yellowing. Furthermore, from the viewpoint of the “structural entanglement”, the polymer polyol has a unit structure that is structurally highly similar to the acrylic compound having a polymerizable unsaturated group contained in the ink at a portion other than the reactive functional group. It is preferable that the main chain has a straight chain that does not include a cyclic structure (for example, an alicyclic ring, an aromatic ring, or a heterocyclic ring structure). Since the main chain is a linear molecule, the ink easily diffuses and penetrates into the cross-linked body forming the primer layer, and the melamine-containing layer and the main agent undergo a cross-linking reaction via a curing agent. It becomes possible to firmly adhere to the layer.

  According to a preferred embodiment of the present invention, in the primer composition used for the production of the decorating material according to the present invention, the ratio of the isocyanate group of the curing agent to the OH group of the main agent is 0 in NCO / OH (mol ratio). It is preferable that it is 3 or more and 2.0 or less. When the blending ratio is within this range, the primer layer can be firmly adhered to the melamine-containing layer of the melamine decorative material, and the primer layer can be firmly adhered to the ink layer.

    According to the preferable aspect of this invention, it is preferable that the peeling strength (the coating film tensile test of JISK5600) of the primer layer with respect to the melamine content layer of a melamine cosmetic material is 2 MPa or more and 4 MPa or less. Thereby, the primer layer can be firmly adhered to the melamine-containing layer of the melamine decorative material. The strength is higher than the adhesion strength between the substrate and the melamine-containing layer.

Relationship between cured state of primer composition and wettability and adhesion of ink The primer composition for forming the primer layer of the decorating material according to the present invention undergoes a crosslinking reaction after applying it to the surface of the melamine-containing layer. As the crosslinking reaction proceeds, the wettability and adhesion of the colored ink and the transparent ink to the primer layer vary. According to a preferred embodiment of the present invention, the primer composition preferably has a small change with time in the wettability and adhesion of the colored ink and the transparent ink to the primer layer. As the primer composition having such properties, those having a small hydroxyl value and a relatively large weight average molecular weight of a polymer polyol which is a preferred main component contained in the primer composition can be preferably used.

According to a preferred embodiment of the present invention, the hydroxyl value of the polymer polyol is preferably 5 mgKOH / g or more and 200 mgKOH / g or less. By using a polymer polyol having a relatively small hydroxyl value within this range, it is possible to control the crosslinking reaction between the main agent and the curing agent to be slow or slow so that the primer layer can be colored. It becomes possible to appropriately control the penetration and diffusion of the ink and the transparent ink. Moreover, it becomes possible to control the change in the line width of the colored ink and the transparent ink to be small after curing the primer layer. Furthermore, when colored ink and transparent ink are applied to the primer layer, the extent of wetting and spreading of these inks with respect to the primer layer can be made not to vary greatly depending on the cured state. As a result, it is possible to obtain an ink layer that has high color developability and high designability and can realize stable decoration. The more preferable hydroxyl value of the polymer polyol is 5 mgKOH / g or more and 160 mgKOH / g or less, more preferably 5 mgKOH / g or more and 100 mgKOH / g or less, and most preferably 5 mgKOH / g or more and 60 mgKOH / g or less. Here, the “hydroxyl value” means the number of mg of KOH required for acetylating the OH group contained in 1 g of the polymer polyol.

  According to a preferred embodiment of the present invention, the primer composition preferably comprises a curing agent at a ratio of terminal group equivalents of 0.6 to 2.4 with respect to the hydroxyl value of the polymer polyol.

Weight average molecular weight of polymer polyol According to a preferred embodiment of the present invention, the polymer polyol preferably has a weight average molecular weight of 20,000 to 60,000. By using a polymer polyol in this range having a relatively large weight average molecular weight, it is possible to appropriately control the wetting and spreading of the ink to the primer layer when the colored ink and the transparent ink are applied to the surface of the primer layer. As a result, it is possible to obtain an ink layer that has high color developability, high designability, and can realize stable decoration. Also, good ink wettability is advantageous because an ink layer with high color developability can be obtained even when the amount of ink applied to the primer layer is small. The more preferable weight average molecular weight of the polymer polyol is preferably 30,000 or more and 60,000 or less.

  The primer composition can appropriately contain a thinner such as butyl acetate according to the means for applying the primer composition described later. Thereby, the viscosity and wettability of the primer composition can be adjusted.

  According to one preferable aspect of the present invention, the primer layer of the decorating material according to the present invention is preferably colorless and transparent. The colorless and transparent primer layer is preferable because it can be decorated to take advantage of the white color of the low-pressure melamine decorative material. Moreover, according to another preferable aspect of this invention, a primer layer may contain a coloring material (it demonstrates by the below-mentioned ink layer) according to the design of a decorating material.

Ink Layer The ink layer contained in the decorating material according to the present invention is formed on part or all of the surface of the primer layer. And this ink layer is formed with the ink which contains at least the compound which has a polymerizable unsaturated group which can act with respect to the reaction product of the hardening | curing agent and main ingredient which a primer composition contains. Moreover, it is preferable that the compound which has a polymerizable unsaturated group which can act with respect to the reaction product of the hardening | curing agent and main ingredient which the said primer composition contains is an acryl-type compound which has a polymerizable unsaturated group.

  In the present invention, the ink includes at least a colored ink containing at least an acrylic compound having a polymerizable unsaturated group and a color material, and an acrylic compound having no polymerizable material and having a polymerizable unsaturated group. Both transparent inks are used.

  In the present invention, the ink layer is formed before the primer layer is completely cured, preferably at an appropriate time during which the primer layer is incompletely cured. Thereby, the acrylic compound having a polymerizable unsaturated group contained in the ink forming the ink layer can appropriately permeate and diffuse into the reaction product (crosslinked product) forming the primer layer. Further, after the ink is cured, the acrylic compound having a polymerizable unsaturated group contained in the ink forms a polymer in a state of permeating and diffusing into the reaction product, and this polymer has a structure with the reaction product. Can be intertwined closely (in a condensed state). As a result, the primer layer and the ink layer can be firmly adhered. Here, the interface between the primer layer and the ink layer includes a boundary between these two layers, and as long as the structural entanglement occurs in the region on the surface side of the primer layer or the bottom surface side of the ink layer. Means a region having a predetermined thickness including a part of the region.

Colored ink The colored ink layer, which is a part of the ink layer constituting the decorating material according to the present invention, is formed of colored ink. Thereby, it is possible to obtain a decorating material in which various patterns, characters, figures, symbols and other patterns are colored with various variations. In the present invention, the colored ink can be applied to a part of the surface of the primer layer. As described above, this colored ink is a compound having a polymerizable unsaturated group capable of acting on a reaction product of a colorant, a curing agent contained in a primer composition, and a main agent, preferably a polymerizable unsaturated group. And at least an acrylic compound.

As the color material contained in the color material coloring ink, known pigments, dyes, and combinations thereof can be used. According to a preferred embodiment of the present invention, it is preferable to use a pigment as the color material. This makes it possible to form a colored ink layer having high chemical stability (for example, light resistance).

As the pigment pigment, both inorganic pigments and organic pigments can be used. As the inorganic pigment, carbon blacks, iron oxide, titanium oxide and the like can be used. Organic pigments include insoluble azo pigments, condensed azo pigments, azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye type chelates, acidic dye type chelates), dyeing lakes (basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, A daylight fluorescent pigment is mentioned.

  Examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154 167, 172, 180.

  Examples of pigments used in magenta ink and light magenta ink include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 21, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 , 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50.

  Examples of pigments used for cyan ink and light cyan ink include C.I. I. Pigment blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, or C.I. I. Bat Blue 4,60.

  Examples of pigments other than the yellow, magenta (light magenta) and cyan (light cyan) include C.I. I. Pigment green 7, 10 or C.I. I. Pigment brown 3, 5, 25, 26, or C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63.

  The said pigment may be used individually by 1 type, and may use 2 or more types together.

A compound having a polymerizable unsaturated group that can act on the reaction product of the curing agent and the main agent contained in the primer composition contained in the compound colored ink having a polymerizable unsaturated group can be cured by active energy rays. Compounds can be used. As the compound curable by active energy rays, it is preferable to use an acrylic compound having a polymerizable unsaturated group. Preferable examples of the acrylic compound having a polymerizable unsaturated group include at least one selected from an acrylic polymerizable monomer, an acrylic polymerizable oligomer, an acrylic prepolymer, and a low molecular weight acrylic polymer. Among these, an acrylic polymerizable monomer, an acrylic polymerizable oligomer, and an acrylic polymerizable prepolymer are more preferable, and an acrylic polymerizable monomer is most preferable. Thereby, it is possible to realize good adhesion with the primer layer, good adhesion with the clear layer described later, high color development of the ink layer, and the like. As the acrylic polymerizable monomer, for example, an acrylic polymerizable monomer mainly containing 1,6-hexanediol diacrylate can be preferably used.

Active energy ray In the present invention, the term “active energy ray” refers to an energy ray that affects the electron orbit of an irradiated object such as an electron beam, ultraviolet rays, and infrared rays and can trigger a radical polymerization reaction. As long as it is an energy ray to be induced, it is not limited to these. Specific examples of the active energy ray include infrared rays having a wavelength of 800 nm or more, visible light having a wavelength of 400 to 800 nm, ultraviolet rays having a wavelength of 400 nm or less, and electron beams. Among these, ultraviolet rays, visible rays, and infrared rays are more preferable from the viewpoint that the price of the device for producing them is relatively low.

Polymerization initiator According to a preferred embodiment of the present invention, the colored ink preferably contains a polymerization initiator. The polymerization initiator is a compound that absorbs external energy of the active energy ray and generates a polymerization initiating species. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together. In the present invention, a radical polymerization initiator can be preferably used as the polymerization initiator, and a photo radical polymerization initiator can be more preferably used. As the radical photopolymerization initiator, an ultraviolet-sensitive polymerization initiator can be more preferably used. Specifically, α-aminoacetophenone compound, α-hydroxyketone compound, acylphosphine oxide compound, aromatic onium salt compound, organic peroxide, thio compound, hexaarylbiimidazole compound, ketoxime ester compound, borate compound, An azinium compound, a metallocene compound, an active ester compound, a compound having a carbon halogen bond, or the like can be preferably used. Specific examples of the polymerization initiator include radical polymerization initiators described in JP 2008-208190 A and JP 2010-013574 A.

  According to a preferred embodiment of the present invention, since the colored ink used in the present invention is applied to the surface of the primer layer and then cured by irradiation with active energy rays, a solventless system is used. It is preferable that the ink is. As a result, the solvent remains in the ink layer formed from the cured colored ink, so that the solvent resistance can be deteriorated and the occurrence of VOC can be prevented.

  The layer thickness of the ink layer formed on part or all of the surface of the primer layer with colored ink is preferably 1 to 50 μm. Moreover, when providing the clear layer mentioned later on the surface of an ink layer, it is preferable that the layer thickness of an ink layer is 1-30 micrometers. Thereby, high specular gloss can be given to the surface of a clear layer, and it becomes possible to obtain the decorating material which has favorable image clarity.

  The colored ink can contain various additives such as a surfactant and a pigment dispersant when a pigment is used as a coloring material, as necessary.

Transparent ink The transparent ink layer which is a part of the ink layer which comprises the decorating material by this invention is formed with a transparent ink. In the present invention, the transparent ink is applied to a part or all of the region where the colored ink on the surface of the primer layer is not applied. As described above, this transparent ink is a compound having a polymerizable unsaturated group that can act on the reaction product of the curing agent and the main agent contained in the primer composition without containing a colorant, preferably polymerizable unsaturated. It contains at least an acrylic compound having a group. According to a preferred embodiment of the present invention, the transparent ink preferably has the same composition as the colored ink except that it does not contain a color material. As a result, it is possible to save the trouble of individually preparing components other than the color material, and it is possible to reduce the number of manufacturing steps and costs. In addition, the matter regarding components other than the color material already demonstrated about colored ink is applied also about transparent ink.

Embodiment of ink layer formed by applying colored ink and transparent ink In the present invention, the ink layer is formed from the colored ink and the transparent ink, and the transparent ink is applied to a part or all of the region to which the colored ink is not applied. Applied. In other words, the ink layer constituting the decorating material according to the present invention includes a colored ink layer formed by applying colored ink to a part of the surface of the primer layer, and a region where the colored ink layer on the surface of the primer layer is not formed. The transparent ink layer is formed by applying a transparent ink to a part or all of the transparent ink layer. Here, the “region where the color ink is not applied” includes a region where the color ink is hardly applied and a region where the color ink is hardly applied.

  Specifically, the colored ink is applied to a plurality of independent regions on the surface of the primer layer to form a colored ink layer, while the colored ink layer is formed on the plurality of independent regions on the surface of the primer layer where the colored ink layer is not formed. There are cases where a transparent ink layer is formed by applying a transparent ink. Further, in this aspect, the colored ink and the transparent ink are applied to a partial region of the surface of the primer layer, and the entire remaining region is a region where neither the colored ink nor the transparent ink is applied, that is, A mode in which the primer layer is an exposed region (in contact with the outside world) is also included.

  Moreover, in the said aspect, as a specific example, when a colored ink layer (for example, island-shaped or spotted colored ink layer) is formed by applying colored ink to a part of the surface of the primer layer, the primer The case where a light-colored colored ink layer is formed by forming fine dots of colored ink on a part of the surface of the layer, or a combination thereof, can be mentioned. When there is a small area where the colored ink is applied on the entire surface of the primer layer, if a clear layer to be described later is further provided on the entire surface of the primer layer, the remaining area where the colored ink is not applied, that is, A clear layer is directly formed in a wide area where the primer layer is exposed. However, in this case, it is difficult to obtain adhesion between the primer layer and the clear layer because the clear paint is difficult to penetrate and diffuse into the primer layer in a state where the curing reaction of the primer layer has progressed considerably. .

  On the other hand, even in the state where the crosslinking reaction of the primer layer has advanced considerably, in the region where the colored ink is applied, the colored ink layer and the clear layer are the two layers until the colored ink is completely cured. Therefore, the adhesion between the primer layer and the clear layer can be ensured through the colored ink layer.

  In short, when there is only a small area where the adhesion between the primer layer and the clear layer can be secured via the colored ink layer, while the primer layer and the clear layer are in direct contact with each other and the adhesion between the two is difficult to obtain. There is a high tendency for the clear layer to peel from the primer layer. Therefore, in such a case, the adhesion between the primer layer and the clear layer can be realized through the transparent ink layer by applying the transparent ink to a part or all of the region where the colored ink is not applied. Is possible. As a result, it is possible to prevent the clear layer from peeling off from the primer layer.

Embodiment of Transparent Ink Layer Formed by Applying Transparent Ink As described above, the transparent ink layer formed by applying the transparent ink is an area sufficient to ensure adhesion between the primer layer and the clear layer. Therefore, according to a preferred embodiment of the present invention, the appropriate amount per unit area of the transparent ink applied to the surface of the primer layer is preferably smaller than the applied amount per unit area of the colored ink. .

  Specifically, the area where the transparent ink layer per unit area exists is narrower than the area where the colored ink layer per unit area exists, and the transparent ink layer is formed in the entire area where the colored ink layer is not formed. Can be mentioned. In addition, the entire area where the colored ink layer is not formed is further divided into a formation area and a non-formation area of the transparent ink layer, and these are mixed, so that the transparent ink layer per unit area An embodiment in which the existing area is narrower than the existing area of the colored ink layer can be mentioned. Moreover, the aspect which combined these aspects can also be mentioned.

  As a specific example of this combined mode, when the colored ink layer is not formed on the peripheral portion of the primer layer surface, the transparent ink layer is formed on the peripheral portion of the primer layer surface, and transparent at the central portion of the primer layer surface. An embodiment in which the ink layer formation region and the non-formation region are mixed (for example, scattered in islands or spots) can be exemplified (see FIG. 2). Thereby, it becomes possible to ensure good adhesion between the primer layer and the clear layer through the entire ink layer composed of the transparent ink layer and the colored ink layer.

Clear Layer According to a preferred embodiment of the present invention, the decorating material according to the present invention comprises a clear layer further laminated on the surface of the ink layer, and the clear layer comprises a compound having a polymerizable unsaturated group contained in the ink. It is preferably formed from a clear paint containing a compound having a polymerizable unsaturated group having the same polymerization reaction mechanism. According to a preferred aspect of the present invention, the compound having a polymerizable unsaturated group contained in the clear paint is preferably an acrylic compound having a polymerizable unsaturated group.

  Further, according to another preferred aspect of the present invention, the clear layer has a region where the ink layer is formed on the surface of the primer layer and whether the region where the ink layer is not formed is present in any manner. Regardless of the case, it is preferable that the primer layer is formed over the entire region where the ink layer can be formed and covers the primer layer or the ink layer or both.

  According to a more preferred aspect of the present invention, the decorative material according to the present invention is an acrylic material in which the ink layer and the clear layer have a polymerizable unsaturated group contained in the colored ink and / or transparent ink forming the ink layer. The interface between these two layers is that the polymer of the compound and the polymer of the acrylic compound having a polymerizable unsaturated group contained in the clear paint forming the clear layer are produced by the same polymerization reaction mechanism. It is more preferable that it adheres by the chemical bond produced in (1). Here, the interface between the ink layer and the clear layer includes a boundary between these two layers, and as long as it is a region where the above-described chemical bond occurs, a part of the region on the surface side of the ink layer and the bottom side of the clear layer. It means a region having a predetermined thickness including the region of the part.

  By providing the clear layer, the decorative material according to the present invention can obtain excellent image clarity and gloss. Moreover, it becomes possible to protect a decorating material from external stresses, such as contamination and an injury.

  Further, by providing the clear layer, even when the melamine decorative material undergoes a volume change due to moisture, in addition to the ink layer described above, the clear layer also has a resistance against the deformation force of the melamine decorative material. As a result, the flexible primer layer can reliably absorb the deformation force of the melamine decorative material. Therefore, it becomes possible to ensure the protection of the ink layer and the clear layer, and it is based on the melamine decorative material, and even when the primer layer, the ink layer and the clear layer are provided on this, it is excellent A decorative material having high durability can be obtained.

Clear paint The clear paint forming the clear layer constituting the decorating material according to the present invention is a compound having a polymerizable unsaturated group having the same polymerization reaction mechanism as the compound having a polymerizable unsaturated group contained in the ink, preferably An acrylic compound having a polymerizable unsaturated group is included. According to a preferred embodiment of the present invention, the clear paint for forming the clear layer is a compound having a polymerizable unsaturated group, preferably an acrylic compound having a polymerizable unsaturated group, which is included in the colored ink and the transparent ink described above. It is preferable to include a compound having the same or the same polymerizable unsaturated group, preferably an acrylic compound having a polymerizable unsaturated group.

  Since the acrylic compound having a polymerizable unsaturated group contained in the clear paint is the same or the same as the acrylic compound having a polymerizable unsaturated group contained in the colored ink and the transparent ink, irradiation of both active energy rays is performed. The polymerization reaction mechanism by is the same (even if the types of active energy rays are different). Accordingly, the clear layer and the ink layer can be firmly adhered by a chemical bond generated near the interface between these two layers. Furthermore, the acrylic compound having a polymerizable unsaturated group contained in the clear coating penetrates and diffuses into the ink layer, and is structurally entangled with the acrylic compound having a polymerizable unsaturated group that forms the ink layer, thereby clearing. It becomes possible to improve the adhesion between the ink layer and the ink layer.

  As the acrylic compound having such a polymerizable unsaturated group, an acrylic polymerizable oligomer, a prepolymer, and a low molecular acrylic polymer can be preferably used. According to a more preferred aspect of the present invention, the acrylic compound having a polymerizable unsaturated group is an acrylic urethane-based polymerizable compound. Specific examples thereof include acrylic urethane-based polymerizable monomers, oligomers, prepolymers, and low molecular acrylic urethane polymers. This makes it possible to protect the surface of the ink layer with a transparent water-resistant coating. Moreover, it becomes possible to obtain the decorating material which has high surface hardness.

  Moreover, the clear paint can contain the same thing as the polymerization initiator which the colored ink and transparent ink which were already demonstrated.

  The clear paint may contain a solvent (water and / or organic solvent). Further, the clear paint can appropriately contain various additives such as a thinner such as butyl acetate, a matting agent, and a rheology control agent. Furthermore, you may include a color material in the range which does not impair the transparency of a clear layer.

  The clear layer formed on the entire surface of the primer layer on which the ink can be applied by the clear paint preferably has a layer thickness of 30 to 150 μm. From the viewpoint of image clarity and durability of the clear layer, the layer thickness is more preferably 50 to 120 μm.

According to a preferred aspect of the present invention, in the decorating material according to the present invention, it is preferable that the thicknesses of the primer layer, the ink layer, and the clear layer satisfy the following relational expressions.
The thickness of the primer layer <the thickness of the ink layer <the thickness of the clear layer. Thereby, the dispersion and absorption by the primer layer of the stress caused by the volume change of the melamine decorative material can be reliably performed. In addition, since the planar accuracy of the soft primer layer can be increased, the influence of stress can be suppressed while maintaining high coating quality.

According to a preferred embodiment of the strip present invention, in the decorative material according to the present invention, among the side surfaces of the decorative material, the side surface of the substrate at least part of the melamine decorative material, i.e. a side of the decorative material It is preferable that an edge material is further provided on the side surface excluding the melamine-containing layer, the primer layer, the ink layer, and the portion where the clear layer is optionally formed.

  The base material of the low-pressure melamine decorative material has a porous structure mainly composed of wood. Since there is no melamine layer on the side surface of the low-pressure melamine decorative material and the wood is exposed, when the primer composition or ink is applied to the low-pressure melamine decorative material, these compositions penetrate into the base material. Then, moisture or moisture may permeate from this portion, and the base material may be deformed, or the primer layer, the ink layer, and possibly the clear layer may be peeled due to this deformation. Therefore, by providing an edge material on the side surface of the decorative material, moisture and moisture penetrate into the side surface or the inside of the base material of the low-pressure melamine decorative material, particularly when the decorative material according to the present invention is used in a watering device. Thus, it is possible to prevent the base material from being deformed and the primer layer, the ink layer and the clear layer from being peeled off due to the deformation. This edge material can be provided by sticking to the side surface of a melamine decorative material, for example using an adhesive agent.

  According to a more preferred embodiment of the present invention, the edge material is a primer layer formed by laminating the entire side surface of the decorating material, that is, the side surface of the melamine decorative material (base material and melamine-containing layer), and further on the surface of the melamine decorative material. More preferably it is provided on the side of the layer and optionally the clear layer. If there is a region where neither colored ink nor transparent ink is applied to the peripheral part of the primer layer, the clear layer may not be sufficiently adhered in that region, and the clear layer may peel off, but the entire side surface of the decorating material This can be prevented by providing an edge material on the surface.

  As a material used for the edge material, any material can be used without any limitation as long as it can avoid the penetration of moisture into the side surface or inside of the base material of the melamine decorative material. For example, a known natural resin or synthetic resin can be used. Among these, a polypropylene resin, a polyethylene resin, an ABS resin, a PET resin, a DAP tree, an acrylic resin, and the like can be preferably used. The rim material is preferably a long thin plate having a thickness of 0.5 to 3 mm.

  According to the preferable aspect of this invention, it is preferable that an edge material has the design which matches the design of the ink layer of a decorating material.

Use According to a preferred embodiment of the present invention, the decorating material according to the present invention has strong adhesion, excellent durability, and design properties, and is therefore preferable for watering equipment such as kitchens, toilets, bathrooms, and toilets. Can be used. As a concrete example of the decorative material for the water supply device, for example, when the water supply device is a system kitchen, the floor plate, the wall cabinet, the peripheral unit and the like constituting the door plate, and the bottom plate of each storage A side plate, a top plate, etc. can be mentioned preferably.

According to another aspect of the manufacturing method of the present invention of the decorative material, the present invention is, strong adhesion, excellent durability, providing a manufacturing method excellent design property which can realize decorative material as its object Yes. And the manufacturing method of the decorating material by this invention is the following.
Preparing a cosmetic material having a melamine-containing layer on its surface;
On the surface of the melamine-containing layer provided in the decorative material, a curing agent having a functional group capable of chemically bonding to an amino group in the melamine resin contained in the melamine-containing layer, and a function capable of crosslinking reaction with the curing agent. Applying a primer composition comprising a main agent having a plurality of groups;
Curing the primer composition to form a primer layer that is incompletely cured;
A polymerizable unsaturated group capable of acting on a reaction product of a curing agent and a main agent contained in a coloring material, the primer composition, or a part of the surface of the primer layer in an incomplete curing state. A step of applying a colored ink containing at least a compound having a colorant and a transparent ink containing at least a compound having no polymerizable material and having the polymerizable unsaturated group, and then curing the colored ink and the transparent ink to form an ink layer And at least.

In the method of manufacturing the decorative material according to prepare the invention of the decorative material is first prepared decorative material. The cosmetic material used in the production method according to the present invention is as described above.

Application of primer composition In the method for producing a decorative material according to the present invention, the surface of the melamine-containing layer provided in the decorative material is then chemically bonded to the amino group in the melamine resin contained in the melamine-containing layer. Primer composition comprising a curing agent having at least one functional group selected from possible functional groups, preferably isocyanate groups and carbodiimide groups, and a main agent having a plurality of functional groups capable of crosslinking reaction with the curing agent Apply. The details of the curing agent and the main agent contained in the primer composition are as described above.

  Further, as already described, when the primer composition is applied to the surface of the melamine-containing layer, at least one functional group selected from an isocyanate group and a carbodiimide group included in the curing agent included in the primer composition is a melamine cosmetic material. It chemically reacts with amino groups in the melamine resin contained in the melamine-containing layer. Thereby, the melamine-containing layer and the primer layer can be attached by at least one chemical bond selected from a urea bond and an amide bond generated near the interface between these two layers.

  As a method for applying the primer composition to the surface of the melamine-containing layer provided in the melamine decorative material, a general coating method such as spray coating, roll coater coating, or flow coater coating can be used. In applying the primer composition, it is considered that there is no mixing of foreign substances and coating unevenness.

Formation of primer layer in which primer composition is incompletely cured In the method for producing a decorative material according to the present invention, the primer composition is then cured, and the primer layer in an incompletely cured state is prepared. Form.

  In the present invention, the “incompletely cured state” means a state from the start to the end of the crosslinking reaction between the curing agent and the main agent contained in the primer composition. Whether or not the curing is incomplete can be determined, for example, by the following simple test. Specifically, first, a primer composition is applied to a melamine decorative material, and then cured under predetermined conditions. Next, 0.2 ml of 1,6-hexanediol diacrylate is dropped on the surface of the primer layer. After 5 seconds, using “Kimwipe” (manufactured by Nippon Paper Crecia Co., Ltd.), the portion where the acrylate was dropped was reciprocated by hand to wipe off the acrylate. If the trace does not remain on the surface of the primer layer even if the Kimwipe is slid by 10 reciprocations by hand, it is determined that the state is “completely cured”. On the other hand, when the Kimwipe is slid by 10 reciprocations or less by hand, when the trace remains on the surface of the primer layer or when the primer layer is removed because it is swollen or dissolved by the acrylate, “incomplete curing” ".

  As the primer layer cross-linking reaction proceeds, the permeability and adhesion of the colored ink and transparent ink to the primer layer change, so that the primer layer is cured so that the wettability and adhesion of these inks are optimal. It is preferable to control the incomplete state.

According to a preferred embodiment of the present invention, in order to control the state of incomplete curing of the primer layer, for example, the intensity of the peak (2269 cm ⁻¹ ) derived from the NCO group and the CH ₃ group in the infrared spectroscopic measurement Based on the NCO / CH ₃ ratio obtained by taking a ratio with the intensity of the peak (2946 cm ⁻¹ ), the isocyanate group residual ratio of the curing agent contained in the primer composition can be controlled within a specific range. A preferable range of the NCO / CH ₃ ratio is 0.8 or more and 1.1 or less. In addition, it is considered to control the penetrability / diffusibility of the ink to the primer layer while maintaining good adhesion between the primer layer and the melamine decorative material.

  According to the preferable aspect of this invention, it is preferable to perform the drying containing a heating as a method of hardening a primer composition. Thereby, the solvent (diluent) in a primer composition volatilizes, the viscosity of a primer composition rises, and the crosslinking reaction of a hardening | curing agent and a main ingredient advances. Specific examples of drying include room temperature drying or forced drying. Specific examples of forced drying include general drying methods such as IR (infrared) drying and hot air drying. Moreover, when performing forced drying, it is preferable to dry at the base-material temperature of the range of 40-70 degreeC. Thereby, for example, it becomes possible to prevent a curing failure due to the remaining of the solvent. In addition, it is possible to prevent warping from occurring in the wood that is the base material of the melamine decorative material. Furthermore, excessive curing can be prevented by preventing excessive drying. A more preferable substrate temperature is 50 to 65 ° C.

  The primer layer can be appropriately cured. Thereby, it becomes possible to adjust hardening of a primer composition to an appropriate state. As a result, the primer layer and the ink layer can be firmly adhered to each other, and furthermore, an excellent ink having a high color developability by securing an appropriate penetration and diffusion state of the colored ink and the transparent ink into the primer layer. It becomes possible to obtain a layer. According to a preferred embodiment of the present invention, the curing is preferably performed at a temperature of 20 to 40 ° C. and a relative humidity of 5 to 95%, for example, exceeding 0 hour and within 18 hours.

Application of colored ink and transparent ink to the surface of the primer layer in an incompletely cured state In the method for producing a decorative material according to the present invention, the surface of the primer layer in an incompletely cured state A colored ink and a transparent ink are applied to a part or all of the above. Details of the ink, the colored ink, and the transparent ink are as described above.

  Moreover, as already explained, when these inks are applied to the surface of the primer layer that is incompletely cured, the acrylic compound having a polymerizable unsaturated group contained in the ink forms a primer layer undergoing a crosslinking reaction. By appropriately penetrating and diffusing into the crosslinked body and then curing the ink, it is possible to structurally entangle the reaction product. As a result, the primer layer and the ink layer can be firmly adhered by the structural entanglement generated at the interface between these two layers.

Application of Colored Ink and Transparent Ink by Inkjet Printing According to a preferred embodiment of the present invention, in the method for producing a decorating material according to the present invention, a part of the surface of the primer layer that is incompletely cured or It is preferable that the method of applying the colored ink and the transparent ink to the whole is an ink jet method. By performing ink jet printing, it is possible to easily perform high-quality decoration rich in color variation and design variation on the primer layer. In addition, it is possible to flexibly meet various design requirements in a short time, at low cost, and to provide a method for manufacturing a decorative material with high practical value.

Inkjet Printing Apparatus The inkjet printing apparatus used for inkjet printing of colored ink and transparent ink may be either serial type or line type. For example, when emphasizing design, it is preferable to use a serial type ink jet printing apparatus.

  FIG. 3 shows a schematic configuration diagram of a serial type (shuttle scan type) ink jet printing apparatus. Each of the colored ink and the transparent ink is supplied from the ink tank 8 to the head unit portion 2 through an ink supply tube (not shown). The head unit 2 is fixed by a fixed shaft 5 made of a long metal shaft, and reciprocates at a variable speed by a power unit 4 that can reciprocate. The power unit 4 capable of reciprocating motion incorporates an ink supply tube (not shown) and a head control electrical wiring (not shown). At both ends of the fixed shaft 5 of the head unit 2, a maintenance unit 3 for performing head maintenance and cleaning is provided. Further, outside these, a control unit 6 (for example, a personal computer) and an ink tank 8 for controlling the ink jet printing apparatus are arranged.

  The head unit 2 is composed of seven sets of headsets in which two heads are arranged for each color to have, for example, 200 dpi, and two ultraviolet irradiation means (for example, metal halide lamps). The headsets are arranged in order from the left, for example, for black ink, cyan ink, magenta ink, yellow ink, light cyan ink, light magenta ink, and transparent ink. In addition, in order to enrich variations in the discharge methods of colored ink and transparent ink in bidirectional printing, in the example of the above seven sets of heads, eight sets of heads provided with a transparent ink headset on the leftmost side It can also be a set. In FIG. 3, a total of two ultraviolet irradiation means are provided on both sides of the headset, but one may be provided on one side.

  A print medium stage 7 on which the print medium can be fixed is disposed immediately below the head. The print medium 9 is conveyed in a direction perpendicular to the reciprocating motion of the head along the horizontal plane, that is, in the sub-scanning direction. The movement in the sub-scanning direction during printing may be performed with the head movable, or the stage movable.

Application Mode of Colored Ink and Transparent Ink on Primer Layer Surface In the method for producing a decorating material according to the present invention, the primer composition was applied while the primer composition was incompletely cured. Colored ink and transparent ink are applied to part or all of the region, preferably by inkjet printing, in the following manner.

  In this embodiment, a colored ink is printed on a part of the printable area on the surface of the primer layer to form a colored ink layer made of the colored ink, and a part or all of the remaining part where the colored ink is not printed is formed. Transparent ink is printed to form a transparent ink layer made of transparent ink. For example, colored ink is applied to a plurality of independent regions on the surface of the primer layer to form a colored ink layer, while transparent ink is applied to a plurality of independent regions on the surface of the primer layer where the colored ink layer is not formed. And a case where a transparent ink layer is formed. Further, in this aspect, the colored ink and the transparent ink are applied to a part of the printable region on the surface of the primer layer, and the remaining region is a region where neither the colored ink nor the transparent ink is applied, That is, an embodiment in which the primer layer is an exposed region (in contact with the outside world) is also included.

  Moreover, in the said aspect, as a specific example, when a colored ink layer (for example, an island-like or spotted colored ink layer) is formed by applying a colored ink to a part of the primer layer surface, the primer layer The case where a light colored colored ink layer is formed by forming fine dots of colored ink on a part of the surface, or a combination thereof, can be mentioned. If there is a small area where the colored ink is applied over the entire surface of the primer layer, and then a further clear layer is provided over the entire surface of the primer layer, the remaining area where the colored ink is not applied, i.e., the primer layer The clear paint will be applied directly to the wide area that is exposed. However, in this case, it is difficult to obtain adhesion between the primer layer and the clear layer because it is difficult for the clear paint to penetrate and diffuse into the primer layer in a state where the crosslinking reaction of the primer layer has advanced considerably. .

  On the other hand, even in the state where the crosslinking reaction of the primer layer has advanced considerably, in the region where the colored ink is applied, the colored ink layer and the clear layer are the two layers until the colored ink is completely cured. Therefore, the adhesion between the primer layer and the clear layer can be ensured through the colored ink layer.

  In short, when there is only a small area where the adhesion between the primer layer and the clear layer can be secured via the colored ink layer, while the primer layer and the clear layer are in direct contact with each other and the adhesion between the two is difficult to obtain. There is a high tendency for the clear layer to peel from the primer layer. Therefore, in such a case, the adhesion between the primer layer and the clear layer can be realized through the transparent ink layer by applying the transparent ink to a part or all of the region where the colored ink is not applied. Is possible. As a result, it is possible to prevent the clear layer from peeling off from the primer layer.

Application Mode of Transparent Ink As described above, the transparent ink layer formed by applying the transparent ink only needs to be formed in a region sufficient to ensure adhesion between the primer layer and the clear layer. According to a preferred aspect of the invention, it is preferable that the amount of the transparent ink applied to the primer layer surface per unit area is less than the amount of the colored ink applied per unit area.

  Specifically, the area where the transparent ink layer per unit area exists is narrower than the area where the colored ink layer per unit area exists, and the transparent ink layer is formed in the entire area where the colored ink layer is not formed. Can be mentioned. In addition, the entire area where the colored ink layer is not formed is further divided into a formation area and a non-formation area of the transparent ink layer, and these are mixed, so that the transparent ink layer per unit area An embodiment in which the existing area is narrower than the existing area of the colored ink layer can be mentioned. Moreover, the aspect which combined these aspects can also be mentioned.

  As a specific example of the combined mode, when the colored ink is not applied to the peripheral portion of the primer layer surface, the transparent ink is applied to the peripheral portion of the primer layer surface, and the transparent ink is applied to the central portion of the primer layer surface. A method of applying so that the application area and the non-application area are mixed (for example, scattered in islands or spots) can be used (see FIG. 2). Thereby, it becomes possible to ensure good adhesion between the primer layer and the clear layer through the entire ink layer composed of the transparent ink layer and the colored ink layer.

  According to another preferred embodiment of the present invention, the transparent ink is preferably thinned and printed as an application mode of the transparent ink that ensures adhesion between the primer layer and the clear layer. By performing thinning printing, the application area of the transparent ink can be reduced. Accordingly, the adhesion between the primer layer and the clear layer can be ensured with a small amount of the transparent ink used compared with the case where the thinning printing is not performed, which is efficient and economical.

  The thinning-out printing of the transparent ink can be appropriately performed as long as the adhesion between the primer layer and the clear layer can be ensured through the entire ink layer composed of the colored ink layer and the transparent ink layer. In the present invention, “thinning printing” refers to printing in which not all pixels in one band are subjected to printing in one pass. Here, a plurality of pixels positioned on one line extending in the main scanning direction of the print area is referred to as a “band” as a print unit, and the printable area is composed of a plurality of bands corresponding to the area. Is done. As a specific example of thinning printing, for example, printing is performed by printing one dot or more empty dot widths that are not printed in between, and thinning out ink droplets ejected per unit area at predetermined intervals. In addition, ink droplets ejected per unit area may be printed by being thinned at random intervals, or ink droplets may be thinned and printed in a manner in which predetermined intervals and random intervals are mixed regularly or irregularly. May be.

  According to another preferred embodiment of the present invention, in the method for producing a decorating material according to the present invention, the application amount per unit area of the transparent ink is 20% or more and less than 100% (area) of the application amount of the colored ink. % Or volume%). That is, the application amount per unit area of the transparent ink is 20% or more and 100% as a ratio (percentage: area%) that the area of the transparent ink layer on the primer layer surface occupies the area of the colored ink layer on the primer layer surface. It is preferable that it is less than. Moreover, the application amount per unit area of the transparent ink is 20% or more and less than 100% as a ratio (percentage; volume%) of the volume of the transparent ink layer on the surface of the primer layer to the volume of the colored ink layer. Is preferred.

  In the third aspect, for example, by adjusting the discharge amount of the transparent ink and the discharge amount of the colored ink and printing on the surface of the primer layer, the colored ink printing region and the colored ink non-printing region are printed. It is possible to make the glossiness in the substantially uniform. In other words, the gloss ratio that depends on the difference in printing duty on the surface of the primer layer can be minimized (maximum gloss / minimum gloss is 1 or near it), and high-quality decoration without gloss unevenness. Can be realized. In particular, even when the clear layer is not formed, it is advantageous in that glossiness can be imparted to the surface of the decorating material, that is, the surface of the ink layer. Note that the print duty is defined by the following equation and means a unit of the calculated value D.

D = {number of actual printing dots / (vertical resolution × horizontal resolution)} × 100 (%)
(In the formula, “number of actual print dots” is the number of actual print dots per unit area, and “vertical resolution” and “horizontal resolution” are resolutions per unit area, respectively.)

  In order to adjust the discharge amount of the transparent ink and the discharge amount of the colored ink, for example, it is preferable to adjust the discharge amount of the transparent ink according to the print duty value of the colored ink. Specifically, when the printing duty of the colored ink is low, the discharge amount of the transparent ink is increased, and when the printing duty of the colored ink is high, the discharge amount of the transparent ink is decreased. When the printing duty of the colored ink is 20 to 60%, particularly 30 to 50%, it is desirable to adjust the discharge amount of the transparent ink.

  In another adjustment method, when the printing duty of the colored ink is low, the total discharge amount of the colored ink and the transparent ink is adjusted to a fixed amount. When the printing duty of the colored ink is high, Regardless of the printing duty, the discharge amount of the transparent ink can be adjusted to a constant small amount. Specifically, when the printing duty of the colored ink is low, the total discharge amount of the colored ink and the transparent ink is adjusted to a range of 20 to 60% in total of the printing duty, and when the printing duty of the colored ink is high, The discharge amount of the transparent ink can be adjusted so as to be constant within the range of 1 to 20% with the printing duty.

Curing of colored ink and transparent ink In the method for producing a decorating material according to the present invention, the colored ink and transparent ink applied to the surface of the primer layer that is incompletely cured are then cured, and the ink Form a layer. Curing of these inks is preferably controlled so that the strength of the ink layer formed after curing is good and these ink layers are firmly adhered to the primer layer. As will be described later, when the clear layer is formed, it is preferable to apply the clear paint in a state where the ink layer is incompletely cured.

  As already described, the colored ink and the transparent ink are in a state in which the acrylic compound having a polymerizable unsaturated group contained in the colored ink and the transparent ink appropriately penetrates and diffuses into the crosslinked body during the crosslinking reaction forming the primer layer. By being cured, the crosslinked body forming the primer layer and the acrylic polymer contained in the ink can form a densely (condensed) entangled state with each other. As a result, the primer layer and the ink layer can be firmly adhered.

  An active energy ray can be used as a method of curing the colored ink and the transparent ink. According to a preferred embodiment of the present invention, a method of curing by either thermosetting or photocuring is preferable. As a result, curing time can be shortened, heat-sensitive materials can be cured, and the light intensity and wavelength can be adjusted to enable delicate control of the coating film characteristics. Light can be turned on and off instantaneously. Compared to thermosetting, the time required for starting up the equipment can be shortened and work efficiency can be improved. Since it can be used without solvent, it can be used as an environmental pollutant such as volatile organic compounds (VOC) and hazardous air pollutants (HAP). Since there is no generation of carbon dioxide and no generation of carbon dioxide, various advantages such as excellent environmental compatibility are brought about.

  According to a preferred embodiment of the present invention, in order to realize such strength and adhesion of the ink layer, for example, after applying a colored ink and a transparent ink to the primer layer, the active layer is immediately irradiated to cure. It is preferable to start. In addition, it is preferable to appropriately control the illuminance and the integrated light amount of the active energy rays to prevent poor curing due to oxygen inhibition that may occur, for example, when these are insufficient. According to the preferable aspect of this invention, it is preferable to use an ultraviolet-ray as an active energy ray.

  The coloring ink and / or the transparent ink may be cured under heating conditions, regardless of the method of thermal curing or photocuring. When heating, it is preferable to carry out at the highest temperature of the base material temperature of 40-70 degreeC. Thereby, for example, it is possible to prevent warping from occurring in wood that is the base material of the low-pressure melamine decorative material. Furthermore, by preventing excessive drying, it is possible to prevent excessive curing of the ink layer. A more preferable substrate temperature is 50 to 65 ° C.

Process for forming a clear layer
Application of Clear Paint According to a preferred embodiment of the present invention, in the method for producing a decorating material according to the present invention, the same polymerization as the compound having a polymerizable unsaturated group contained in the ink is then performed on the surface of the ink layer. It is preferable to apply a clear paint containing a compound having a polymerizable unsaturated group having a reaction mechanism, preferably an acrylic compound having a polymerizable unsaturated group. Thereby, as already explained, the ink layer and the clear layer are a polymer of an acrylic compound having a polymerizable unsaturated group contained in the colored ink and / or transparent ink forming the ink layer, and the clear layer. Acrylic compound polymer having a polymerizable unsaturated group contained in the clear paint to be formed is produced by the same polymerization reaction mechanism, and is attached by a chemical bond generated at the interface between these two layers. Is possible.

  Further, according to another preferred embodiment of the present invention, the clear paint is used on the surface of the primer layer whether or not there is a region to which the colored ink and the transparent ink are applied and a region to which these inks are not applied. Rather, it is preferably applied over the entire area of the primer layer surface where these inks can be applied.

  By providing the clear layer, the decorative material obtained by the production method according to the present invention can obtain excellent image clarity and gloss. Moreover, according to the manufacturing method by this invention, it becomes possible to protect the decorating material obtained by this from external stresses, such as a contamination and an injury.

  As a method for applying the clear paint to the surface of the colored ink layer and the transparent ink layer, a general coating method such as spray coating, roll coater coating, or flow coater coating can be used. In application, it is considered that there is no mixing of foreign matters and uneven application.

Drying of clear paint When a clear paint contains a solvent, it is preferable to perform drying including heating after application. Specific examples of drying include room temperature drying or forced drying. Specific examples of forced drying include general drying methods such as IR (infrared) drying and hot air drying. Moreover, when performing forced drying, it is preferable to dry at the base-material temperature of the range of 40-70 degreeC. Thereby, for example, it becomes possible to prevent a curing failure due to the remaining of the solvent. In addition, it is possible to prevent warping from occurring in the wood that is the base material of the melamine decorative material. Furthermore, by preventing excessive drying, it is possible to prevent excessive curing of the clear paint. A more preferable substrate temperature is 50 to 65 ° C.

According to a preferred embodiment of the curing invention clear coating, in the method of manufacturing the decorative material according to the present invention, then, it is irradiated with an active energy ray to the coated clear coating, thereby curing the clear coating, A clear layer is formed.

  The curing of the clear paint is preferably started in a state where the curing of the ink layer is incomplete. As already described, since the acrylic polymerizable compound preferably contained in the clear paint and the acrylic polymerizable compound preferably contained in the colored ink and / or the transparent ink have the same polymerization mechanism, the ink layer and the clear A layer can be attached by a chemical bond generated at the interface between these two layers. However, if the ink layer has already been completely cured at the time of applying the clear paint, or if the curing reaction has progressed considerably, there is no longer a target that the polymerizable compound contained in the clear paint can be polymerized. No or very little. Therefore, in order to realize a strong adhesion state between the clear layer and the ink layer, it is preferable to cure the clear paint in an appropriate state before the ink layer is completely cured.

  As a method for curing the clear paint, either heat curing or photocuring can be used, but photocuring is preferable. Thereby, a clear layer having an excellent surface hardness can be obtained. Regardless of the method of thermal curing or photocuring, it may be performed under heating conditions. When heating, it is preferable to perform the curing at the maximum temperature in the range of 40 to 70 ° C. Thereby, for example, it becomes possible to prevent a curing failure due to the remaining of the solvent. In addition, it is possible to prevent warping from occurring in the wood that is the base material of the melamine decorative material. Furthermore, by preventing excessive drying, it is possible to prevent excessive curing of the clear layer. A more preferable substrate temperature is 50 to 65 ° C.

  According to a preferred embodiment of the present invention, in order to realize the surface strength and adhesion of the clear layer, for example, after applying the clear paint to the colored ink layer, the transparent ink layer, and the primer layer, it is dried when a solvent is contained. Immediately after that, the active energy ray is irradiated to start curing. In addition, it is preferable to appropriately control the illuminance and the integrated light amount of the active energy rays to prevent poor curing due to oxygen inhibition that may occur, for example, when these are insufficient. It is preferable to control the residual ratio of the solvent contained in the clear coating so that the solvent does not remain excessively and whitening or cracking of the clear layer does not occur. According to the preferable aspect of this invention, it is preferable to use an ultraviolet-ray and IR as an active energy ray.

Complete curing of primer layer (post-curing)
According to a preferred aspect of the present invention, in the method for producing a decorating material according to the present invention, the colored ink and the transparent ink are applied on the primer layer in a state where the primer layer is not completely cured. It is preferable to completely cure the primer layer. The complete curing treatment can be performed by the same method as the method for curing the primer layer already described. Further, complete curing of the primer layer can be performed in the same process as curing of the colored ink and the transparent ink. Here, “performing in the same step” includes including the complete curing of the primer layer in the curing step of the colored ink and the transparent ink, and replacing it (the same applies hereinafter). Further, when a clear layer is further provided on the colored ink layer and the transparent ink layer, it is preferable to completely cure after applying the clear paint. In particular, when the clear paint contains a solvent or is a thermosetting paint, the process of drying the solvent or the process of curing the clear layer and the process of post-curing the primer layer can be performed in the same process. it can. Further, the primer layer can be completely cured over both of these processes.

Step of providing edge material on side surface of decorating material According to a preferred embodiment of the present invention, in the method for producing a decorating material according to the present invention, at least the base material portion of the melamine decorative material among the side surfaces of the decorating material It is preferable to further include a step of providing an edge material on the side surface of the decorative material, that is, the side surface of the decorating material, excluding the melamine-containing layer, the primer layer, the ink layer, and the portion where the clear layer is optionally formed.

  The base material of the low-pressure melamine decorative material has a porous structure mainly composed of wood. Since there is no melamine layer on the side surface of the low-pressure melamine decorative material and the wood is exposed, when the primer composition or ink is applied to the low-pressure melamine decorative material, these compositions penetrate into the base material. Then, moisture or moisture may permeate from this portion, and the base material may be deformed, or the primer layer, the ink layer, and possibly the clear layer may be peeled due to this deformation. Therefore, by providing an edge material on the side surface of the decorative material, moisture and moisture penetrate into the side surface or the inside of the base material of the low-pressure melamine decorative material, particularly when the decorative material according to the present invention is used in a watering device. Thus, it is possible to prevent the base material from being deformed and the primer layer, the ink layer and the clear layer from being peeled off due to the deformation. This edge material can be provided by sticking to the side surface of a melamine decorative material, for example using an adhesive agent.

  According to a more preferred embodiment of the present invention, in the method for producing a decorative material according to the present invention, the entire side surface of the decorative material, that is, the side surface of the melamine cosmetic material (base material and melamine-containing layer), further a primer layer, It is preferable to include a step of further providing an edge material on the side surface of the ink layer and optionally the clear layer. If there is a region where neither colored ink nor transparent ink is applied to the peripheral part of the primer layer, the adhesion of the clear layer in that region is insufficient, and the clear layer may peel off from the primer layer. This can be prevented by providing an edge material on the entire side surface.

  According to a preferred aspect of the present invention, in the method for producing a decorating material according to the present invention, an edge material is formed (coated) on the entire side surface of the decorating material without forming (painting) a primer layer, an ink layer, and a clear layer. Is preferably provided. For low-pressure melamine cosmetics that contain a lot of air inside, if the entire surface is painted to block air permeability, the deformation will increase, and as a result, the painted surface may be greatly deformed or cracked. By providing the edge material without painting the side surfaces, the deformation can be reduced. This also makes it possible to make the primer layer thinner. Furthermore, even if the primer layer is thinned, deformation can be absorbed and the amount of deformation can be reduced, so that the waviness of the painted surface can be reduced and a beautiful painted surface can be realized.

Moreover, according to the preferable aspect of this invention, in the manufacturing method of the decorating material by this invention, it is preferable to provide an edge material after drying an ink layer and a clear layer. By drying the side surface without painting, deformation due to expansion and contraction of internal air due to the low-pressure melamine decorative material can be alleviated, and the coating quality of the decorative material (finished product) can be improved.

Grinding treatment According to a preferred embodiment of the present invention, in the method for producing a decorating material according to the present invention, before the edge material is provided on the side surface of the decorating material, the side surface of the decorating material can be further ground. preferable. As above-mentioned, the base material is exposed in the side part of the base material of a low-pressure melamine cosmetic material among the side surfaces of a decorating material, and the shape of the side surface is uneven. Therefore, it is possible to make the side surface flat by performing a grinding process as a pretreatment for providing the edge material on the side surface of the decorative material. As a result, the edge material can be easily and hermetically provided on the side surface of the decorative material.

  According to a preferred embodiment of the present invention, the edge material is preferably provided after sequentially forming a primer layer, an ink layer, and optionally a clear layer on the surface of the melamine-containing layer of the melamine decorative material. This makes it possible to prevent chipping of the melamine decorative material during the grinding process. When affixing the edge after forming the ink layer, it is preferable to grind the ink layer after completely curing it so that the ink layer is not soiled with the grinding powder.

  The following examples further illustrate the present invention. The present invention is not limited to these examples.

Materials used
Low-pressure melamine decorative material As a low- pressure melamine decorative material, low-pressure melamine particle board t15 mm (18 U) (JIS A5908) manufactured by Caindle Co. was used.

Primer composition The following was prepared as a primer composition.
Primer D5
Main agent: Acrylic polyol (weight average molecular weight 55000, hydroxyl value 52 mg KOH / g) 48 mass% (heating residue), normal butyl acetate 52 mass%
Curing agent: isocyanurate type HDI (NCO content 12.4% by mass) 60% by mass, normal butyl acetate 40% by mass
Diluent: methyl isobutyl ketone (MIBK), butyl acetate The above main agent, curing agent and diluent are mixed so that the mixing ratio (mass ratio) thereof is the main agent: curing agent: diluent = 6: 1: 6. did. That is, the curing agent was added in a molar ratio of 1.1 to the hydroxyl value of the main resin.

Primer D1
Main agent: Acrylic polyol (weight average molecular weight 20000, hydroxyl value 156 mg KOH / g) 48 mass% (heat residue), normal butyl acetate 52 mass%
Curing agent: isocyanurate type HDI (NCO content 12.4% by mass) 60% by mass, normal butyl acetate 40% by mass
-Diluent: Mixed solvent of methyl isobutyl ketone (MIBK) and butyl acetate The mixing ratio (mass ratio) of the above main agent, curing agent and diluent becomes main agent: curing agent: diluent = 2: 1: 2. Mixed. That is, the curing agent was added in a molar ratio of 1.1 to the hydroxyl value of the main resin.

Primer G
Main agent: Acrylic polyol (weight average molecular weight 38000, hydroxyl value 36 mg KOH / g) 32% by mass (heating residue), cellosolve acetate 22% by mass, butyl acetate 45% by mass, silica 1% by mass
Curing agent: isocyanurate type HDI (NCO content 12.4% by mass), 60% by mass, normal butyl acetate 40% by mass,
-Diluent: Mixed solvent of methyl isobutyl ketone (MIBK) and butyl acetate The mixing ratio (mass ratio) of the above main agent, curing agent and diluent is the main agent: curing agent: diluent = 8: 1: 3. Mixed. That is, the curing agent was added in a molar ratio of 1.2 with respect to the hydroxyl value of the main resin.

Primer C
Main agent: Acrylic polyol (weight average molecular weight 42000, hydroxyl value 92 mgKOH / g) 48 mass% (heating residue), ethylbenzene 21 mass%, xylene 21 mass%, normal butyl acetate 10 mass%
Curing agent: Adduct type HDI (NCO content 8.6% by mass) 51% by mass, ethyl acetate 49% by mass
Diluent: ethyl acetate 5% by mass, isobutyl acetate 20% by mass, butyl acetate 25% by mass, methoxypropyl acetate 50% by mass
The main agent, curing agent and diluent were mixed so that the mixing ratio (mass ratio) thereof was main agent: curing agent: diluent = 4: 1: 3. That is, the curing agent was added in a molar ratio of 0.65 with respect to the hydroxyl value of the main resin.

Primer B
Main agent: Polyester polyol (weight average molecular weight 30000, hydroxyl value 10 mg KOH / g) 48 mass% (heating residue), normal butyl acetate 52 mass%
Curing agent: Adduct type XDI (NCO content 6% by mass) 51% by mass, ethyl acetate 49% by mass
Diluent: 5% by mass of ethyl acetate, 20% by mass of isobutyl acetate, 25% by mass of normal butyl acetate, 50% by mass of methoxypropyl acetate
The main agent, curing agent and diluent were mixed so that the mixing ratio (mass ratio) thereof was main agent: curing agent: diluent = 7: 1: 3. That is, the curing agent was added in a molar ratio of 2.30 with respect to the hydroxyl value of the main resin.

Primer (carbodiimide)
・ Main agent: Aqueous acrylic resin dispersion (Nisshinbo Chemical “Carbodilite” PX-05A) 90.75% by mass
Curing agent: polycarbodiimide (“Carbodilite” V-02-L2 manufactured by Nisshinbo Chemical Co., Ltd.) 9.25% by mass

Primer (chlorinated polypropylene (chlorinated PP))
Main agent: Chlorinated PP (weight average molecular weight 100,000, chlorination rate 20-22%) 10% by mass
・ Diluent: 90% by mass of mixed solvent of methylcyclohexane and butyl acetate

Measurement of the molecular weight of the polyol The weight average molecular weight of the polyol, which is a component of each of the above primer compositions, was measured by using HLC-8120GPC (differential refractometer (RI-8020, manufactured by Tosoh Corp.)) manufactured by Tosoh Corporation and software (Tosoh Corporation). Equipped with Multi Station-8020) manufactured by Co., Ltd. Specifically, 80 mg of each polyol was weighed and dissolved in 20 ml of THF as a sample, 100 μL of this sample was injected into the following column H or L, and tetrahydrofuran (THF) was used as a developing solvent (flow rate: 1 ml / min). Then, high-speed gel permeation chromatography was performed at a column temperature of 40 ° C. The standard polystyrene used as the standard substance was prepared by weighing 10 mg each of 5 or 6 standard polystyrenes having different molecular weights, dissolving them in 100 ml of THF (20 ° C.), and allowing them to stand for 24 hours.

Column used: Column H: Four columns 5 connected to column 6 below. It was used for the purpose of transferring a polyol having a weight average molecular weight of 100,000 to 1,000,000.
Column L: the following column 6, column 4, column 3, column 2, and column 1 connected in order. It was used for the purpose of transferring a polyol having a weight average molecular weight of 100,000 or less.
TSKgel G2000HXL (Column 1) manufactured by Tosoh Corporation
TSKgel G3000HXL (column 2) manufactured by Tosoh Corporation
TSKgel G4000HXL (column 3) manufactured by Tosoh Corporation
TSKgel G5000HXL (column 4) manufactured by Tosoh Corporation
TSKgel GMHXL (Column 5) manufactured by Tosoh Corporation
Guard column HXL-H (column 6) manufactured by Tosoh Corporation

Colored inks Colored inks (cyan ink (C ink), magenta ink (M ink), yellow ink (Y ink), and black ink (K ink)) containing the following basic components and coloring materials were prepared. The color materials used for C ink, M ink, Y ink and K ink are C.I. I. Pigment blue 15: 3 (3 mass%), C.I. I. Pigment red 122 (3 mass%), C.I. I. Pigment Yellow 74 (3 mass%) and Carbon Black (CI Pigment Black 7) (3 mass%).
Acrylic polymerizable monomer mainly containing basic component 1,6-hexanediol diacrylate 70-80% by mass
UV-sensitive photopolymerization initiator 10% by mass
Dispersant 10% by mass
Additive (surfactant)

Transparent ink A transparent ink containing the following components was prepared.
Acrylic polymerizable monomer mainly containing 1,6-hexanediol diacrylate 70-80% by mass
UV-sensitive photopolymerization initiator 10% by mass
Dispersant 10% by mass
Additive (surfactant)

Contains clear compound polymerizable unsaturated group-containing acrylic compound and UV-sensitive photopolymerization initiator in solid content of about 50% by mass, with butyl acetate about 40% by mass, propylene glycol monomethyl ether acetate and ethyl acetate remaining An ultraviolet curable clear paint was prepared.

Preparation of decorating material The decorating material of the Example mentioned later was created in the following procedures and conditions.
Pretreatment of low-pressure melamine cosmetic material The surface of the low-pressure melamine particle board was wiped with a cloth dampened with cyclohexane, degreased and dried.

Formation of Primer Layer Each primer composition described above was applied to the surface of a pretreated low-pressure melamine particle board using a bar coater # 4, dried in a hot air drying oven (60 ° C.) for 30 minutes, and the dried film A primer layer having a thickness of 3 to 5 μm was formed.

Formation of Colored Ink Layer and Transparent Ink Layer The surface of the primer layer obtained was ink jet printed with the above color ink and transparent ink using an ink jet printer, and immediately irradiated with ultraviolet rays to give a layer thickness of 7.5 μm, 22. Uniform ink layers of 5 μm and 30 μm with no exposed portions of the primer were formed. Inkjet printing conditions and ultraviolet irradiation conditions were as follows.

Inkjet printing conditions The carriage moving speed of the inkjet printer was 1000 mm / s, and printing was performed with a width of 32 mm. Inkjet printing was performed by sending a low-pressure melamine particle board in the sub-scanning direction and repeating this each time ink application and ultraviolet (UV) irradiation were performed in two passes in the main scanning direction. That is, in the printing in the main scanning direction, ink application and UV irradiation are performed in the outward pass of the first pass, only UV irradiation is performed in the return pass, and then, in the same way as in the first pass, ink is applied in the forward pass of the second pass. Application and UV irradiation were performed, and only UV irradiation was performed on the return path. FIG. 4 shows a schematic configuration of each ink nozzle row and UV irradiation means in the used ink jet printer head. Here, T represents transparent ink, Y represents yellow ink, M represents magenta ink, C represents cyan ink, and K represents black ink. The forward path in the main scanning direction is from the left to the right of the page.

Moreover, ultraviolet curing was performed on the conditions of illumination intensity: 0.5-0.8 W / cm < ² >, integrated light quantity: 0.1-0.2 J / cm < ² >. The illuminance and the integrated light quantity were measured using an EYE UV METER equipped with a light receiver having a wavelength of light to be received of 365 nm.

Formation of clear layer The above-mentioned clear paint was applied to the surface of the obtained ink layer using a curtain coater, dried in a hot air drying oven (60 ° C.) for 30 minutes, and then irradiated with ultraviolet rays to obtain a solid layer thickness. Obtained a clear layer of 60 ± 10 μm. The ultraviolet curing was performed at a predetermined peak illuminance and integrated light amount using a high-pressure mercury lamp (lamp length (emission length): 1400 mm) as a lamp light source at a feed rate of the low-pressure melamine particle board at 1.3 m / min.

Evaluation
Adhesion test 1
Cut the surface of the cross-cut test coating film of the former JIS K5400-8.5 (currently JIS D0202) with a cutter (11 mm in the horizontal direction and 11 in the vertical direction at 2 mm intervals), and a 2 mm × 2 mm cutting mass 100 pieces were made. Thereafter, cellophane tape (CT-24 manufactured by Nichiban Co., Ltd.) was attached, and the state of the coating film after tape peeling was confirmed according to the following evaluation criteria.

Evaluation criteria (circle): There is no peeling of a film | membrane after tape peeling.
(Triangle | delta): A film | membrane peels partially after tape peeling.
X: 100 masses of the film are peeled off by the tape peeling.

Adhesion test 2
It conformed to the pull-off test of JIS K 5600-5-7.

Evaluation criteria ○: Peeling occurred in the substrate ×: Peeling occurred at the interface between the substrate and the coating film

Color test 1 (visual appearance) of the colored ink The colored ink printed in an arbitrary area on the surface of the primer layer with a width of 32 mm was visually evaluated according to the following evaluation criteria.
Evaluation criteria ○: Excellent color developability (no print streaks and uniform color development)
Δ: Good color developability (print streaks can be seen in part)
×: Color development is inferior (color unevenness due to printing stripes is conspicuous)

Color test of colored ink 2
Measure the line width of the colored ink for each of the samples that were subjected to the primer layer curing (temperature 40 ° C., relative humidity 90% for 2 hours) and those that were not performed. The value (%) divided by the line width was determined.

Examples 1 to 3, Comparative Examples 1 and 2 (Primer layer + ink layer 1)
Each primer paint described in the following Table 1 is applied to the surface of the pretreated low-pressure melamine decorative material of 100 mm × 100 mm so as to have a wet layer thickness of 9 μm, dried at 60 ° C. for 30 minutes, and the layer thickness is 3 A primer layer of ˜5 μm was formed. This is taken out from the drying oven, allowed to stand at room temperature for 30 minutes, cooled, and then M ink is solid printed on the entire surface of the primer layer using an ink jet printer and cured to form an ink layer having a layer thickness of 7.5 μm. And the decorating material sample of Examples 1-3 and Comparative Examples 1 and 2 was obtained. The obtained samples were left in an environment of a temperature of 40 ° C. and a relative humidity of 80% for 2 weeks, and then adhesion tests 1 and 2 were performed. The results were as shown in Table 1.

Examples 4 to 8 (Primer layer + Ink layer 2)
Each primer paint described in Table 2 below was applied to the surface of the pretreated low-pressure melamine decorative material of 100 mm × 100 mm so as to have a wet layer thickness of 9 μm, dried at 60 ° C. for 30 minutes, and a layer thickness of 3 A primer layer of ˜5 μm was formed. This was taken out from the drying oven, allowed to cool at room temperature for 30 minutes, (1) immediately, (2) cured for 2 hours in an environment with a temperature of 40 ° C. and a relative humidity of 90%, and (3) a temperature of 40 ° C. After curing for 15 hours in an environment with a relative humidity of 90%, using an ink jet printer, four colors of C ink, M ink, Y ink, and K ink were applied to the entire surface in equal amounts and cured to a layer thickness of 30 μm. The decorative material samples of Examples 4 to 8 were obtained. The obtained sample was subjected to an adhesion test 1 and an ink color test 1 and 2. The results were as shown in Table 2.

Example 9 (Primer layer + Ink layer 2: Primer curing conditions)
A sample was prepared in the same manner as in Example 4 except that the drying time of the primer coating was set to 150 minutes. Further, the same evaluation as in Example 4 was performed. The results were as shown in Table 2. Moreover, the primer layer # 1 produced by the same method as Example 4 and the primer layer # 2 produced by the same method as Example 9 were evaluated for the cured state of the primer layer by the following method.

  First, 0.2 ml of 1,6-hexanediol diacrylate was dropped on the surface of the primer layer. After 5 seconds, one “Kimwipe” (manufactured by Nippon Paper Crecia Co., Ltd.) was used, and the portion where the acrylate was dropped was slid by 10 reciprocations by hand.

  As a result, the primer layer # 2 did not leave any trace on the surface even when the Kimwipe was slid 10 times by hand. Therefore, it was considered that the primer layer did not dissolve in 1,6-hexanediol diacrylate and was almost completely cured. On the other hand, primer layer # 1 was considered to be in an incompletely cured state because the primer layer peeled off when the Kimwipe was slid 5 times by hand.

Example 10 (Formation of clear layer)
The primer paint D5 is applied to the surface of the pretreated low-pressure melamine decorative material of 100 mm × 100 mm so that the wet layer thickness is 9 μm, and dried at 60 ° C. for 30 minutes, and a primer layer having a layer thickness of 3 to 5 μm is formed. Formed. After removing this from the drying oven, leaving it to stand at room temperature for 30 minutes and cooling, immediately using an ink jet printer, four colors of C ink, M ink, Y ink, and K ink were applied and cured to obtain a layer thickness. Formed an ink layer of 22.5 μm. Next, a clear layer having a layer thickness of 60 μm was formed on the entire surface, and a decorative material sample of Example 10 was obtained. The obtained sample was a coating film having excellent image clarity and specular gloss. Moreover, the pencil hardness (JIS K 5600-5-4) of the surface was 2H, and it had sufficient scratch resistance.

Examples 11 and 12 (transparent ink)
The primer paint D5 is applied to the surface of the pretreated low-pressure melamine decorative material of 100 mm × 100 mm so that the wet layer thickness is 9 μm, and dried at 60 ° C. for 30 minutes, and a primer layer having a layer thickness of 3 to 5 μm is formed. Formed. Remove this from the drying oven, let it stand at room temperature for 30 minutes, cool it, and immediately apply and cure the transparent ink by the following method using an inkjet printer to form a transparent ink layer with a layer thickness of 22.5 μm. did. Next, a clear layer having an average film thickness of 60 μm was formed on the entire surface, and decorative material samples of Examples 11 and 12 were obtained. An adhesion test 1 was performed on the obtained sample.

The transparent ink layer of the decorative material sample of Example 11 was formed so that one square pattern with a side of 1 mm was arranged on every 4 mm ^{2 on} the entire surface of the primer layer. Moreover, the transparent ink layer of the decorating material sample of Example 12 was 10 mm wide from the end of the primer layer to the back, and an ink layer was formed over the entire circumference of the four sides along the edge of the primer layer.

  As a result of the adhesion test 1, in the decorative material of Example 12, each layer did not peel at all, and excellent adhesion was obtained. On the other hand, in the decorating material of Example 12, the portion where the ink layer was formed did not peel at all, but the clear layer peeled off at the central portion where the ink layer was not formed.

Example 13 (Affixing of rim material)
The end of the sample produced in the same manner as the sample of Example 10 was ground to form a flat end surface with the wood part exposed. Next, after adhering an edge material (made of polypropylene, tape-shaped having a width of 18 mm and a thickness of 1 mm) to the four end surfaces using an adhesive, the edges of the edge material were ground, and the surface was a clear layer. The decorative material of Example 13 was obtained by aligning the back surface with the height of the back surface of the low-pressure melamine decorative material so as to be flush with the height. It was confirmed that the obtained sample did not swell the base material due to water absorption from the end portion, and sufficient durability was obtained as a decorating material used for the door of the water supply member.

DESCRIPTION OF SYMBOLS 101 Colored ink layer, 102 Transparent ink layer (entire surface), 103 Transparent ink layer (island shape or patch shape), 1 serial type inkjet printing apparatus, 2 head unit part, 3 maintenance part, 4 power part, 5 fixed axis, 6 control Part, 7 printing medium stage, 8 ink tank, 9 printing medium, 10 decorating material, 11 decorative material, 12 base material, 13 melamine-containing layer, 14 primer layer, 15 ink layer, 16 clear layer

Claims (22)

A cosmetic material comprising a melamine-containing layer on its surface;
A primer layer formed on the surface of the melamine-containing layer provided in the decorative material;
A decorative material formed by laminating at least an ink layer formed on a part or all of the surface of the primer layer,
The primer layer is formed from a reaction product of a curing agent having at least one functional group selected from an isocyanate group and a carbodiimide group and a main agent having a plurality of functional groups capable of crosslinking reaction with the curing agent. ,
The ink layer is formed from a colored ink containing at least a coloring material and an acrylic compound having a polymerizable unsaturated group, and a transparent ink containing at least an acrylic compound having no polymerizable material and having a polymerizable unsaturated group. A decorative material in which a transparent ink is applied to a part or all of a region where a colored ink is not applied. The melamine-containing layer and the primer layer are formed by a chemical reaction between an amino group in the melamine resin contained in the melamine-containing layer and at least one functional group selected from the isocyanate group and carbodiimide group. The primer layer and the ink layer are adhered by at least one chemical bond selected from a urea bond and an amide bond generated at the interface, and the reaction product generated at the interface between the two layers and the ink layer The decorating material according to claim 1, wherein the decorative material is attached by structural entanglement with a polymer of an acrylic compound having a polymerizable unsaturated group.   The decorating material according to claim 1 or 2, wherein an application amount per unit area of the transparent ink is smaller than an application amount per unit area of the colored ink.   The decorating material according to any one of claims 1 to 3, wherein the transparent ink is thinned out and applied.   The decorating material according to any one of claims 1 to 4, wherein the isocyanate group is a urethane resin two-component isocyanate group.   The decorating material according to claim 5, wherein the isocyanate group is a urethane resin-based two-component diisocyanate group.   The decorating material as described in any one of Claims 1-6 whose functional group which the said main ingredient has is OH group and / or NH group.   The decorating material according to claim 7, wherein the main agent having a plurality of OH groups and / or NH groups is a polymer polyol which may optionally have a plurality of NH groups.   The decorating material according to claim 8, wherein the polymer polyol is at least one selected from polyether polyol, polyester polyol, acrylic polyol, polyurethane polyol, and polycarbonate polyol.   The acrylic compound having the polymerizable unsaturated group contained in the colored ink and the transparent ink is at least one selected from acrylic polymerizable monomers, oligomers and prepolymers. The decorative material according to item.   The decorating material according to any one of claims 1 to 10, wherein the ink layer is formed by applying the colored ink and the transparent ink to the surface of the primer layer by inkjet printing.   The said ink layer is formed by hardening | curing the acrylic compound which has the said polymerizable unsaturated group which the said colored ink and transparent ink contain with an active energy ray. The decorative material according to one item.   The decorating material of Claim 12 whose said active energy ray is an ultraviolet-ray.   The clear layer is further laminated | stacked on the surface of the said ink layer, The said clear layer is formed from the clear coating material containing the acrylic compound which has a polymerizable unsaturated group, It is any one of Claims 1-13 The decorative material described.   The ink layer and the clear layer include a polymer of an acrylic compound having a polymerizable unsaturated group included in the colored ink and the transparent ink forming the ink layer, and a polymerizable non-polymer included in the clear paint forming the clear layer. 15. The additive according to claim 14, wherein the polymer of the acrylic compound having a saturated group is produced by the same polymerization reaction mechanism, and is attached by a chemical bond generated at the interface between these two layers. Decoration material.   The additive according to claim 14 or 15, wherein the acrylic compound having a polymerizable unsaturated group contained in the clear paint is at least one selected from an acrylic polymerizable oligomer and a prepolymer, and a low molecular acrylic polymer. Decoration material. The decorating material as described in any one of Claims 14-16 with which the thickness of each of the said primer layer, a decoration layer, and a clear layer satisfy | fills the following relational expressions.
Primer layer thickness <ink layer thickness <clear layer thickness   The decorating material as described in any one of Claims 1-17 whose peeling strength prescribed | regulated by JISK5600 is 2 MPa or more and 4 MPa or less.   The said clear layer is formed by hardening | curing the acrylic compound which has the said polymerizable unsaturated group which the said clear coating contains with an active energy ray, It is any one of Claims 14-18. Decorating material.   The decorating material according to claim 19, wherein the active energy ray is at least one selected from ultraviolet rays and infrared rays.   The decorating material as described in any one of Claims 1-20 by which an edge material is provided in the side surface of the base-material part of a decorative material among the side surfaces of a decorating material.   The decorating material according to any one of claims 1 to 21, which is used for water-circulating devices.

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