JP6864420B2 - Building board and paint composition - Google Patents

Description

The present invention relates to a building board and a coating composition for forming an ink receiving layer of the building board, and more particularly to a building board provided with an ink receiving layer having excellent ink color development and color reproducibility.

In recent years, building boards with various designs have been used, but in order to produce building boards with high design, a printing method using an inkjet printer or the like is used, and the ink used for printing is ultraviolet rays. Curable ink is used. Further, in such a building board, it is common to provide an ink receiving layer on the base material and perform printing on the ink receiving layer, instead of printing directly on the base material. As a paint for forming an ink receiving layer of a building board, for example, as described in Japanese Patent Application Laid-Open No. 2010-112073 (Patent Document 1), a water-based emulsion paint is widely used.

Japanese Unexamined Patent Publication No. 2010-112073 describes a building board having a UV ink image layer on an undercoat paint layer which is an ink receiving layer, and uses an acrylic resin emulsion having a glass transition temperature of 35 to 90 ° C. as the undercoat paint. Furthermore, the wettability of the ink is improved by using a component such as a fluorine-based or silicon-based surface conditioner as a wetting agent in the UV ink.

Japanese Unexamined Patent Publication No. 2010-112073

As described in Japanese Patent Application Laid-Open No. 2010-112073, by using a paint containing an acrylic resin having a relatively high glass transition temperature for the ink receiving layer, the color development of the ink can be improved, but the building board has a high design. It is important to consider the color reproducibility of the ink in order to produce the ink. However, it cannot be said that these performances have been sufficiently studied in Japanese Patent Application Laid-Open No. 2010-112073, and there is still room for improvement as an ink receiving layer.

Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide a building board provided with an ink receiving layer having excellent ink color development and color reproducibility. Another object of the present invention is to provide a coating composition that can be used to form an ink receiving layer of such a building board.

The ink receiving layer usually contains particles such as pigments together with the binder resin, and it is considered that such particles have a great influence on the color development property of the ink. The present inventor examined the color development property of the ink by the ink receiving layer, and found that by blending particles such as extender pigments and resin beads in the ink receiving layer, the ultraviolet curable ink is easily wetted and spread, and the color of the ink is developed. It turned out that the sex can be improved. On the other hand, it was also found that if the proportion of the extender pigment or the resin beads becomes too high, it becomes difficult to conceal the color of the base material itself, and the color reproducibility of the ink deteriorates.

Therefore, as a result of diligent studies to achieve the above object, the present inventor has controlled the ratio of the coloring pigment, the extender pigment and the resin beads in the ink receiving layer to develop the color of the active energy ray-curable ink composition. We have found that the properties and color reproducibility can be improved, and have completed the present invention.

That is, the building board of the present invention is a clear formed so as to cover at least the base material, the ink receiving layer formed on the base material, the ink layer formed on the ink receiving layer, and the ink layer. A building board with layers
The ink receiving layer contains a color pigment, a component (X) composed of at least one of an extender pigment and a resin bead, and a binder resin, and the ratio of the color pigment to the total of the color pigment and the component (X) is 10. .0 to 65.0% by volume,
The ink layer is formed by an ink composition.

In a preferred example of the building board of the present invention, the ^{L * value in the L *} C ^* h color system of the ink receiving layer is 50.0 to 98.0, and the C ^* value is 0.5 to 30. It is 0.0.

In a preferred example of the building board of the present invention, the coloring pigment contains a white pigment and a coloring pigment other than the white pigment, and the volume ratio (A / B) of the white pigment (A) and the coloring pigment (B) other than the white pigment. ) Is 99.99 / 0.01 to 50/50.
In a preferred example of the building board of the present invention, the ink composition is an active energy ray-curable ink.

Further, the coating composition of the present invention is a coating composition for forming an ink receiving layer of a building board, and is a coloring pigment, a component (X) composed of at least one of an extender pigment and a resin bead, and a binder. The color pigment contains a resin, and the ratio of the color pigment to the whole of the component (X) is 10.0 to 65.0% by volume.

According to the building board of the present invention, it is possible to provide a building board provided with an ink receiving layer having excellent ink color development and color reproducibility. Further, according to the coating composition of the present invention, it is possible to provide a coating composition that can be used for forming an ink receiving layer of such a building board.

It is schematic sectional drawing of one Embodiment of the building board of this invention.

<Building board>
The building board of the present invention will be described in detail below. The building board of the present invention includes a base material, an ink receiving layer formed on the base material, an ink layer formed on the ink receiving layer, and a clear layer formed so as to cover at least the ink layer. The ink receiving layer includes a coloring pigment, a component (X) composed of at least one of an extender pigment and a resin bead, and a binder resin, and the entire coloring pigment and the component (X). The ratio of the coloring pigment to the ink layer is 10.0 to 65.0% by volume, and the ink layer is formed by the ink composition.

The base material constituting the building board of the present invention is not particularly limited as long as it is a building material. Specific examples of building materials include ceramic siding boards, flexible boards, calcium silicate boards, gypsum slag bar light boards, wood piece cement boards, asbestos cement boards, pulp cement boards, precast concrete boards, and lightweight aerated concrete (ALC). Examples include ceramic building material boards such as boards and gypsum boards, and metal building material boards such as aluminum, iron and cement. The surface texture of the base material is not particularly limited, and may have a smooth surface or an uneven shape. Further, the base material may be subjected to a base treatment with a sealer, a primer or the like.

The ink receiving layer constituting the building board of the present invention is arranged on the base material mainly for the purpose of fixing the ink layer. In the building board of the present invention, the ink receiving layer contains a coloring pigment, a component (X) composed of at least one of an extender pigment and a resin bead, and a binder resin, and covers the entire coloring pigment and the component (X). The proportion of the coloring pigment to occupy is required to be 10.0 to 65.0% by volume. By controlling the ratio of the coloring pigment and the component (X) in this way, the color development property and the color reproducibility of the ink composition can be improved. In particular, if the color reproducibility of the ink is high, the amount of ink used can be reduced, which is also effective from this point. If the proportion of the coloring pigment is less than 10.0% by volume, the base material hiding property is lowered, and it becomes difficult to improve the color reproducibility of the ink. On the other hand, when the ratio of the coloring pigment exceeds 65.0% by volume, the ratio of the component (X) becomes too low, and the effect of improving the color development property of the ink cannot be obtained. Further, in the ink receiving layer, the ratio of the coloring pigment and the coloring pigment to the whole of the component (X) is preferably 12.0 to 55.0% by volume, preferably 12.0 to 40.0% by volume. More preferably.

The total content of the coloring pigment and the component (X) in the ink receiving layer is preferably 25 to 65% by volume. Further, in the ink receiving layer, the binder resin forms a continuous phase and connects particles such as the coloring pigment and the component (X), but the content of the binder resin is 35 to 75% by volume. Is preferable.

In the building board of the present invention, the ink receiving layer has an ^{L *} value of 50.0 to 98.0 and a C ^* value of 0.5 to 30.0 in the ^{L *} C ^* h color system. Is preferable. Further, more preferably, the L ^* value is 75.0 to 98.0 and the C ^* value is 0.5 to 20.0.
The L ^* C ^* h color system is a color system defined in JIS Z8781-4 (2013), and L ^* is a numerical value representing lightness. Further, C ^* is a numerical value representing saturation. ^{By setting the L *} value and C ^* value of the ink receiving layer in the above-specified range, the color expression of the ink can be further improved. In particular, when the L ^* value is 75.0 to 98.0 and the C ^* value is 0.5 to 20.0, the color reproducibility of the yellow and red colors of the printed matter should be improved. Can be done.

In the present ^invention, L * ^{C *} h ^{L *} value and ^{C *} values in color system is determined according to JIS Z8781-4 (2013). The specific measurement method is determined by a method according to JIS Z 8722 (2009). For example, a tristimulus value direct reading type color difference meter "CR400" (trade name, manufactured by Konica Minolta Co., Ltd.) is used as a C light source. There is a method of measuring a color with a viewing angle of 2 ° and a diffuse illumination light receiving method (d / 0).

In the above ink receiving layer, ^{in order to make the L * value in the L *} C ^* h color system 50.0 to 98.0 and the C ^* value 0.5 to 30.0, a white pigment is used as the coloring pigment. It is effective to adjust the mixing ratio of them by using a coloring pigment other than the white pigment. In the ink receiving layer, ^{from the viewpoint of adjusting the L *} value and the C ^* value within the specified ranges, the coloring pigment contains at least a white pigment and a coloring pigment other than the white pigment, and the white pigment (A) and the white pigment. The volume ratio (A / B) of the coloring pigments (B) other than the above is preferably 99.99 / 0.01 to 50/50, and more preferably 99.99 / 0.01 to 70/30. ..

In the building board of the present invention, the ink receiving layer can be formed by applying a coating composition to the surface of a base material and then forming a film by drying or the like. The dry film thickness of the ink receiving layer is preferably 5 to 40 μm.

The coating composition used for forming the ink receiving layer (hereinafter referred to as an ink receiving layer coating composition) comprises a coloring pigment, a component (X) composed of at least one of an extender pigment and a resin bead, and a binder resin. The ratio of the coloring pigment to the total of the coloring pigment and the component (X) is 10.0 to 65.0% by volume.

In the above-mentioned coating composition for an ink receiving layer, the coloring pigment has an effect of enhancing the base material hiding property. Known materials can be used as the coloring pigments, for example, inorganic pigments such as titanium oxide and carbon black, yellow iron oxide, petals, nickel titanium yellow, bismuth yellow, cobalt blue, cobalt aluminum blue, and ultramarine blue, and phthalocyanine. Examples thereof include organic pigments such as system pigments and azo pigments, but it is more preferable to use red, yellow, and black pigments that are often used for decorating building boards. These pigments may be used alone or in combination of two or more.

In the above-mentioned coating composition for an ink receiving layer, the average particle size of the coloring pigment is preferably 40 to 1000 nm. _{In the present invention, the average particle size refers to a 50% particle size (D 50} ) of the volume-based particle size distribution, and is a particle size distribution measured using a particle size distribution measuring device (for example, a laser diffraction / scattering type particle size distribution measuring device). Can be obtained from. The particle size is represented by the sphere-equivalent diameter obtained by the laser diffraction / scattering method.

In the above-mentioned coating composition for an ink receiving layer, the content of the coloring pigment is adjusted so as to satisfy the above-mentioned specified content range in the ink receiving layer, and is preferably 2 to 25% by mass.

In the coating composition for an ink receiving layer, the component (X) comprises at least one of an extender pigment and resin beads. Since the extender pigment and the resin beads have the effect of improving the wettability of the ink composition without coloring the coating film, they contribute to the improvement of the color development property of the ink. The extender pigment and the resin beads usually have a transparent color in the coating film, but if the amount is too high, the base material hiding property cannot be obtained.

Known materials can be used as the extender pigment, and examples thereof include talc, mica, barium sulfate, clay, calcium carbonate, silica, kaolin, and glass beads. These pigments may be used alone or in combination of two or more.

The resin beads are particulate resins, and for example, the resin is subjected to a treatment such as cross-linking, and the particle shape is maintained even in the coating film. Therefore, the resin beads in the ink receiving layer are dispersed in the binder resin. The resin beads are not particularly limited, but resins such as acrylic resin, polyurethane resin, polyamide resin, urea / formaldehyde resin, silicone resin, fluororesin, phenol resin, melamine / formaldehyde resin, acrylonitrile resin, and styrene resin. Particles can be mentioned. These resin beads may be used alone or in combination of two or more.

In the coating composition for an ink receiving layer, the average particle size of the component (X) is preferably 0.1 to 200 μm.

In the coating composition for the ink receiving layer, the content of the component (X) is adjusted to satisfy the range of the specified content in the ink receiving layer, and may be 2 to 35% by mass. preferable.

In the coating composition for the ink receiving layer, as the binder resin, a binder resin usually used in the coating industry can be used, for example, acrylic resin, silicone resin, acrylic silicone resin, polyester resin, rosin resin, petroleum resin, and kumaron. Examples thereof include resins, phenol resins, polyurethane resins, melamine resins, urea resins, epoxy resins, cellulose resins, xylene resins, alkyd resins, aliphatic hydrocarbon resins, butyral resins, maleic acid resins, fumaric acid resins, vinyl resins and the like. Among these binder resins, acrylic resin, acrylic silicone resin, polyurethane resin and vinyl resin are preferable from the viewpoint of improving the color development of the ink, and further, from the viewpoint of imparting flexibility to the ink receiving layer, from the viewpoint of imparting flexibility to the ink receiving layer. Polyurethane resin and vinyl resin are suitable. These binder resins may be used alone or in combination of two or more.

Examples of the acrylic resin include a polymer obtained by polymerizing one or more acrylic components selected from acrylic acid, methacrylic acid and esters, amides and nitriles thereof. Specific examples of the acrylic component include compounds shown in the following (a) to (h). However, when the compound shown in the following (h) is used as the acrylic component, a siloxane condensation reaction also occurs in competition with the polymerization reaction. Therefore, in the present invention, the acrylic resin containing the compound shown in the following (h) as a constituent unit. Is classified as an acrylic silicone resin. Further, the acrylic resin also contains a polymer obtained by polymerizing an acrylic component and another monomer such as styrene. In this case, the ratio of the repeating unit derived from the acrylic component is in the acrylic resin. More than 50% by mass.
(A): Ester of (meth) acrylic acid and alcohol having 1 to 24 carbon atoms For example, methyl methacrylate, 2-isocyanatoethyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth). Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) Examples thereof include acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate.
(B): Monoesteride of polyhydric alcohol and (meth) acrylic acid For example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxy Examples thereof include butyl (meth) acrylate and polyethylene glycol mono (meth) acrylate.
(C): Carboxylic group-containing polymerizable unsaturated monomer For example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and the like can be mentioned.
(D): Epoxy group-containing polymerizable unsaturated monomer Examples thereof include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.
(E): Aminoalkyl (meth) acrylate For example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and the like can be mentioned. ..
(F): (Meta) acrylamide or a derivative thereof For example, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide. , N-methylolacrylamide, N-methylolacrylamide methyl ether, N-methylolacrylamide butyl ether and the like.
(G): (Meta) acrylonitrile or a derivative thereof Examples thereof include (meth) acrylonitrile and 3-amino (meth) acrylonitrile.
(H): Alkoxysilyl group-containing (meth) acrylic acid ester or a derivative thereof For example, γ- (meth) acryloxypropyldimethoxysilane, γ- (meth) acryloxipropyltrimethoxysilane, γ- (meth) acryloxipropyl. Examples thereof include methyldiethoxysilane and γ- (meth) acryloxypropyltriethoxysilane.
The acrylic silicone resin is usually a resin having a block made of repeating units such as forming an acrylic resin and a block made of repeating units such as forming a silicone resin. For example, in the above-mentioned synthesis of acrylic resin, the above-mentioned A method in which the compound shown in (h) is blended and the acrylic polymerization reaction and the siloxane condensation reaction are competitively polymerized, or a silane compound such as dichlorodimethylsilane is polymerized by a conventional method to have a siloxane bond in the main skeleton. It can be produced by synthesizing a polymer (silicone resin) and then graft-polymerizing the above-mentioned acrylic component to the polymer by a conventional method or binding an acrylic resin by a conventional method.

Polyurethane resin is a polymer having a plurality of urethane bonds (NHCOO), and can be synthesized by reacting a polyol with a polyisocyanate according to a conventional method.

Examples of the polyol include acrylic polyols, polyester polyols, polyurethane polyols, and polyether polyols. The acrylic polyol is obtained by copolymerizing a hydroxyl group-containing (meth) acrylic acid ester and a compound having a polymerizable unsaturated group. Examples of the hydroxyl group-containing (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. .. Examples of the compound having a polymerizable unsaturated group include styrene, vinyltoluene, (meth) acrylic acid, fumaric acid, maleic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylonitrile. These compounds having a polymerizable unsaturated group may be used alone or in combination of two or more. Polyester polyols include polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and phthalic acid and maleic acid. , Trimellitic acid, adipic acid, glutaric acid, succinic acid, sebacic acid, pimeric acid, suberic acid and other polybasic carboxylic acids are dehydrated and condensed. Further, the hydroxyl group-containing fatty acid ester obtained by decomposing natural oils such as soybean oil, linseed oil, rice bran oil, cottonseed oil, tung oil, castor oil, and palm oil with the above polyhydric alcohol is contained as all or part of the polyhydric alcohol. You can also do it. The polyurethane polyol is obtained by reacting the above-mentioned polyhydric alcohol with a polyisocyanate described later under the condition of excess alcohol. The polyether polyol is obtained, for example, by adding an alkylene oxide such as ethylene oxide or propylene oxide to the polyhydric alcohol or the hydroxyl group-containing fatty acid ester. These polyols may be used alone or in combination of two or more.

The polyisocyanate includes, for example, an aliphatic, aromatic or aromatic aliphatic polyisocyanate, and specific examples thereof include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4 , 4'-Methylenebis (cyclohexylisocyanate), methylcyclohexanediisocyanate, bis (isocyanatemethyl) cyclohexane, isophorone diisocyanate, diisocyanate dimerate, lysine diisocyanate and the like, as well as modified products of these isocyanate compounds. Specific examples of the modified product include a biuret modified product, an isocyanurate modified product, an adduct modified product (for example, a trimethylolpropane adduct), an allophanate modified product, and a uretdione modified product. These polyisocyanates may be used alone or in combination of two or more. In the synthesis of the polyurethane resin, the polyisocyanate preferably has 0.5 to 1.5 equivalents of isocyanate groups with respect to the hydroxyl groups of the polyol, and more preferably 0.8 to 1.2 equivalents.

The vinyl resin is a polymer of a compound having a vinyl group (CH ₂ = CH −), and can be synthesized according to a conventional method. However, in the present invention, the vinyl group-containing monomer used in the synthesis of the vinyl resin excludes the acrylic component used in the synthesis of the acrylic resin described above. Examples of the vinyl group-containing monomer include vinyl chloride, vinyl acetate, styrene and the like. These monomers may be used alone or in combination of two or more. As the vinyl resin, polyvinyl chloride, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer and the like are preferable. Further, the vinyl resin also contains a polymer obtained by polymerizing a vinyl group-containing monomer and another monomer such as maleic acid or an acrylic component. In this case, a repeating unit derived from the vinyl group-containing monomer is included. The ratio of is more than 50% by mass in the vinyl resin.

In the coating composition for the ink receiving layer, the glass transition temperature (Tg) of the binder resin is determined.
It is preferably 30 ° C. or higher. When the glass transition temperature is within the above-specified range, the color development property of the ink can be further improved. In the present invention, the glass transition temperature of the binder resin is measured by using a differential scanning calorimetry (DSC) device according to JIS K 7121-1987.

In the coating composition for the ink receiving layer, the content of the binder resin is preferably adjusted so as to satisfy the range of the specified content in the ink receiving layer, for example.
It is 10 to 40% by mass.

In addition to the above-mentioned components, the above-mentioned coating composition for an ink receiving layer includes additives commonly used in the coating industry, such as water, an organic solvent, a film forming aid, a wetting agent, a dispersant, an emulsifier, and a viscosity adjusting agent. Agents, anti-settling agents, anti-skin agents, anti-dripping agents, antifoaming agents, anti-color separation agents, leveling agents, desiccants, plasticizers, fungicides, antibacterial agents, pesticides, preservatives, light stabilizers , Ultraviolet absorber, antistatic agent, conductivity imparting agent and the like may be appropriately selected and blended within a range that does not impair the object of the present invention.

The coating composition for an ink receiving layer can be prepared by mixing the coloring pigment, the component (X) and the binder resin with various components appropriately selected if necessary. The binder resin is preferably blended in the form of a solution, emulsion or dispersion. Further, as the coating composition for the ink receiving layer, various coating forms such as water-based and organic solvent-based can be used.

As a method for applying the coating composition for the ink receiving layer, a conventionally known coating method can be used without particular limitation. Specific examples thereof include air spray coating, airless spray coating, electrostatic coating, roll coater coating, and flow coater coating. In particular, when the surface of the base material has irregularities, airless spray coating or electrostatic coating is suitable from the viewpoint of followability to the uneven shape and compatibility with the coating speed. In these coating methods, coating may be repeated until a desired film thickness is obtained. It is effective that the surface temperature of the base material at the time of coating is heated to 30 to 80 ° C. in order to form a good printed surface.

The ink layer constituting the building board of the present invention is formed by printing on the ink receiving layer using the ink composition for the purpose of designing the building board. In the building board of the present invention, the ink layer can be formed by ordinary printing means, but a printing means using an inkjet printer (that is, an inkjet method) is preferable. Examples of the inkjet printer include an inkjet printer that ejects an ink composition by a charge control method or an ink-on-demand method. The ink composition may be used alone or as an ink set in which two or more kinds are combined. Further, it is effective from the viewpoint of ink color development that the surface temperature of the base material at the time of printing is heated to 30 to 80 ° C.
The form of the ink composition is not particularly limited, and various inks such as water-based inks, organic solvent-based inks, and active energy ray-curable inks can be used. Above all, it is preferable to use an active energy ray-curable ink because it dries quickly and has a small burden on the environment.

The ink composition contains a coloring pigment for the purpose of designing a building board. Known materials can be used as the coloring pigment, for example, carbon black, yellow iron oxide, petals, composite oxides (nickel / titanium type, chromium / titanium type, bismuth / vanadium type, cobalt / aluminum type, cobalt / titanium type). Inorganic pigments such as aluminum / chromium type, ultramarine blue), titanium oxide, quinacridone type, diketoprolopiel type, benzimidazolone type, isoindolinone type, anthrapyrimidine type, phthalocyanine type, slene type, dioxazine type, Examples include azo-based organic pigments. From the viewpoint of weather resistance, it is preferable to use an inorganic pigment.

The content of the coloring pigment in the ink composition is not particularly limited, but is preferably 2 to 20% by mass in the case of an active energy ray-curable ink. Further, it is preferably 0.2 to 10% by mass for water-based inks and organic solvent-based inks.

The ink composition preferably contains a dispersant. As the dispersant, anionic dispersants, cationic dispersants and nonionic dispersants are preferable in water-based inks, and basic dispersants (or basic groups) in organic solvent-based inks and active energy ray-curable inks. Dispersants having (or) acidic dispersants (or dispersants having acidic groups), and dispersants having both basic and acidic groups are preferable. As the dispersant, a commercially available product can be preferably used.
When the ink composition is a water-based ink, it preferably contains a binder resin in addition to the coloring pigment. As the binder resin, for example, acrylic resin, polyester resin, polyurethane resin, vinyl chloride resin and the like are preferably used. These resins may be used alone or in combination of two or more. Further, it is preferable that the resin is dispersed in water and used in the form of a resin dispersion liquid. The binder resin is preferably contained in the ink composition in an amount of 1.0 to 10.0% by mass.
Further, in the above-mentioned water-based ink, in addition to the solvent such as diethylene glycol monobutyl ether and ethylene glycol, and the above-mentioned components, additives usually used in the ink industry, such as antioxidants, silane coupling agents, and plasticizers. Agents, rust preventives, pH adjusters, defoamers, charge control agents, stress relievers, penetrants, surface adjusters and the like may be appropriately selected and blended within a range that does not impair the object of the present invention.
When the ink composition is an organic solvent-based ink, it preferably contains a binder resin in addition to the coloring pigment. As the binder resin, for example, acrylic resin, polyester resin, polyurethane resin, vinyl chloride resin and the like are preferably used. These resins may be used alone or in combination of two or more. The binder resin is preferably contained in the ink composition in an amount of 1.0 to 10.0% by mass.
As the organic solvent to be blended in the organic solvent-based ink, a lactone-based solvent such as γ-butyrolactone, a glycol ether-based solvent such as dipropylene glycol monomethyl ether, or the like is preferably used. Furthermore, in addition to the above-mentioned components, additives commonly used in the ink industry, such as antioxidants, silane coupling agents, plasticizers, rust inhibitors, pH adjusters, defoamers, charge control agents, etc. A stress relaxation agent, a penetrant, a surface conditioner and the like may be appropriately selected and blended within a range that does not impair the object of the present invention.

When the ink composition is an active energy ray-curable ink, it contains an active energy ray-polymerizable monomer. The active energy ray-polymerizable monomer is a monomer that undergoes a polymerization reaction when irradiated with active energy rays such as ultraviolet rays, and has, for example, an acryloyloxy group or a methacryloyloxy group as a functional group exhibiting reactivity when irradiated with active energy rays. Those are suitable. The polymer obtained after the polymerization of the active energy ray-polymerizable monomer functions as a binder. The active energy ray-polymerizable monomer can be classified into a monofunctional monomer having 1 functional group, a bifunctional monomer having 2 functional groups, and a polyfunctional monomer having 3 or more functional groups, depending on the number of functional groups. ..

Among the above active energy ray-polymerizable monomers, the monofunctional monomer preferably has a molecular weight of 1000 or less, and specific examples thereof include stearyl acrylate, acryloyl morpholine, tridecyl acrylate, lauryl acrylate, N, N-dimethylacrylamide. , Decyl acrylate, 2-phenoxyethyl acrylate, isodecyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, isooctyl acrylate, octyl acrylate, dicyclopentenyloxyethyl acrylate, cyclohexyl acrylate, N-vinyl Caprolactam, isoamyl acrylate, 2-ethylhexyl-diglycol acrylate, EO (ethylene oxide) modified 2-ethylhexyl acrylate, neopentyl glycol acrylate benzoic acid ester, N-vinyl-2-pyrrolidone, N-vinylimidazole, tetrahydrofurfuryl acrylate, Examples thereof include methoxydipropylene glycol acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, cyclic trimethylolpropaneformal acrylate, ethoxy-diethylene glycol acrylate, 4-hydroxybutyl acrylate and the like. .. These monofunctional monomers may be used alone or in combination of two or more.

Among the above active energy ray-polymerizable monomers, the bifunctional monomer preferably has a molecular weight of 1000 or less, and specific examples thereof include 1,10-decanediol diacrylate and 2-methyl-1,8-octanediol. Diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1,9-nonandiol diacrylate, 1,8-octanediol diacrylate, 1,7-heptanediol diacrylate, polytetramethylene Glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, tripropylene glycol diacrylate, 1,4 -Butanediol diacrylate, dipropylene glycol diacrylate and the like can be mentioned. These bifunctional monomers may be used alone or in combination of two or more.

Among the above active energy ray-polymerizable monomers, the trifunctional or higher functional polyfunctional monomer preferably has a molecular weight of 2000 or less, and specific examples thereof include trimethylol propanetriacrylate, ethoxylated trimethylolpropanetriacrylate, and propoxy. Trimethylol Propanetriacrylate, Pentaerythritol Triacrylate, Glycerin Triacrylate, Tetramethylol Methantriacrylate, Pentaerythritol Tetraacrylate, Pentaerythritol Tetraacrylate, EO Modified Diglycerin Tetraacrylate, Ditrimethylol Propanetetraacrylate, Di Examples thereof include pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. These polyfunctional monomers may be used alone or in combination of two or more.

In the above active energy ray-curable ink composition, the content of the active energy ray-polymerizable monomer is preferably 1 to 95% by mass, more preferably 70 to 95% by mass. Further, from the viewpoint of improving the substrate followability and crack resistance of the ink layer, it is preferable to add a large amount of the monofunctional monomer, and the content of the monofunctional monomer in the active energy ray-curable ink composition is determined. It is preferably 20 to 85% by mass. When a metal siding material is used as the base material, the base material followability and crack resistance of the ink layer may be required.

Among the active energy ray-polymerizable monomers, acryloylmorpholine, 4-hydroxybutyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, from the viewpoint of improving the scratch resistance of the ink layer. Dicyclopentenyl acrylate, tetrahydrofurfuryl acrylate, methoxydipropylene glycol acrylate, ethoxy-diethylene glycol acrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, 3-methyl -1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, trimethylol propane triacrylate, ethoxylated trimethylol propane triacrylate , Propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate and the like are preferably mentioned, and such an active energy ray-polymerizable monomer having excellent scratch resistance is 0.5 to 60 mass in the total mass of the ink composition. %, More preferably 5 to 60% by mass.

Further, the active energy ray-curable ink composition may use an acrylate oligomer. The acrylate oligomer is _{an oligomer having one or more acryloyloxy groups (CH 2} = CHCOO−), and the number of functional groups is preferably 3 to 6. The acrylate oligomer preferably has a molecular weight of 2000 to 20000. The molecular weight is a polystyrene-equivalent weight average molecular weight. Specific examples of the acrylate oligomer include an amino acrylate oligomer [an _{acrylate oligomer having a plurality of amino groups (-NH 2} )], a urethane acrylate oligomer [an acrylate oligomer having a plurality of urethane bonds (-NHCOO-)], and an epoxy acrylate oligomer [ An acrylate oligomer having a plurality of epoxy groups], a silicone acrylate oligomer [an acrylate oligomer having a plurality of siloxane bonds (-SiO−)], an ester acrylate oligomer [an acrylate oligomer having a plurality of ester bonds (-COO−)] and a butadiene acrylate oligomer [butadiene]. An acrylate oligomer having a plurality of units] and the like. The content of the acrylate oligomer in the active energy ray-curable ink composition is, for example, 0.4 to 20% by mass.

It is preferable to add a photopolymerization initiator, a light stabilizer, a polymerization inhibitor and the like to the active energy ray-curable ink composition, and further, in addition to the above-mentioned components, additions usually used in the ink industry. Agents such as water, organic solvents, antioxidants, silane coupling agents, plasticizers, rust inhibitors, pH regulators, defoamers, charge controllers, stress relievers, penetrants, surface modifiers, etc. It may be appropriately selected and blended within a range that does not impair the object of the invention.

In the above active energy ray-curable ink composition, the surface tension at the printing temperature is preferably 20 to 35 mN / m, and the viscosity at the printing temperature is preferably 5 to 15 mPa · s. .. The temperature of the ink during printing is preferably 35 to 50 ° C.
The ink composition can be prepared by mixing the coloring pigment with various components appropriately selected if necessary.

When the ink composition is a water-based ink or an organic solvent-based ink, it is preferable that the ink layer formed after printing is naturally dried or forcibly dried. When the inkjet ink composition is an active energy ray-curable ink, the ink layer formed by printing is irradiated with active energy rays such as ultraviolet light using a metal halide lamp, a high-pressure mercury lamp, an ultraviolet LED, or the like. Then, it is preferable to cure it. The wavelength of the active energy ray irradiated to cure the ink layer preferably overlaps with the absorption wavelength of the photopolymerization initiator, and the main wavelength of the active energy ray is preferably 360 to 425 nm.

The clear layer constituting the building board of the present invention is arranged so as to cover at least the ink layer for the purpose of mainly protecting the surface of the ink layer. For example, when the entire surface of the ink receiving layer is covered with the ink layer, the clear layer is formed only on the surface of the ink layer, and when a part of the ink receiving layer is exposed, the clear layer is the ink layer. It is formed on the surface of the ink receiving layer and the surface of the exposed ink receiving layer.

In the building board of the present invention, the clear layer can be formed, for example, by applying a coating composition for a clear layer to the surfaces of an ink layer and, in some cases, an exposed ink receiving layer, and then forming a film by drying or the like. As a coating method for the clear layer coating composition, a conventionally known coating method can be used without particular limitation. Specifically, air spray coating, airless spray coating, electrostatic coating, roll coater coating, flow coater Painting etc. can be mentioned.

Various conventionally known paints can be used as the paint composition for the clear layer, but a paint having good weather resistance is particularly preferable. Specifically, the coating composition for the clear layer preferably contains any one of an acrylic resin, an acrylic silicone resin, a silicone resin, an acrylic urethane resin, a polyurethane resin, and a fluororesin, and more preferably contains an acrylic silicone resin. .. The acrylic silicone resin can exhibit the weather resistance of the silicone resin in addition to the adhesiveness of the acrylic resin.
Further, among these resins, two or more kinds of resins can be used in combination.

Examples of the acrylic resin used in the coating composition for a clear layer include a polymer obtained by polymerizing one or more acrylic components selected from acrylic acid, methacrylic acid and its esters, amides, nitriles and the like. And those described in paragraph 0033 can be used.
The acrylic silicone resin is usually a resin having a block made of repeating units such as forming an acrylic resin and a block made of repeating units such as forming a silicone resin. For example, in the above-mentioned synthesis of acrylic resin, the above-mentioned A method in which the compound shown in (h) is blended and the acrylic polymerization reaction and the siloxane condensation reaction are competitively polymerized, or a silane compound such as dichlorodimethylsilane is polymerized by a conventional method to have a siloxane bond in the main skeleton. It can be produced by synthesizing a polymer (silicone resin) and then graft-polymerizing the above-mentioned acrylic component to the polymer by a conventional method or binding an acrylic resin by a conventional method.
The silicone resin is not particularly limited, but a resin having an unsaturated double bond in the molecular structure, such as an alkyd-modified silicone resin, may be used, or may be used for graft polymerization of an acrylic component. May use a monomer other than the acrylic component.

Further, from the viewpoint of improving weather resistance, it is preferable to add an ultraviolet absorber or a light stabilizer to the clear layer coating composition, and further, in addition to the above-mentioned components, it is usually used in the coating industry. Additives such as binder resin, pigment, water, organic solvent, film forming aid, wetting agent, dispersant, emulsifier, viscosity modifier, anti-settling agent, anti-skinning agent, anti-sagging agent, defoaming agent, Color-coding inhibitors, leveling agents, desiccants, plasticizers, fungicides, antibacterial agents, insecticides, preservatives, antistatic agents, conductivity-imparting agents, etc. are appropriately selected within a range that does not impair the object of the present invention. May be blended.

The coating composition for a clear layer can be prepared by mixing various components appropriately selected as necessary. The binder resin is preferably blended in the form of a solution, emulsion or dispersion. Further, as the coating composition for the clear layer, various coating forms such as water-based and organic solvent-based can be used.

Next, an embodiment of the building board of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view of an embodiment of a building board of the present invention. The building board 1 of FIG. 1 is arranged on the base material 2, the ink receiving layer 3 arranged on the base material 2, the ink layer 4 arranged on the ink receiving layer 3, and the ink layer 4. The clear layer 5 is provided. In the building board 1 of FIG. 1, since the entire surface of the ink receiving layer 3 is covered with the ink layer 4, the clear layer 5 is formed only on the surface of the ink layer 4.

<Paint composition>
The coating composition of the present invention will be described in detail below. The coating composition of the present invention is a coating composition for forming an ink receiving layer of a building board, and comprises a coloring pigment, a component (X) composed of at least one of an extender pigment and a resin bead, and a binder resin. The proportion of the coloring pigment and the coloring pigment in the whole of the component (X) is 10.0 to 65.0% by volume. Further, the embodiment of the coating composition of the present invention is as described in the description of the coating composition for the ink receiving layer of the building board of the present invention. Specifically, in the coating composition of the present invention, the coloring pigment contains at least a white pigment and a coloring pigment other than the white pigment, and the volume ratio (A /) of the white pigment (A) and the coloring pigment (B) other than the white pigment. B) is preferably 99.99 / 0.01 to 50/50.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

<Preparation example of paint composition for ink receiving layer>
According to the formulation shown in Tables 1 to 10, the raw material and titania beads (φ1.4 mm) were mixed and then dispersed by a bead mill. After the dispersion, the titania beads were removed to prepare paints 1 to 54 for the ink receiving layer, respectively.

The compounding agents shown in Tables 1 to 10 are as follows.
1) Titanium oxide, density 3.8 g / cm ³ , (TITONE R-62N, manufactured by Sakai Chemical Co., Ltd.)
2) Yellow iron oxide, density 4.1 g / cm ³ , (TAROX LL-XLO, manufactured by Titan Kogyo Co., Ltd.)
3) Valve handle, density 5.2 g / cm ³ , (130ED, manufactured by Toda Pigment Co., Ltd.)
4) Carbon black, density 2.0 g / cm ³ , (Asahi # 50, manufactured by Asahi Carbon Co., Ltd.)
5) Heavy calcium carbonate, density 2.7 g / cm ³ , average particle size 2 μm (manufactured by Maruo Calcium Co., Ltd.)
6) Boncoat YG651 (manufactured by DIC Corporation, resin component 47% by mass, density of resin component)
1.2 g / cm ³ , glass transition temperature 47 ° C)
7) SN Deformer 1316 (manufactured by San Nopco Ltd.)
8) ASE-60 (manufactured by Rohm and Hearth)
9) Proxel AM (manufactured by Arch Chemicals)
10) Toughtic AR650M (manufactured by Toyobo Co., Ltd., density 1.2 g / cm ³ , average particle size)
30 μm)

<Preparation example of active energy ray-curable ink composition>
The raw materials and zirconia beads (φ0.5 mm) were mixed according to the formulation shown in Tables 11 and 12, and then dispersed by a bead mill. After dispersion, the zirconia beads were removed, a color ink composition was prepared, and an active energy ray-curable ink set was prepared.

The compounding agents shown in Tables 11 and 12 are as follows.
11) Cobalt blue (Sicopal Blue K 6310, manufactured by BASF)
12) Iron oxide (yellow) (Sicotrans Yellow L1916, manufactured by BASF)
13) Iron oxide (red) (Sicotrans Red L2817, manufactured by BASF)
14) DISPERBYK-2155 (manufactured by BYK)
15) BYK-UV3500 (manufactured by BYK)

The surface tension of the active energy ray-curable ink composition was measured at a temperature of 45 ° C. using a tensiometer (CBVP-Z manufactured by Kyowa Surface Chemistry). The viscosity of the active energy ray-curable ink composition was measured at a temperature of 45 ° C. and a shear rate of 10 s- ¹ using a rheometer (MCR301 manufactured by AntonioPysica).

<Preparation example of paint composition for clear layer>
The raw materials were mixed according to the formulation shown in Table 13 to prepare a clear paint.

The compounding agents shown in Table 13 are as follows.
16) Polydurex G613, manufactured by Asahi Kasei Corporation, solid content 41.5% by mass
17) TINUVIN 1130, manufactured by BASF 18) TINUVIN 292, manufactured by BASF

<Manufacturing example of building board (decorative test board)>
1. 1. A water-based sealer (manufactured by Dai Nippon Toryo Co., Ltd., product name: water-based mighty sealer multi) is applied to the surface of the base material slate plate (150 mm x 70 mm x 5 mm, manufactured by TP Giken Co., Ltd.) with an air spray so ^{that the coating amount is 100 g / m 2.} Then, the substrate was prepared by drying at room temperature for 2 hours.

2. Ink Receiving Layer Sealer With the painted base material heated to 60 ° C, the above-mentioned ink receiving layer coating composition is applied to the sealer-coated surface of the base material in an amount of 120 g / m ² (equivalent to a dry film thickness of 30 μm). It was painted with airless spray so that it would be. Then, it was dried at 100 degreeC for 3 minutes to form an ink receiving layer. The temperature of the surface of the base material was measured using an infrared radiation type non-contact thermometer (ISK-8700II, manufactured by AS ONE Corporation).

3. 3. Ink layer After forming the ink receiving layer, the active energy ray-curable ink composition (ink A (yellow, red, blue) or ink B (yellow, red, blue)) prepared above is applied using an inkjet printer. A gradation pattern for each single color (a solid image in which the recording density was recorded stepwise from 10% to 150% in 20% increments) and a mixed color gradation pattern for each color combination were formed. At this time, the temperature at which the ink was ejected was 45 ° C.
After patterning, a metal halide lamp, is irradiated with ultraviolet light at an accumulated light intensity of 50 mJ / cm ² per one peak irradiance 800 mW / cm ^2, to cure the ink composition.

4. Clear layer After the ink composition is cured, it is heated using a small drying oven (MO-931, manufactured by Toyama Sangyo Co., Ltd.), and the surface temperature of the cured coating film is 50 ° C. The paint was applied so that the coating amount was 80 g / m ² (equivalent to a dry film thickness of 25 μm). After painting, it was dried at 80 ° C. for 20 minutes to form a clear layer. The temperature of the surface of the base material was measured using an infrared radiation type non-contact thermometer (ISK-8700II, manufactured by AS ONE Corporation).

<Examples 1 to 102, Comparative Examples 1 to 6>
A decorative test plate was prepared according to the above manufacturing example of the decorative test plate. The combinations of the ink receiving layer coating composition and the clear layer coating composition used are shown in Tables 14 to 33.

<Evaluation>
According to the method shown below, the L ^* value and C ^* value of the ink receiving layer, the substrate hiding property of the ink receiving layer, the color development property of the ink, and the color reproducibility of the decorative test plate were evaluated. The results are shown in Tables 14-33.

1. 1. L ^* value, C ^* value of the ink receiving layer The lightness (L ^* ) and saturation ( ^{L *) and saturation (L *) and saturation (L *) in the L *} C ^* h color system before forming the ink receiving layer and allowing it to stand for one day to form the ink layer. C ^* ) was measured. The measurement was carried out using a tristimulus value direct reading type color difference meter "CR400" (manufactured by Konica Minolta), using a C light source as a light source, a viewing angle of 2 °, and a diffusion illumination light receiving method (d / 0). ..

2. Substrate Concealment of Ink Receiving Layer An ink receiving layer was formed, allowed to stand for one day, and visually evaluated before forming the ink layer.
The results are shown in Tables 14-33. The evaluation results are shown below.
◯: The color of the slate plate is completely hidden.
X: The color of the slate plate is not completely concealed.

3. 3. Color development of ink The color development was evaluated by observing the solid images of each gradation pattern one day after the preparation of the decorative test plate with the naked eye and a microscope. The results are shown in Tables 14-33. The evaluation criteria are as follows.
◯: The original color of the ink is printed uniformly, and unevenness and dullness are hardly observed.
Δ: Some unevenness and some dullness are observed in the gradation pattern.
X: Unevenness and dullness are observed in the gradation pattern.

4. Color Reproducibility of Decorative Test Board For all solid images of each gradation pattern one day after the decoration test board is manufactured, the brightness (L ^* ) and saturation (C ^* ) in the ^{L *} C ^{* h color system are determined.} Using a tristimulus value direct reading type color difference meter "CR400" (trade name, manufactured by Konica Minolta), a C light source was used as a light source, a viewing angle of 2 °, and a diffused illumination light receiving method (d / 0) were used for color measurement. From each of the obtained values, a ^{color space solid in the L *} c ^* h color system was created, and the color reproducibility of the image was evaluated. The results are shown in Tables 14-33. The evaluation criteria are as follows, and the comparison reference plate is as follows.
-For Examples 1 to 16 and Comparative Example 3, Example 17 was used as a comparison reference plate.
-For Examples 18 to 33, Example 34 was used as a comparison reference plate.
-For Examples 35 to 50, Example 51 was used as a comparison reference plate.
-For Examples 52 to 67 and Comparative Example 6, Example 68 was used as a comparison reference plate.
-For Examples 69 to 84, Example 85 was used as a comparison reference plate.
-For Examples 86 to 101, Example 102 was used as a comparison reference plate.

Further, in Comparative Examples 1, 2, 4, and 5, the color reproducibility was not evaluated because the substrate hiding property was not sufficiently obtained.

(Evaluation criteria)
◯: A wider color reproduction range can be obtained as compared with the comparison reference plate, and the color reproducibility of yellow and red systems is particularly good.
Δ: A wider color reproduction range can be obtained as compared with the comparison reference plate.
X: The color reproduction range is almost the same as that of the comparison reference plate.

As is clear from Tables 11 to 24, when the ratio of the coloring pigment and the coloring pigment contained in the ink receiving layer to the whole of the component (X) is 10.0 to 65.0% by volume, the color of the ink is developed. It was found that an ink receiving layer having excellent properties can be obtained. On the other hand, when the paints 52 and 53 for the receiving layer having the above ratio of less than 10.0% are used, it is difficult to obtain sufficient color reproducibility because the concealing property of the base material is low (comparison). Examples 1, 2, 4, 5). When the paint 54 for the receiving layer exceeding 65.0% by volume was used, the color-developing property of the ink was not sufficiently obtained. (Comparative Examples 3 and 6)
Further, as is clear from Tables 14 to 33, when the L ^* value of the ink receiving layer is 50.0 to 98.0 and the C ^* value is 0.5 to 30.0, the color pigment is used. A wider color reproduction range was obtained as compared with the ink receiving layer containing only the white pigment. When the L ^* value was 75.0 to 98.0 and the C ^* value was 0.5 to 20.0, the color reproducibility of the yellow and red systems tended to be particularly good.

1 Building board 2 Base material 3 Ink receiving layer 4 Ink layer 5 Clear layer

Claims (3)

A building board including a base material, an ink receiving layer formed on the base material, an ink layer formed on the ink receiving layer, and a clear layer formed so as to cover at least the ink layer. ,
The ink receiving layer contains a coloring pigment, a component (X) composed of at least one of an extender pigment and a resin bead, and a binder resin, and is colored to include four types of white, red, yellow, and black. The ratio of the colored pigment to the total of the pigment (C) and the component (X) is 10.0 to 65.0% by volume, and the ratio (A / C) of the white pigment (A) to the colored pigment (C) is , 74.94 to 99.45% by volume,
In the ink receiving layer, the L * value in the L * C * h color system is 50.0 to 98.0, and the C * value is 0.5 to 30.0.
A building board characterized in that the ink layer is formed of an ink composition. The building board according to claim 1, wherein the ink composition is an active energy ray-curable ink composition. A coating composition for forming an ink receiving layer of a building board, which is a coloring pigment (C) containing four types of white, red, yellow, and black , and at least one of an extender pigment and a resin bead. and component (X) consisting of, and a binder resin, the proportion of colored pigment to the total of the colored pigment (C) and the component (X) is 10.0 to 65.0% by volume, wear color pigments the proportion of the white pigment (a) to total (C) (a / C) is a coating composition, characterized in 74.94 to 99.45 vol% der Rukoto.

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