JP2018003329A - Building board and paint composition - Google Patents

Abstract

Provided is a building board provided with an ink receiving layer excellent in ink color development, thermal sensitivity and flexibility. A substrate 2, an ink receiving layer 3 formed on the substrate 2, a colored ink layer 4 formed on the ink receiving layer 3, and formed so as to cover at least the colored ink layer 4. It is the building board 1 provided with the made clear layer 5, Comprising: The said ink receiving layer 3 is resin (X) whose heat softening temperature is 90-193 degreeC or more, Comprising: From at least one among vinyl resin and urethane resin It is the building board 1 formed with the coating composition containing resin (X) which becomes. [Selection] Figure 1

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 excellent in ink color development, thermal sensitivity and flexibility. is there.

  In recent years, building boards to which various designs have been applied have been used, and in order to produce a building board having high design properties, a printing method using an ink jet printer or the like is used. Moreover, in such a building board, it is common to perform printing on an ink receiving layer by providing an ink receiving layer on the substrate instead of printing directly on the substrate. As a paint for forming an ink receiving layer of a building board, for example, as described in JP 2008-57131 A (Patent Document 1) and JP 2010-1112073 A (Patent Document 2), an aqueous emulsion Paint is widely used.

  Japanese Patent Application Laid-Open No. 2008-57131 describes acrylic resin paints based on acrylic emulsions and acrylic silicone resin paints based on acrylic silicone emulsions as water-based paints for ink receiving layers. Japanese Patent Application Laid-Open No. 2010-112073 describes that an undercoat paint layer on which a UV ink image layer is printed is formed of an acrylic resin emulsion having a glass transition temperature of 35 to 90 ° C.

  JP2013-63570A (Patent Document 3) states that an acrylic resin, an acrylic silicone resin, an acrylic styrene resin, an acrylic urethane resin, a urethane resin, a polyester resin, or the like can be used for the undercoat paint (receiving layer paint). Disclosure.

JP 2008-57131 A JP 2010-112073 A JP 2013-63570 A

  As described in JP 2010-112073 A, although the color development of the ink can be improved by using a paint containing an acrylic resin having a relatively high glass transition temperature for the ink receiving layer, on the other hand, the ink receiving layer There has been a problem that the flexibility of the resin is lowered. For this reason, there is a need for an ink receiving layer that can achieve both the color development and flexibility of the ink.

  Moreover, in JP2013-63570A, resins other than acrylic resins are disclosed. However, when a paint containing these resins is used, the adhesion to the ink layer or the surface protective layer is not sufficient, or There were problems such as insufficient color development of the ink.

  In addition, when an ink-receiving layer is formed on a building board using a water-based paint, it is generally necessary to heat the building board and volatilize the solvent. The temperature of is difficult to be uniform. In the method of decorating the building board, from the viewpoint of increasing productivity, after the building board is heated to form the ink receiving layer, the ink is immediately decorated before the temperature of the building board drops to room temperature. To do is widely done. In addition, there is a case where the building board coated with the ink receiving layer is not immediately decorated with ink, so that the coating conditions and printing conditions are constant throughout the year. In general, it is common to heat the building board before decorating with ink. In this case, since the surface temperature of the building board is difficult to be uniform and the film-forming state of the ink receiving layer is not uniform over the entire surface of the building board, the color development of the ink layer laminated on the ink receiving layer varies. There was a problem that it occurred (poor warmth).

  SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-described problems of the prior art and provide a building board provided with an ink receiving layer that is excellent in ink color development, warmth and flexibility. 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.

  As a result of intensive studies to achieve the above object, the present inventor, when using a vinyl resin or urethane resin having a heat softening temperature in a specific range, sufficiently secures the flexibility of the ink and It has been found that the warmth can be improved, and the present invention has been completed.

  That is, the building board of the present invention is formed so as to cover a base material, an ink receiving layer formed on the base material, a colored ink layer formed on the ink receiving layer, and at least the colored ink layer. The ink receiving layer is a resin (X) having a thermal softening temperature of 90 to 193 ° C., and the resin (X) is made of at least one of a vinyl resin and a urethane resin. It is formed by the coating composition containing this.

  In the suitable example of the building board of this invention, the said coating composition contains an acrylic resin (Y) further.

  In the other suitable example of the building board of this invention, mass ratio (X / Y) of the said resin (X) and the said acrylic resin (Y) is 85 / 15-15 / 85.

  In another preferred embodiment of the building board of the present invention, the colored ink layer is formed of an active energy ray curable ink composition.

  In another preferred embodiment of the building board of the present invention, the active energy ray-curable ink composition contains 2 to 20% by mass of a color pigment.

  The coating composition of the present invention is a coating composition for forming an ink receiving layer of a building board, and is a resin (X) having a thermal softening temperature of 90 to 193 ° C., which is a vinyl resin and a urethane resin. It is characterized by including resin (X) which consists of at least one.

  According to the building board of the present invention, it is possible to provide a building board provided with an ink receiving layer excellent in ink color development, thermal sensitivity and flexibility. Moreover, according to the coating composition of this invention, the coating composition which can be used in order to form the ink receiving layer of this building board can be provided.

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

<Building board>

  Below, the building board of this invention is demonstrated in detail. The building board of the present invention includes a substrate, an ink receiving layer formed on the substrate, a colored ink layer formed on the ink receiving layer, and a clear formed so as to cover at least the colored ink layer. The ink receiving layer is a resin (X) having a thermal softening temperature of 90 to 193 ° C., and includes a resin (X) made of at least one of a vinyl resin and a urethane resin. It is formed by a coating composition.

  The base material which comprises the building board of this invention is not specifically 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 chip cement boards, asbestos cement boards, pulp cement boards, precast concrete boards, lightweight cellular concrete (ALC) Examples include ceramics building material plates such as plates and gypsum boards, and metal building material plates such as aluminum, iron and stainless steel. The surface property of the substrate is not particularly limited, and may be a surface having a smooth surface or an uneven shape. In addition, 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 disposed on the substrate mainly for the purpose of fixing the colored ink layer. In the building board of the present invention, the ink-receiving layer is a resin (X) having a thermal softening temperature of 90 to 193 ° C., and includes a resin (X) made of at least one of a vinyl resin and a urethane resin. It is formed by. By using a coating composition containing such a resin (X), an ink receiving layer excellent in ink color development, warmth and flexibility can be formed on a substrate.

  The coating composition used for forming the ink receiving layer (hereinafter referred to as a coating composition for an ink receiving layer) is a resin (X) having a thermal softening temperature of 90 to 193 ° C., and is at least one of a vinyl resin and a urethane resin. It is necessary to contain resin (X) which consists of one side. Here, the resin (X) is composed of at least one of a vinyl resin and a urethane resin having a heat softening temperature of 90 to 193 ° C., and such a vinyl resin or urethane resin has an ink coloring property, a thermal sensitivity, and Even when compared with an acrylic resin that is highly flexible and has the same degree of thermal softening temperature, sufficient color development, warmth and flexibility can be ensured.

The heat softening temperature of the resin (X) needs to be 90 to 193 ° C, preferably 92 to 192 ° C, and more preferably 95 to 190 ° C.
If the heat softening temperature is increased, the color development and temperature sensitivity of the ink can be further improved, but if the heat softening temperature of the resin (X) exceeds 193 ° C., the flexibility of the ink receiving layer is obtained. It may not be possible.

  In the present invention, the heat softening temperature of the resin (X) is measured using a thermomechanical analyzer (TMA) according to JIS K 7196-1991.

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 this invention, the vinyl group containing monomer used for the synthesis | combination of a vinyl resin remove | excludes the acrylic component used for the synthesis | combination of the acrylic resin mentioned later. Examples of the vinyl group-containing monomer include vinyl chloride, vinyl acetate, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, pt-butyl styrene, p-methoxy styrene, p. -Phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-hydroxystyrene, vinyltrimethoxysilane, vinyltriethoxysilane and the like. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the thermosoftening temperature of a vinyl resin can be 90-193 degreeC by adjusting the kind of monomer, a polymerization degree, etc. As the vinyl resin, polyvinyl chloride, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer and the like are preferable. The vinyl resin also includes 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 used. Is more than 50% by mass in the vinyl resin.

  The urethane resin is a polymer having a plurality of urethane bonds (NHCOO) and can be synthesized by reacting a polyol and a polyisocyanate according to a conventional method. The heat softening temperature of the urethane resin can be adjusted to 90 to 193 ° C. by adjusting the type and degree of polymerization of the polyol and polyisocyanate.

  Examples of the polyol include acrylic polyol, polyester polyol, polyurethane polyol, polyether polyol, and the like. 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, 4-hydroxybutyl (meth) acrylate and the like. . Examples of the compound having a polymerizable unsaturated group include styrene, vinyl toluene, (meth) acrylic acid, fumaric acid, maleic acid, (meth) acrylic acid ester, (meth) acrylamide, (meth) acrylonitrile and the like. 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, phthalic acid and maleic acid. , Trimellitic acid, adipic acid, glutaric acid, succinic acid, sebacic acid, pimelic acid, suberic acid and other polybasic carboxylic acids. Also, it contains hydroxyl group-containing fatty acid esters 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 as all or part of the polyhydric alcohol. You can also. The polyurethane polyol is obtained by reacting the polyhydric alcohol with a polyisocyanate described later under conditions 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. In addition, these polyols may be used independently and may be used in combination of 2 or more type.

  Examples of the polyisocyanate include aliphatic or aromatic polyisocyanates. Specific examples include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4′-. In addition to methylene bis (cyclohexyl isocyanate), methylcyclohexane diisocyanate, bis (isocyanate methyl) cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, lysine diisocyanate, and the like, modified products of these isocyanate compounds can be mentioned. Specific examples of the modified product include a biuret modified product, an isocyanurate modified product, an adduct modified product (for example, trimethylolpropane adduct), an allophanate modified product, and a uretdione modified product. In addition, these polyisocyanate may be used independently and may be used in combination of 2 or more type. In the synthesis of the urethane resin, the polyisocyanate preferably has an isocyanate group of 0.5 to 1.5 equivalent, more preferably 0.8 to 1.2 equivalent, based on the hydroxyl group of the polyol.

  In the ink receiving layer, the content of the resin (X) is preferably 2 to 40% by mass, and more preferably 3 to 15% by mass. When the content is 2 to 40% by mass, the resulting ink-receiving layer is likely to further improve the color development, warmth and flexibility of the ink. In the ink-receiving layer coating composition, the content of the resin (X) is preferably adjusted so as to satisfy the specified content range in the ink-receiving layer. 5 to 20% by mass.

  The ink-receiving layer coating composition preferably further contains an acrylic resin (Y). The acrylic resin is a resin that has high color developability of the ink and is excellent in transparency and durability. Further, the glass transition temperature of the acrylic resin is preferably from 30 to 100 ° C. from the viewpoint of improving durability and flexibility. When the glass transition temperature of the acrylic resin is 30 ° C. or higher, the durability is hardly lowered, and when the glass transition temperature of the acrylic resin is 100 ° C. or lower, the flexibility is hardly lowered.

In the present invention, the glass transition temperature (Tg) of an acrylic resin refers to that calculated using the following FOX equation.
1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... + Wn / Tgn

  In the FOX formula, Tg is a glass transition temperature (K) of a polymer composed of n types of monomers, and Tg (1, 2, i, n) is a glass transition temperature (K) of a homopolymer of each monomer. Yes, W (1, 2, i, n) is the mass fraction of each monomer, and W1 + W2 +... + Wi +.

  Examples of the acrylic resin include polymers obtained by polymerizing one or more acrylic components selected from acrylic acid, methacrylic acid and esters thereof, amides, nitriles, and the like. Specific examples of the acrylic component include compounds as shown in the following (a) to (h). However, when the compound shown in the following (h) is used as an acrylic component, a siloxane condensation reaction also occurs in competition with the polymerization reaction. Therefore, in the present invention, an acrylic resin containing the compound shown in the following (h) as a structural unit Are classified as acrylic silicone resins. The acrylic resin also includes 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 within 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 include acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and the like.

(B): Monoesterified product 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): Carboxyl group-containing polymerizable unsaturated monomer Examples include acrylic acid, methacrylic acid, maleic acid, and maleic anhydride.

(D): Epoxy group-containing polymerizable unsaturated monomer Examples include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.

(E): Aminoalkyl (meth) acrylate Examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like. .

(F): (meth) acrylamide or a derivative thereof For example, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide N-methylol acrylamide, N-methylol acrylamide methyl ether, N-methylol acrylamide butyl ether and the like.

(G): (Meth) acrylonitrile or a derivative thereof Examples thereof include (meth) acrylonitrile and 3-amino (meth) acrylonitrile.

(H): alkoxysilyl group-containing (meth) acrylic acid ester or derivative thereof For example, γ- (meth) acryloxypropyldimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyl Examples thereof include methyldiethoxysilane and γ- (meth) acryloxypropyltriethoxysilane.

  In the ink receiving layer, the acrylic resin content is preferably 2 to 35% by mass. When the content is 2 to 35% by mass, the resulting ink-receiving layer is likely to further improve the color development, transparency and durability of the ink. In the ink-receiving layer coating composition, the acrylic resin content is preferably adjusted so as to satisfy the specified content range in the ink-receiving layer, for example, 0.5 to 20 % By mass.

  In the ink receiving layer or the ink receiving layer coating composition, the mass ratio (X / Y) of the resin (X) to the acrylic resin (Y) is preferably 85/15 to 15/85. If the mass ratio of both resins is within the above specified range, the effects of both resins can be exhibited in a more balanced manner.

  The ink-receiving layer coating composition may contain a pigment usually used in the coating industry. Examples of the pigment include coloring pigments and extender pigments. Known materials can be used as the color pigment, and examples thereof include inorganic pigments such as titanium oxide and carbon black, and organic pigments such as phthalocyanine pigments and azo pigments. As the extender pigment, known materials can be used, and examples thereof include talc, mica, barium sulfate, clay, calcium carbonate and the like. These pigments may be used alone or in combination of two or more.

  In the ink receiving layer, the pigment content is preferably 10 to 70% by mass from the viewpoint of further improving the color developability of the ink. In the ink-receiving layer coating composition, the pigment content is preferably adjusted so as to satisfy the specified content range in the ink-receiving layer, for example, 3 to 30% by mass. is there.

  In addition to the components described above, the ink-receiving layer coating composition includes additives commonly used in the coating industry, such as a binder resin, water, an organic solvent, a film forming aid, a wetting agent, a dispersant, and an emulsifier. , Viscosity modifier, anti-settling agent, anti-skinning agent, anti-sagging agent, antifoaming agent, anti-coloring agent, leveling agent, drying agent, plasticizer, anti-fungal agent, antibacterial agent, insecticide, antiseptic, light Stabilizers, ultraviolet absorbers, antistatic agents, conductivity-imparting agents, and the like may be appropriately selected and blended within a range that does not impair the object of the present invention.

  The ink-receiving layer coating composition can be prepared by mixing the resin (X) and various components appropriately selected as necessary. In addition, it is preferable to mix | blend resin, such as resin (X) and an acrylic resin, with the form of a solution, an emulsion, or a dispersion. In addition, the coating composition for the ink-receiving layer can be used in various coating forms such as aqueous and organic solvent.

  As a method for applying the ink-receiving layer coating composition, a conventionally known application method can be used without any particular limitation. Specific examples include air spray coating, airless spray coating, electrostatic coating, roll coater coating, and flow coater coating. In particular, when the substrate surface has irregularities, airless spray coating or electrostatic coating is suitable from the viewpoint of conformability to the irregular shape and the adaptability of the coating speed. In these coating methods, coating may be repeated until a desired film thickness is obtained. In addition, it is effective when the surface temperature of the base material at the time of coating is heated to 30 to 80 ° C. to form a good printing surface.

  The ink receptive layer can be formed by applying the ink receptive layer coating composition on a substrate and then allowing it to stand at room temperature or under moderate heating and drying. The ink receiving layer preferably has a dry film thickness of 5 to 40 μm from the viewpoint of further improving the color developability of the ink.

  The colored ink layer constituting the building board of the present invention is formed by printing on the ink receiving layer using an ink composition for the purpose of giving a design to the building board. In the building board of the present invention, the colored ink layer can be formed by ordinary printing means, but printing means using an ink jet printer (that is, an ink jet method) is preferable. Examples of the ink jet printer include an ink jet printer that ejects an ink composition by a charge control method or an ink on demand method. In addition, the said ink composition may be used independently and may be used as an ink set which combined 2 or more types. Moreover, it is effective from the viewpoint of the color development property of the ink that the surface temperature of the base material during printing is heated to 30 to 80 ° C.

  The form of the ink composition is not particularly limited, and various ink compositions such as a water-based ink composition, an organic solvent-based ink composition, and an active energy ray-curable ink composition can be used. Among them, it is preferable to use an active energy ray curable ink composition from the viewpoint of quick drying and a small environmental load, and by coloring an active energy ray curable ink layer on the ink receiving layer of the present application, more color development is possible. A design having excellent properties can be formed.

  The ink composition used for forming the colored ink layer (hereinafter referred to as a colored ink layer ink composition) contains a colored pigment for the purpose of giving a design to a building board. As the coloring pigment, known materials can be used. For example, carbon black, yellow iron oxide, petite, composite oxide (nickel / titanium system, chromium / titanium system, bismuth / vanadium system, cobalt / aluminum system, cobalt / (Aluminum / chromium, ultramarine blue), titanium oxide and other inorganic pigments, quinacridone, diketopropile, benzimidazolone, isoindolinone, anthrapyrimidine, phthalocyanine, selenium, dioxazine, Examples thereof include organic pigments such as azo series. From the viewpoint of weather resistance, it is preferable to use an inorganic pigment.

  In the ink composition, the content of the color pigment is not particularly limited. In the case of an active energy ray-curable ink composition, the content is preferably 2 to 20% by mass from the viewpoint of color developability of the ink. In the case of a water-based ink composition or an organic solvent-based ink composition, the content is preferably 0.2 to 10% by mass from the viewpoint of the color developability of the ink.

  The colored ink layer ink composition preferably contains a dispersant. As the dispersant, an anionic dispersant, a cationic dispersant, and a nonionic dispersant are preferable in the aqueous ink composition, and a basic dispersant (or a dispersant having a basic group) is used in the non-aqueous ink composition. ), An acidic dispersant (or a dispersant having an acidic group), and a dispersant having both a basic group and an acidic group. In addition, a commercial item can be used conveniently for a dispersing agent.

  When the ink composition is a water-based ink composition, it preferably contains a binder resin in addition to the color pigment. As the binder resin, for example, an acrylic resin, a polyester resin, a polyurethane resin, a vinyl chloride resin, or the like is preferably used. These resins may be used alone or in combination of two or more. The resin is preferably dispersed in water and used in the form of a resin dispersion. The binder resin is preferably contained in the ink composition at 1.0 to 10.0% by mass.

  In the aqueous ink composition, a solvent such as diethylene glycol monobutyl ether or ethylene glycol, and besides the above-described components, additives commonly used in the ink industry, such as antioxidants and silane coupling agents. , Plasticizers, rust inhibitors, pH adjusters, antifoaming agents, charge control agents, stress relieving agents, penetrating agents, surface adjusting agents, etc. may be appropriately selected and blended within a range that does not impair the purpose of the present invention Good.

  When the ink composition is an organic solvent-based ink composition, it preferably contains a binder resin in addition to the color pigment. As the binder resin, for example, an acrylic resin, a polyester resin, a polyurethane resin, a vinyl chloride resin, or the like is 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 at 1.0 to 10.0% by mass.

  As the organic solvent blended in the organic solvent-based ink composition, a lactone solvent such as γ-butyrolactone, a glycol ether solvent such as dipropylene glycol monomethyl ether, or the like is preferably used. In addition to the components described above, additives commonly used in the ink industry, such as antioxidants, silane coupling agents, plasticizers, rust inhibitors, pH adjusters, antifoaming agents, charge control agents, A stress relaxation agent, a penetrating agent, 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 composition, it contains an active energy ray polymerizable monomer. An active energy ray-polymerizable monomer is a monomer that undergoes a polymerization reaction upon irradiation with active energy rays such as ultraviolet rays, and has, for example, an acryloyloxy group or a methacryloyloxy group as a functional group that exhibits reactivity upon irradiation with active energy rays. Those are preferred. 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 active energy ray polymerizable monomers, the monofunctional monomer preferably has a molecular weight of 1000 or less. Specific examples include stearyl acrylate, acryloylmorpholine, 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 Ruhexyl acrylate, neopentyl glycol acrylic acid benzoate, N-vinyl-2-pyrrolidone, N-vinylimidazole, tetrahydrofurfuryl acrylate, methoxydipropylene glycol acrylate, (2-methyl-2-ethyl-1,3-dioxolane) -4-yl) methyl acrylate, cyclic trimethylolpropane formal acrylate, ethoxy-diethylene glycol acrylate, 4-hydroxybutyl acrylate and the like. In addition, these monofunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the active energy ray polymerizable monomers, the bifunctional monomer preferably has a molecular weight of 1000 or less. Specific examples include 1,10-decanediol diacrylate and 2-methyl-1,8-octanediol. Diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1,9-nonanediol 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, hydroxypivalate neopentyl glycol diacrylate, tripropylene glycol diacrylate 1,4-butanediol diacrylate, and dipropylene glycol diacrylate, and the like. In addition, these bifunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the active energy ray polymerizable monomers, the trifunctional or higher polyfunctional monomer preferably has a molecular weight of 2000 or less. Specific examples thereof include trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxy. Trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated glycerin triacrylate, tetramethylol methane triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, EO-modified diglycerin tetraacrylate, ditrimethylolpropane tetraacrylate, di Examples include pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.In addition, these polyfunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

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

  Among the active energy ray polymerizable monomers, from the viewpoint of improving the scratch resistance of the ink layer, acryloylmorpholine, 4-hydroxybutyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, 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, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, and the like preferably. From the same viewpoint, the content of the active energy ray polymerizable monomer having excellent scratch resistance is preferably 0.5 to 60.0% by mass in the total mass of the ink composition, and is preferably 5.0 to More preferably, it is 60.0 mass%.

The colored ink layer ink composition may also use an acrylate oligomer. An acrylate oligomer is an oligomer having one or more acryloyloxy groups (CH ₂ ═CHCOO—), and the number of functional groups is preferably 3-6. The acrylate oligomer preferably has a molecular weight of 2000 to 20000. In addition, this molecular weight is a weight average molecular weight of polystyrene conversion. Specific examples of the acrylate oligomer include aminoacrylate oligomer [acrylate oligomer having a plurality of amino groups (-NH ₂ )], urethane acrylate oligomer [acrylate oligomer having a plurality of urethane bonds (-NHCOO-)], epoxy acrylate oligomer [ Acrylate oligomer having a plurality of epoxy groups], silicone acrylate oligomer [acrylate oligomer having a plurality of siloxane bonds (—SiO—)], ester acrylate oligomer [acrylate oligomer having a plurality of ester bonds (—COO—)] and butadiene acrylate oligomer [butadiene Acrylate oligomer having a plurality of units] and the like. In addition, in the said ink composition for colored ink layers, content of an acrylate oligomer is 0.4-20.0 mass%, for example.

  The active energy ray-curable ink composition preferably contains a photopolymerization initiator, a light stabilizer, a polymerization inhibitor, and the like, and in addition to the above-described components, additions commonly used in the ink industry Such as water, organic solvents, antioxidants, silane coupling agents, plasticizers, rust inhibitors, pH adjusters, antifoaming agents, charge control agents, stress relaxation agents, penetrants, surface conditioners, etc. You may mix and select suitably in the range which does not injure the objective of invention.

  In the 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. . In addition, it is preferable that the temperature of the ink composition at the time of printing is 35-50 degreeC.

  The ink composition can be prepared by mixing the color pigment and various components appropriately selected as necessary.

  When the ink composition for the colored ink layer is a water-based ink composition or an organic solvent-based ink composition, it is preferable that the ink layer formed after printing is naturally dried or forcedly dried. In addition, when the colored ink layer ink composition is an active energy ray curable ink composition, the ink layer formed after printing is made of ultraviolet light using a metal halide lamp, a high-pressure mercury lamp, an ultraviolet LED, or the like. It is preferable to cure by irradiation with active energy rays. The wavelength of the active energy ray irradiated for curing 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 colored ink layer for the purpose of mainly protecting the surface of the colored ink layer. For example, when the entire surface of the ink receiving layer is covered with the colored ink layer, the clear layer is formed only on the surface of the colored ink layer, and when a part of the ink receiving layer is exposed, the clear layer is It is formed on the surface of the colored ink layer and the exposed surface of the ink receiving layer.

  In the building board of the present invention, the clear layer can be formed, for example, by applying the clear layer coating composition to the surface of the colored ink layer and optionally the exposed ink receiving layer, and then forming a film by drying or the like. . As a coating method of the clear layer coating composition, a conventionally known coating method can be used without any particular limitation. Specifically, air spray coating, airless spray coating, electrostatic coating, roll coater coating, flow coater Examples include painting.

  Various known paints can be used for the clear layer paint composition, and a paint having good weather resistance is particularly preferable. Specifically, the clear layer coating composition preferably includes 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 includes an acrylic silicone resin. . The acrylic silicone resin can exhibit the weather resistance of the silicone resin in addition to the adhesion of the acrylic resin. Of these resins, two or more kinds of resins may be used in combination.

  Examples of the acrylic resin used in the clear layer coating composition include polymers obtained by polymerizing one or more acrylic components selected from acrylic acid, methacrylic acid and esters thereof, amides, and nitriles. And those described in paragraph 0034 can be used.

The acrylic silicone resin is usually a resin having a block composed of a repeating unit constituting an acrylic resin and a block composed of a repeating unit constituting a silicone resin. In the above method, the compound shown in (h) above is blended and the polymerization is conducted by competing the acrylic polymerization reaction and the siloxane condensation reaction, or a silane compound such as dichlorodimethylsilane is polymerized by a conventional method to form a siloxane bond with the main skeleton. Can be produced by synthesizing a polymer (silicone resin) having the following, and then graft-polymerizing the above-mentioned acrylic component to the polymer by a conventional method or bonding an acrylic resin by a conventional method.
The silicone resin is not particularly limited. For example, a silicone resin having an unsaturated double bond in the molecular structure, such as an alkyd-modified silicone resin, 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 the weather resistance, the clear layer coating composition is preferably blended with an ultraviolet absorber or a light stabilizer, and in addition to the above-described components, it is usually used in the coating industry. Additives such as binder resins, pigments, water, organic solvents, film-forming aids, wetting agents, dispersants, emulsifiers, viscosity modifiers, anti-settling agents, anti-skinning agents, anti-sagging agents, antifoaming agents, Color separation preventing agent, leveling agent, drying agent, plasticizer, fungicide, antibacterial agent, insecticide, preservative, antistatic agent, conductivity imparting agent, etc. are appropriately selected within a range that does not impair the purpose of the present invention. May be blended.

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

  Next, the embodiment of the building board of this invention is demonstrated, referring a figure. FIG. 1 is a schematic cross-sectional view of one embodiment of a building board of the present invention. The building board 1 of FIG. 1 includes a base material 2, an ink receiving layer 3 disposed on the base material 2, a colored ink layer 4 disposed on the ink receiving layer 3, and a colored ink layer 4. And a disposed clear layer 5. In the building board 1 of FIG. 1, since the entire surface of the ink receiving layer 3 is covered with the colored ink layer 4, the clear layer 5 is formed only on the surface of the colored ink layer 4. In FIG. 1, the entire surface of the ink receiving layer 3 is covered with the colored ink layer 4, but the colored ink layer 4 may be covered only on a part of the surface of the ink receiving layer 3. In this case, the clear layer 5 is formed on the surface of the ink receiving layer 3 and the surface of the colored ink layer 4 that are not covered with the colored ink layer 4.

<Coating composition>
Below, the coating composition of this invention is demonstrated in detail. The coating composition of the present invention is a coating composition for forming an ink receiving layer of a building board, and is a resin (X) having a thermal softening temperature of 90 to 193 ° C., among vinyl resin and urethane resin. It contains at least one resin (X). The embodiment of the coating composition of the present invention is as described in the description of the coating composition for an ink receiving layer of the building board of the present invention. Specifically, the coating composition of the present invention preferably contains an acrylic resin (Y), where the mass ratio (X / Y) of the resin (X) to the acrylic resin (Y) is 85 / 15-15. More preferably, it is / 85.

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

<Preparation example of coating composition for ink receiving layer>
The raw materials and titania beads (φ1.4 mm) were mixed according to the formulation shown in Tables 1 to 3, and then dispersed by a bead mill. After dispersion, titania beads were removed, and ink-receiving layer coatings 1 to 18 were prepared.

The compounding agents shown in Tables 1 to 3 are as follows.
1) Titanium oxide, density 3.8 g / cm ³ (TITONE R-62N, manufactured by Sakai Chemical Co., Ltd.)
2) Heavy calcium carbonate, density 2.7 g / cm ³ , average particle size 2 μm (manufactured by Maruo Calcium)
3) Aqueous polyurethane dispersion (Superflex 820, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
4) Aqueous polyurethane dispersion (Superflex 470, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
5) Polyurethane aqueous dispersion (Superflex 460, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
6) Aqueous polyurethane dispersion (Superflex 150HS, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
7) Aqueous polyurethane dispersion (Superflex 420, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
8) Yodosol AD57 (Henkel Japan, resin component 50 mass%, resin component density 1.2 g / cm ³ , glass transition temperature 55 ° C.)
9) SN deformer 1316 (manufactured by San Nopco)
10) ASE-60 (Rohm and Haas)
11) Proxel AM (manufactured by Arch Chemicals)

<Example of preparation of active energy ray-curable ink composition>
In accordance with the formulation shown in Tables 4 and 5, the raw material and zirconia beads (φ0.5 mm) were mixed and then dispersed by a bead mill. After dispersion, the zirconia beads were removed to prepare a three-color ink composition, and an active energy ray curable ink set was prepared.

The compounding agents shown in Tables 4 and 5 are as follows.
12) Cobalt blue (Sicopal Blue K 6310, manufactured by BASF)
13) Iron oxide (yellow) (Sicotrans Yellow L1916, manufactured by BASF)
14) Iron oxide (red) (Sicotrans Red L2817, manufactured by BASF)
15) DISPERBYK-2155 (manufactured by BYK)
16) BYK-UV3500 (manufactured by BYK)

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

<Preparation Example of Clear Layer Coating Composition>
According to the formulation shown in Table 6, raw materials were mixed to prepare a clear paint.

The compounding agents shown in Table 6 are as follows.
17) Polydurex G613, manufactured by Asahi Kasei Corporation, solid content 41.5% by mass
18) TINUVIN 1130, manufactured by BASF 19) TINUVIN 292, manufactured by BASF

<Examples of building boards (decorative test boards)>
1. Substrate slate plate (150mm × 70mm × 5mm, TP Giken Co., Ltd.) aqueous sealer to the surface of (Dai Nippon Toryo Co., product name: aqueous Mighty sealer multi) coated with an air spray so that a coating amount 100 g / ^{m 2} And the base material was produced by drying at room temperature for 2 hours.

2. Ink-receiving layer In a state where the base material coated with a sealer is heated to 60 ° C., the above-mentioned coating composition for the ink-receiving layer is applied to the surface of the base material on which the sealer is applied 120 g / m ² (corresponding to a dry film thickness of 30 μm) It was painted with airless spray so that Thereafter, the ink receiving layer was formed by drying at 100 ° C. for 3 minutes. In addition, the temperature measurement of the substrate surface was performed using an infrared radiation type non-contact thermometer (ISK-8700II, manufactured by ASONE Co., Ltd.).

3. Ink layer (ink layer preparation condition 1)
After preparing the ink receiving layer, the active energy ray-curable ink composition (ink A (yellow, red, blue) prepared above) was prepared using an inkjet printer with the substrate temperature adjusted to 60 to 70 ° C. Alternatively, ink B (yellow, red, blue)) is a single color gradation pattern (solid image in which recording density is recorded in steps of 20% from 10% to 150%) and a color mixture level of each color combination. Each tone pattern was formed. At this time, the temperature of the ink when ejecting the ink 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. In addition, the temperature measurement of the substrate surface was performed using an infrared radiation type non-contact thermometer (ISK-8700II, manufactured by ASONE Co., Ltd.).

(Ink layer preparation condition 2)
The operation was performed in the same manner as in ink layer preparation condition 1 except that the substrate temperature was changed from 60 to 70 ° C. to 30 to 40 ° C.

4). Clear layer After curing the ink composition under Ink Layer Preparation Condition 1 or Ink Layer Preparation Condition 2, the coating amount of the above clear paint is 80 g with the surface temperature of the cured coating film adjusted to 50 ° C. / M ² (dry film thickness equivalent to 25 μm). After painting, it was dried at 80 ° C. for 20 minutes to form a clear layer. In addition, the temperature measurement of the substrate surface was performed using an infrared radiation type non-contact thermometer (ISK-8700II, manufactured by ASONE Co., Ltd.).

<Example of sample production for measuring elongation at break>
The above-described coating composition for an ink receiving layer was applied to a polypropylene plate with an airless spray so that the coating amount was 120 g / m ² (equivalent to a dry film thickness of 30 μm). Thereafter, the ink receiving layer was formed by drying at 60 ° C. for 5 minutes. Thereafter, the ink receiving layer was isolated from the polypropylene plate and cut into a size of 30 mm in length and 10 mm in width.

<Examples 1-22, Comparative Examples 1-8>
A decorative test plate was prepared according to the above-described production example of the decorative test plate. Tables 7 to 12 show combinations of the ink receiving layer coating composition and the clear layer coating composition used. A sample for measuring elongation at break was separately prepared.

<Evaluation>
In accordance with the method described below, the flexibility and warmth of the ink receiving layer and the weather resistance of the decorative test plate were evaluated. The results are shown in Tables 7-12.

1. Flexibility of Ink Receiving Layer The flexibility of the ink receiving layer was evaluated by the elongation rate (breaking elongation rate) of the film. The elongation at break was measured at a tensile rate of 20 mm / min using a tensile strength tester (Shimadzu Autograph AG2000B) against an ink receiving layer (length 30 mm, width 10 mm) for measuring the elongation at break. .
○: 15% or more.
Δ: Less than 5 to 15%.
X: Less than 5%.

2. Warm Sensitivity Color development was evaluated by observing with a naked eye and a microscope a solid image of each gradation pattern one day after the production of the decorative test plate. Then, the result of having evaluated the influence on the color development property by the temperature at the time of ink printing is shown to Tables 7-12. The evaluation criteria are as follows.
◯: As a result of evaluating and comparing the color developability when the substrate temperature at the time of ink printing is 30 to 40 ° C. and 60 to 70 ° C., no difference in color developability is observed, and any drying temperature However, the original color of the ink is printed uniformly, and unevenness and dullness are hardly recognized.
X: A difference in color developability due to a difference in substrate temperature during ink printing is recognized. When the substrate temperature during ink printing is 60 to 70 ° C., unevenness and dullness are observed in the gradation pattern.

DESCRIPTION OF SYMBOLS 1 Building board 2 Base material 3 Ink receiving layer 4 Colored ink layer 5 Clear layer

Claims (6)

  A building board comprising: a substrate; an ink receiving layer formed on the substrate; a colored ink layer formed on the ink receiving layer; and a clear layer formed to cover at least the colored ink layer. The ink receiving layer is a resin (X) having a thermal softening temperature of 90 to 193 ° C., and is formed of a coating composition containing a resin (X) made of at least one of a vinyl resin and a urethane resin. An architectural board characterized by that.   The building board according to claim 1, wherein the coating composition further contains an acrylic resin (Y).   The building board according to claim 2, wherein a mass ratio (X / Y) of the resin (X) and the acrylic resin (Y) is 85/15 to 15/85.   The building board according to any one of claims 1 to 3, wherein the colored ink layer is formed of an active energy ray-curable ink composition.   The building plate according to claim 4, wherein the active energy ray-curable ink composition contains 2 to 20% by mass of a color pigment.   A coating composition for forming an ink-receiving layer of a building board, which is a resin (X) having a heat softening temperature of 90 to 193 ° C., and comprising at least one of a vinyl resin and a urethane resin (X) A coating composition comprising:

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