JP7288357B2 - Ink set, laminate, method for producing laminate, and recording method - Google Patents

Description

The present invention relates to an ink set, a layered product, a method for manufacturing a layered product, and a recording method using an ink jet system.

As the ink composition, a water-based ink composition in which various water-soluble dyes are dissolved in water or a mixture of water and an organic solvent, or a solvent-based ink containing no water and containing an organic solvent as a main component. Active energy ray-curable ink compositions containing compositions and active energy ray-polymerizable compounds are widely used.

Further, in the ink composition for color recording, an ink set is generally used in which a black ink is added to an ink set containing the three primary colors of yellow ink, magenta ink, and cyan ink. Various hues can be expressed by adjusting the amount of transfer of each of the three primary colors of the ink composition, particularly in the case of an ink jet system, by adjusting the amount of ejection.

However, a coating film (decorative layer) formed using ink compositions of different colors may have a reduced chroma, which may limit the hues that can be expressed. Therefore, there is a demand for an ink set that does not lower chroma and has wide color expression.

For example, in Patent Document 1, C.I. I. Pigment Yellow 120, a yellow ink, and a C.I. I. A magenta ink containing Pigment Violet 19 is disclosed. Patent Document 1 describes that such an ink set can provide a printed matter (laminate) with high chromaticity and high reflection color density, inconspicuous streak unevenness, and excellent glossiness and flexibility. It is

JP 2013-209668 A

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink set that has a wide range of color expression properties and that can suppress a decrease in chroma.

As a result of intensive studies to solve the above problems, the present inventors have found that the hue distance D calculated from the perceptual chromaticity index in the coating film formed by applying the ink composition to the substrate, and the hue angle The inventors have found that the above problems can be solved by an ink set in which H and are specified, and have completed the present invention. Specifically, the present invention provides the following.

(1) A CIELAB space in a yellow coating film containing a yellow ink containing a yellow pigment and a magenta ink containing a magenta pigment, and formed by applying the yellow ink to a substrate The hue distance D=√(a ^* ^2+b ^* ^2) calculated from the perceptual chromaticity indices a ^* and b ^* defined in is 105 or more and is calculated from the perceptual chromaticity indices a ^* and b ^* The hue angle H = tan ^-1 (b ^* /a ^* ) is 70° or more and 85° or less, and is defined in CIELAB space in a magenta-based coating film formed by applying the magenta ink to a substrate. The hue distance D=√(a ^* ^2+b ^* ^2) calculated from the perceptual chromaticity indices a ^* and b ^* is 73 or more, and the hue angle H= calculated from the perceptual chromaticity indices a ^* and b ^* An ink set in which tan ⁻¹ (b ^* /a ^* ) is −20° or more and 25° or less.

(2) The ink set according to (1), wherein the yellow pigment contained in the yellow ink is an isoindolinone pigment.

(3) The content of the yellow pigment contained in the yellow ink is 2.0 parts by mass or more and 15.0 parts by mass or less per 100 parts by mass of the yellow ink, and the content of the magenta pigment contained in the magenta ink is 2.0 parts by mass or more and 15.0 parts by mass or less per 100 parts by mass of magenta ink.

(4) The ink set according to any one of (1) to (3), which is used in an inkjet method.

(5) A decorative layer, which is a coating film containing at least one of yellow ink and magenta ink contained in the ink set according to any one of (1) or (4), was formed on a substrate. laminate.

(6) A method for producing a laminate, wherein at least one of the yellow ink and the magenta ink contained in the ink set according to any one of (1) and (4) is ejected onto the surface of a substrate by an inkjet method.

(7) A recording method in which at least one of the yellow ink and the magenta ink contained in the ink set according to any one of (1) and (4) is ejected onto the surface of a substrate by an inkjet method.

According to the present invention, the ink set has a wide range of color expressiveness and is capable of suppressing a decrease in chroma.

Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the purpose of the present invention. can do.

<1. Outline of Ink Set>
The ink set according to this embodiment includes at least yellow ink and magenta ink. In this specification, an ink set means an ink set containing ink compositions of different colors such as yellow ink and magenta ink, for example, an ink set consisting of yellow ink, magenta ink and cyan ink. It is a concept that includes an ink set that adds black ink, white ink, etc. to it.

The yellow ink contained in this ink set has a hue distance D of 105 or more and a hue angle H of 70° or more and 85° of a yellow-based coating film formed by applying the yellow ink to a substrate. It is below. Further, the magenta ink contained in this ink set has a hue distance D of 73 or more and a hue angle H of −20° or more and 25 ° or less.

Here, the hue distance D and the hue angle H are values calculated from the perceptual chromaticity indices a ^* and b ^* defined in the CIELAB space, and the hue distance D=√(a ^* ^2+b ^* ^2) , hue angle H=tan ⁻¹ (b ^* /a ^* ). Note that “√” means the root (1/2 power), “^2” means the square, “tan ⁻¹ ” means the reciprocal of the tangent, and the frequency method of the hue angle H ( The unit is °).

According to the opinion of the present inventors, an ink set containing a yellow ink and a magenta ink that satisfies the above conditions suppresses a decrease in chroma due to mixing ink compositions of different colors, resulting in color expression. can be effectively spread.

Ink compositions (eg, cyan ink, black ink, white ink) other than the yellow ink and magenta ink contained in the ink set according to the present embodiment can be used without particular limitation.

The ink set according to the present embodiment is characterized in that the use of two ink compositions, a yellow ink and a magenta ink, can effectively improve color expression. For example, although it is possible to expand the color expression by using three or more conventional ink compositions, a coating film (decorative layer) is formed on the substrate using a larger number of ink compositions. As a result, the consumption of the ink composition in the ink set as a whole increases, and the cost of manufacturing the laminate increases. Moreover, if more ink compositions of different colors are used, the chroma of the coating film (decorative layer) will be lowered. The ink set according to the present embodiment uses only two ink compositions, a yellow ink and a magenta ink, and has a perceptual chromaticity index in the range of 0≦a ^* and 0≦b ^*. can be increased. When forming a coating film (decorative layer) having a color with a perceptual chromaticity index in the range of 0 ≤ a ^* and 0 ≤ b ^* , the consumption of the ink composition is suppressed, and the coating film (decorating layer) is improved. It is possible to effectively suppress the decrease in saturation.

A coating film (decorative layer) for measuring the perceptual chromaticity indices a ^* and b ^* , which are the premises for calculating the hue distance D and the hue angle H, can be formed, for example, by ejecting with an inkjet method. can. For example, there is a method of coating the surface of the substrate with a recording pattern (printing pattern) of 600×600 dpi, 12 pl, and 100% ink composition. The perceptual chromaticity indices a ^* and b ^* can be measured using, for example, X-Rite eXact (manufactured by X-Rite) under the conditions of D50 light source and 2° viewing angle.

Next, the ink composition constituting the ink set will be described.

<2. Ink composition>
The ink composition contains at least a coloring material, a resin, and a solvent (water and/or organic solvent). Alternatively, when the ink composition is an active energy ray-curable ink composition, it contains an active energy ray-polymerizable compound as described later. The colorant and other additives contained in the ink composition are described below.

Each component contained in the water-based ink composition will be described below.

(colorant)
The aqueous ink composition contained in the ink set contains a coloring material. The coloring material is not particularly limited as long as it can form a decorative layer (coating film) that satisfies the predetermined hue distance D and hue angle H. As the coloring material, dyes or pigments commonly used in ink compositions can be used.

The magenta-based colorant contained in the magenta ink is preferably a quinacridone-based pigment, and C.I. I. Pigment Red 122, C.I. I. Pigment Violet 19 and the like are preferred.

From the viewpoint of increasing the area in the range of 0≦a ^* and 0≦b ^* in the CIELAB space, C.I. I. Pigment Violet 19 is preferably used. It is possible to widen the color expressibility in the range of 0≦a ^* and 0≦b ^* . On the other hand, from the viewpoint of increasing the area in the range of 0≦a ^* and 0≧b ^* in the CIELAB space, C.I. I. Pigment Red 122 is preferably used. It is possible to widen the color expressibility in the range of 0≦a ^* and 0≧b ^* .

The yellow colorant contained in the yellow ink is C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 83 and the like. In addition to being able to form a decorative layer (coating film) that satisfies a predetermined hue distance D and hue angle H, it is possible to form a decorative layer (coating film) with high weather resistance. The material is preferably an isoindolinone pigment, and among the isoindolinone pigments, C.I. I. Pigment Yellow 110 is particularly preferred.

In particular, C.I. I. C.I. Pigment Violet 19 was used as a yellow colorant contained in the yellow ink. I. An ink set using Pigment Yellow 110 makes it possible to form a highly weather-resistant decorative layer (coating film). Such an ink set is particularly useful for applications that may be left standing indoors or outdoors for a long period of time (for example, decorative board applications).

For example, conventionally known coloring materials may be used for ink compositions other than magenta ink and yellow ink such as cyan ink and black ink. The coloring material may be any of dyes, inorganic pigments, organic pigments, etc. that are commonly used in conventional ink compositions. For example, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, titanium oxide, chromium oxide, Viridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, diketopyrrolopyrrole, anthraquinone, Benzimidazolone, anthrapyrimidine, azo pigment, phthalocyanine pigment, dioxazine pigment, threne pigment, perylene pigment, perinone pigment, thioindigo pigment, quinophthalone pigment, metal complex pigment, aluminum paste, silica, calcium carbonate , magnesium carbonate, clay, precipitated barium sulfate, and pearl pigments.

In the case of magenta ink, the content of the magenta colorant is preferably 2.0 parts by mass or more in 100 parts by mass of magenta ink, more preferably 3.0 parts by mass or more in 100 parts by mass of magenta ink. , more preferably 4.0 parts by mass or more in 100 parts by mass of magenta ink. Thereby, the coloring property of the decorative layer (coating film) formed on the surface of the substrate can be improved. The content of the magenta colorant is preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less per 100 parts by mass of the magenta ink.

In the case of yellow ink, the content of the yellow colorant is preferably 2.0 parts by mass or more in 100 parts by mass of yellow ink, and more preferably 3.0 parts by mass or more in 100 parts by mass of yellow ink. and 4.0 parts by mass or more per 100 parts by mass of the yellow ink. Thereby, the coloring property of the decorative layer (coating film) formed on the surface of the substrate can be improved. The content of the yellow colorant is preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less per 100 parts by mass of the yellow ink.

In particular, when the ink set is used in an ink jet system, from the viewpoint of the dispersibility of the coloring material, it is particularly preferred that the amount is 2.0 parts by mass or more and 15.0 parts by mass or less per 100 parts by mass of the ink. preferable.

Regarding ink compositions other than magenta ink and yellow ink, the content of the coloring material is not particularly limited, but is preferably 2.0 parts by mass or more based on 100 parts by mass of the ink composition. It is more preferably 3.0 parts by mass or more in 100 parts by mass of the ink composition, and even more preferably 4.0 parts by mass or more in 100 parts by mass of the ink composition. The content of the coloring material is preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less per 100 parts by mass of the ink composition.

When a pigment is used as the coloring material, the average dispersed particle diameter of the pigment is not particularly limited as long as the desired color development is possible. The average particle size of the pigment is preferably 70 nm or more, and preferably 500 nm or less, from the viewpoint of good pigment dispersion stability and sufficient coloring power, although it varies depending on the type of pigment. If the average dispersed particle diameter is 500 nm or less, nozzle clogging of an inkjet head is less likely to occur, and a uniform image with high reproducibility can be obtained, particularly when the ink composition is ejected by an inkjet method. When the average dispersed particle size is 70 nm or more, the obtained laminate can have good weather resistance. The average dispersed particle size of the pigment can be measured at a measurement temperature of 25° C. using a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., model: FPAR-1000).

Aqueous ink compositions, solvent-based ink compositions, and active energy ray-curable ink compositions are described below.

[2-1. Aqueous ink composition]
An aqueous ink composition is an ink composition containing water as a main component and may contain an organic solvent. This ink composition is transferred to the surface of the base material, and in the case of an ink jet method in particular, it is ejected to volatilize water and an organic solvent from the ink composition to form a decorative layer.

Aqueous ink compositions are inexpensive and can form a decorative layer without irradiation with active energy rays. Moreover, when a solvent containing water as a main component is used, the ink composition is safe and environmentally friendly.

[water]
In the water-based ink composition, it is preferable to use deionized water rather than water containing various ions. The content of water is not particularly limited as long as it is a content capable of dispersing or dissolving each component. It is preferably 20% by mass or more, and particularly preferably 30% by mass or more in the total amount of the ink composition. It is preferably 95% by mass or less in the total amount of the ink composition, and more preferably 90% by mass or less in the total amount of the ink composition.

[Organic solvent]
The organic solvent contained in the water-based ink composition is capable of dispersing or dissolving the components contained in the ink composition. Such an organic solvent may be a water-soluble solvent or a water-insoluble solvent. Here, having water solubility means that 5 parts by mass or more can be dissolved in 100 parts by mass of water at 25° C. under 1 atm.

Water-soluble solvents include, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-pentanol, etc. 5 alkyl alcohols; monohydric alcohols such as 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, 3-methoxy-n-butanol; 1 -dimethylformamide, dimethylacetamide, 3-methoxypropanamide, 3-butoxypropanamide, N,N-dimethyl-3-methoxypropanamide, N,N-dibutyl-3-methoxypropanamide, N,N-dibutyl-3 - amides such as butoxypropanamide and N,N-dimethyl-3-butoxypropanamide; ketones or ketoalcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; Ethylene or oxypropylene copolymer; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, isobutylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, 1,3-propanediol, 2 -methyl-1,2-propanediol, 2-methyl-1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1 ,2-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5- diols such as pentanediol and 2-methyl-2,4-pentanediol; triols such as glycerin, trimethylolethane, trimethylolpropane and 1,2,6-hexanetriol; tetravalents such as mesoerythritol and pentaerythritol Alcohols; ethylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl) ether, diethylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl) Ether, triethylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl) ether, propylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl) ether, dipropylene glycol monomethyl (or ethyl, isopropyl, n-butyl) , isobutyl) ether; monoalkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene Dialkyl ethers of polyhydric alcohols such as glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether; monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanol alkanolamines such as amines, N-methyldiethanolamine, N-ethyldiethanolamine and N-butyldiethanolamine; nitrogen-containing complexes such as N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone Cyclic compounds; Cyclic compounds such as γ-butyrolactone and sulfolane.

The content of the water-soluble solvent is preferably 20 parts by mass or more in 100 parts by mass of the ink. The content of the water-soluble solvent is preferably 55 parts by mass or less in 100 parts by mass of the ink. This makes it possible to improve the dispersibility and solubility of the colorant (pigment) and resin contained in the ink composition.

A water-soluble solvent having a boiling point of 250° C. or higher may also be contained. It is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less in 100 parts by mass.

[Pigment Dispersant]
The aqueous ink composition may contain a pigment dispersant. Here, the pigment dispersant means a resin or surfactant that has a function of improving the dispersibility of the pigment in the ink by adhering to a part of the pigment surface.

The pigment dispersant that can be used in the water-based ink composition is not particularly limited. For example, cationic, anionic, nonionic, amphoteric, silicone (silicon), and fluorine surfactants can be used. Among surfactants, polymer surfactants (polymer dispersants) such as those exemplified below are preferable.

As the pigment dispersant that can be used in the aqueous ink composition, a water-soluble polymer dispersant can be preferably used. Examples of water-soluble polymer dispersants include polyester-, polyacrylic-, polyurethane-, polyamine-, and polycaptolactone-based main chains, and side chains containing amino, carboxy, sulfo, and hydroxy groups. and dispersing agents having polar groups such as For example, (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene and unsaturated carboxylic acid esters such as acrylic acid esters; (partial) amine salts, (partial) ammonium salts and (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters Polyurethanes; Unsaturated polyamides; Polysiloxanes; Long-chain polyaminoamide phosphates; Polyethyleneimine derivatives (poly (lower alkylene imine) and free carboxyl group-containing polyester amides obtained by reaction and their bases); polyallylamine derivatives (polyallylamine and polyester having a free carboxyl group, polyamide or co-condensation product of ester and amide (polyesteramide)) reaction products obtained by reacting with one or more compounds) and the like. Among them, a water-soluble polymer dispersant containing a (meth)acrylic resin is preferable from the viewpoint of ink dispersion stability and image clarity of the decorative layer.

Specific examples of water-soluble polymer dispersants include SMA1440, SMA2625, SMA17352, SMA3840, SMA1000, SMA2000, SMA3000 manufactured by SARTOMER, JONCRYL67 manufactured by BASF Japan, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL680 and JON. CRYL682, JONCRYL690, JONCRYL819, JONCRYL - JDX5050, EFKA4550, EFKA4560, EFKA4585, EFKA5220, EFKA6230, Lubrizol SOLSPERSE20000, SOLSPERSE27000, SOLSPERSE41000, SOLSPERSE41090, SOLSPERSE43000, SOLSPERSE43000 ERSE44000, SOLSPERSE46000, SOLSPERSE47000, SOLSPERSE54000, BYKJET-9150 manufactured by BYK-Chemie, BYKJET-9151, BYKJET-9170, DISPERBYK-168, DISPERBYK-190, DISPERBYK-198, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2015, and the like. These pigment dispersants can be suitably used in aqueous ink compositions.

In the water-based ink composition, when a pigment is used as the colorant, the pigment that can be used is a pigment dispersion in which the pigment is dispersed in a water-soluble solvent using a pigment dispersant. A pigment dispersion in which a self-dispersing pigment is directly modified with a hydrophilic group may be used. In the present embodiment, the pigment that can be used in the water-based ink composition may be a combination of a plurality of the above-described organic pigments and inorganic pigments. A dispersion and a self-dispersing pigment may be used in combination. When using a self-dispersion pigment, a conventionally known self-dispersion pigment can be used.

[resin]
A water-based ink composition may contain a resin. The resin is not essential in the ink composition of the present embodiment, but by containing the resin in the ink composition, the water resistance of the decorative layer formed from the ink composition is improved. At least part of the resin contained in the aqueous ink composition is preferably contained as a resin emulsion. In the aqueous ink composition of the present embodiment, the resin emulsion means an aqueous dispersion in which the continuous phase is a water-soluble solvent and the dispersed particles are resin fine particles. By forming a resin emulsion, the resin can be dispersed in the water-based ink composition as fine resin particles by electrostatic repulsion. The resin emulsion generally has the property of thickening and aggregating when the water-soluble solvent, which is a continuous phase, is reduced due to evaporation, permeation, etc., and has the effect of promoting the fixation of the coloring material (pigment) to the base material.

The resin contained in the aqueous ink composition of the present embodiment is not particularly limited as long as it can exhibit the desired water resistance. Examples include acrylic resins, polystyrene resins, polyester resins, Vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl acetate copolymer resin, polyethylene resin, urethane resin, silicone (silicon) resin, acrylamide resin, epoxy resin, cellulosic resin such as nitrocellulose, or copolymer resin or mixture thereof can be used. These are preferable because they can improve not only water resistance but also solvent resistance. Among them, it can be made excellent in water resistance and solvent resistance, and in particular when the ink composition is ejected by an inkjet method, it can be made excellent in ejection stability, so it contains an acrylic resin. It is preferable that the

The acrylic resin is not particularly limited as long as it is contained as a main component of the monomer constituting the (meth)acrylic acid ester monomer. As the (meth)acrylic acid ester monomer, a known compound can be used, and a monofunctional (meth)acrylic acid ester can be preferably used. Examples thereof include (meth)acrylic acid alkyl esters, (meth)acrylic acid aralkyl esters, (meth)acrylic acid alkoxyalkyl esters, and the like. Specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, -n-propyl (meth)acrylate, -iso-propyl (meth)acrylate, -n-butyl (meth)acrylate , sec-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, (meth)acrylic acid Hexyl, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, iso-octyl (meth)acrylate, nonyl (meth)acrylate, iso-nonyl (meth)acrylate, (meth)acrylic dodecyl acid, tridecyl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopenta (meth)acrylate nyl, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate ) adamantyl acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, anthraninonyl (meth)acrylate, ( meth)piperonyl acrylate, salicyl (meth)acrylate, furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, pyranyl (meth)acrylate , benzyl (meth)acrylate, phenethyl (meth)acrylate, cresyl (meth)acrylate, glycidyl (meth)acrylate, -3,4-epoxycyclohexylmethyl (meth)acrylate, -3 (meth)acrylate ,4-Epoxycyclohexylethyl, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, (meth)acrylic acid Perfluoro-iso-propyl, heptadecafluorodecyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate , methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylamino (meth)acrylate (meth)acrylic acid esters such as ethyl, trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, etc. In addition, "(meth)acryl" means both "acryl" and "methacryl". These monomers are available from Mitsubishi Rayon Co., Ltd., NOF Co., Ltd., Mitsubishi Chemical Co., Ltd., Hitachi Chemical Co., Ltd., and the like.

Commercially available resin emulsions include, for example, Acryt WEM-031U, WEM-200U, WEM-321, WEM-3000, WEM-202U, WEM-3008 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic-urethane resin emulsion), Acryt UW-550CS, UW-223SX, AKW107, RKW-500 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic resin emulsion), LUBRIJET N240 (manufactured by Lubrizol, acrylic resin emulsion), Superflex 150, 210, 470, 500M, 620, 650, E2000, E4800, R5002 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion), Vinyblan 701FE35, 701FE50, 701FE65, 700, 701, 711, 737, 747 (manufactured by Nisshin Chemical Co., Ltd., vinyl chloride-acrylic resin emulsion), Vinyblan 2706, 2685 (manufactured by Nisshin Chemical Co., Ltd., acrylic resin emulsion), Movinyl 743N, 6600, 7470, 7720, (manufactured by Nippon Synthetic Chemical Co., Ltd., acrylic resin emulsion), PRIMAL AC-261P, AC-818 (manufactured by Dow Chemical Company, acrylic resin particle emulsion) can be exemplified, but is not limited to these.

The average particle size of the resin emulsion is preferably 30 nm or more, preferably 50 nm, from the viewpoint of dispersion stability in the ink composition, particularly from the viewpoint of ejection stability when the ink composition is ejected by an inkjet method. The above is more preferable. The upper limit is preferably 300 nm or less, more preferably 250 nm or less. In the present embodiment, the number average particle size of the resin emulsion can be measured using a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., model: FPAR-1000) at a measurement temperature of 25°C.

The weight average molecular weight of the resin emulsion is preferably 10,000 or more, more preferably 100,000 or more, from the viewpoint of the stability of the ink composition and the water resistance of the film. The weight average molecular weight of the resin emulsion is preferably 1,000,000 or less, more preferably 500,000 or less, from the viewpoint of the stability of the ink composition and the water resistance of the film. In the present embodiment, the molecular weight of the resin indicates the mass average molecular weight Mw, which is a value measured by GPC (gel permeation chromatography), using "HLC-8120GPC" manufactured by Tosoh Corporation. , can be measured using a polystyrene standard for a calibration curve as a standard.

The glass transition point (Tg) of the resin emulsion is such that even when recording (printing) on a low-absorbent recording medium or a non-absorbent recording medium, a laminate having a decorative layer having water resistance, solvent resistance, and abrasion resistance can be obtained. Since it can be formed, it is also possible to avoid applying high temperatures to form the laminate, so that a lot of energy is not required, and the laminate is less susceptible to heat damage. Therefore, the temperature is preferably 0° C. or higher, more preferably 10° C. or higher, and more preferably 20° C. or higher. For the same reason, the temperature is preferably 100° C. or lower, more preferably 90° C. or lower, and more preferably 80° C. or lower. The glass transition temperature (Tg) can be measured, for example, with a differential scanning calorimeter "DSC-50" manufactured by Shimadzu Corporation.

The resin emulsion is not limited to cationic, nonionic, or anionic, but the acid value of the resin emulsion is determined from the viewpoint of the water resistance of the decorative layer in the laminate, the storage stability of the ink composition, and the like. Therefore, it is preferably 25 mgKOH/g or less.

In the water-based ink composition, the mass parts of the resin (resin emulsion) contained in 100 mass parts of the ink composition is particularly limited as long as a laminate having desired water resistance and solvent resistance can be formed. However, for example, it is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.5 parts by mass or more based on 100 parts by mass of the ink composition. is preferred, and 1 part by mass or more is preferred. It is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the ink composition.

[Surfactant]
The aqueous ink composition may contain a surfactant as another additive. Surfactants that can be used in the aqueous ink composition of the present embodiment are not particularly limited, but examples include polysiloxane compounds, anionic surfactants, nonionic surfactants, fluorine-based Surfactants, alkylene oxide-modified acetylene glycol-based surfactants, alkylene oxide-unmodified acetylene glycol-based surfactants, and the like can be mentioned.

In the aqueous ink composition of the present embodiment, among others, one of an alkylene oxide-unmodified acetylene glycol-based surfactant, an alkylene oxide-modified acetylene glycol-based surfactant, and a polysiloxane compound is used as a surface tension modifier. It is preferable that the ink composition is contained because it can improve the wetting and spreading property of the ink composition on the substrate.

<2-2. Solvent-based Ink Composition>
A solvent-based ink composition is an ink composition containing no water and containing an organic solvent as a main component. In the solvent-based ink composition of the present embodiment, "not containing water" means that the ink composition is produced without intentionally containing water. Water that is contained due to reasons unintended by the manufacturer, such as water contained in additives, etc., is not considered.

[Organic solvent]
In the solvent-based ink composition, the same organic solvent as the organic solvent contained in the water-based ink composition can be used.

[resin]
The solvent-based ink composition of this embodiment contains a resin. By containing the resin in the ink composition, the water resistance of the decorative layer formed from the ink composition is improved. Resins are not particularly limited, and examples include acrylic resins, polystyrene resins, polyester resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride vinyl acetate copolymer resins, polyethylene resins, urethane resins, rosin-modified resins, phenol resins, and terpenes. resin, polyamide resin, vinyl toluene-α-methylstyrene copolymer, ethylene-vinyl acetate copolymer, cellulose acetate butyrate, silicone (silicon) resin, acrylamide resin, epoxy resin, or copolymer resins thereof, Mixtures can be used.

In the solvent-based ink composition of the present embodiment, among others, the water resistance and solvent resistance can be improved. It is preferable that the resin contains an acrylic resin because it can improve ejection responsiveness and ejection stability.

The acrylic resin is not particularly limited as long as it is contained as a main component of the monomers constituting the (meth)acrylic acid ester monomer, and examples thereof include those similar to those of the aqueous ink composition described above. . The acrylic resin may be a homopolymer of one radically polymerizable monomer, or may be a copolymer of two or more selected radically polymerizable monomers. Preferred acrylic resins for solvent-based ink compositions in the form of methyl methacrylate are polymers of methyl methacrylate, or at least one polymer selected from the group consisting of methyl methacrylate and butyl methacrylate, ethoxyethyl methacrylate, and benzyl methacrylate. It is a copolymer with one or more compounds.

In the solvent-based ink composition of the present embodiment, the mass parts of the resin contained in 100 mass parts of the ink composition is not particularly limited, but for example, 0.05 mass parts or more in the ink composition. Among them, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more. The amount of the resin contained in 100 parts by mass of the ink composition is not particularly limited, but for example, it is preferably 20 parts by mass or less in the ink composition, and especially 15 parts by mass or less. is more preferable.

[Dispersant]
A dispersant may be used as necessary in the solvent-based ink composition of the present embodiment. Any dispersant used in solvent-based ink compositions can be used as the dispersant. As the dispersant, a polymer dispersant is preferably used. Such a dispersant has a main chain of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and has a polar group such as an amino group, a carboxyl group, a sulfone group, or a hydroxyl group as a side chain. is. For polyacrylic dispersants, for example, Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131 , 9132, 9133, and 9151 (manufactured by BYK-Chemie) are used. Polycaprolactone-based dispersants include, for example, Ajisper PB821, PB822, and PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.). Preferable dispersants are polyester dispersants such as Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 (manufactured by Kawaken Fine Chemicals Co., Ltd.), Solsperse 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000 (manufactured by Lubrizol), Floren DOPA-15BHFS, 17HF, 22, G-700, 900, NC-50 0 , GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), Efka 4310, 4320, 4330, 4401, 4402, 4403N, 4570, 7411, 7477, 7700 (manufactured by BASF), or a mixture thereof.

[Surfactant]
In addition, in the solvent-based ink composition of the present embodiment, the purpose is to suppress volatilization and solidification of the solvent-based ink composition in devices such as nozzles and tubes, or to re-dissolve when solidified. Alternatively, a nonionic polyoxyethylene derivative that is liquid at room temperature and atmospheric pressure may be added. For example, polyoxyalkylene alkyl ethers nonionic P-208, P-210, P-213, E-202S, E-205S, E-215, K-204, K-220, S-207, S-215 , A-10R, A-13P, NC-203, NC-207 (manufactured by NOF Corporation), Emulgen 106, 108, 707, 709, A-90, A-60 (manufactured by Kao Corporation), Floren G-70, D-90 (manufactured by Kyoeisha Chemical Co., Ltd.), Poem J-0081HV (manufactured by Riken Vitamin Co., Ltd.), Adekatol NP-620, NP-650, NP-660, NP-675, NP-683, NP-686, Adekacol CS-141E, TS-230E (manufactured by Adeka Co., Ltd.), etc., Sorgen 30V, 40, TW-20, TW-80, Noigen CX-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc. exemplified.

Surfactants are not limited to those described above, and anionic, cationic, amphoteric or nonionic surfactants may be used, and may be appropriately selected according to the purpose of addition.

(Method for producing ink composition)
The method for producing an aqueous ink composition or a solvent ink composition of the present embodiment comprises mixing a coloring material, a resin, and a solvent (water and/or organic solvent) to form an ink composition. A manufacturing method for manufacturing can be mentioned.

For example, a method of adding an organic solvent, water, a coloring material, a resin, a surfactant, and optionally other components, a method of adding a coloring material and a dispersant to a solvent containing water and an organic solvent, and After dispersing, a method of adding a resin, a surfactant and other components as necessary, a coloring material, a resin, a surfactant and, if necessary, a solvent containing water and an organic solvent. A method of dispersing the coloring material after adding the components and the like can be mentioned.

[2-3. Actinic energy ray-curable ink composition]
An active energy ray-curable ink composition is an ink composition containing an active energy ray-polymerizable compound. Active energy ray-polymerizable compounds are irradiated with electromagnetic waves such as far-ultraviolet rays, ultraviolet rays, near-ultraviolet rays, visible rays, infrared rays, X-rays, and gamma rays, as well as active energy rays such as electron beams, proton rays, and neutron beams. It is a compound with an ethylenically unsaturated double bond that is polymerized.

As the colorant contained in the active energy ray-curable ink composition, the same colorant as the colorant contained in the above-described water-based or solvent-based ink composition can be used.

(Active energy ray polymerizable compound)
Examples of active energy ray polymerizable compounds include monofunctional polymerizable compounds and polyfunctional polymerizable compounds. Monofunctional polymerizable compounds include tetrahydrofurfuryl acrylate (THFA), trimethylolpropane formal acrylate (CTFA), (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, (2 -methyl-2-isobutyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (cyclohexanespiro-2-(1,3-dioxolan-4-yl))methyl (meth)acrylate, alkylcycloalkyl Acrylates 4-t-butylcyclohexyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, γ-butyrolactone acrylate, cresol acrylate , 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, paracumylphenoxyethylene glycol acrylate, nonylphenoxypolyethylene Glycol acrylate, 1-adamantyl acrylate, cyclohexyl acrylate, 3-3-5-trimethylcyclohexane acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acryloylmorpholine, N-vinylcaprolactam, imide acrylate, isooctyl acrylate, tridecyl acrylate , lauryl acrylate, 2-hydroxyethyl acrylate, stearyl acrylate, isodecyl acrylate, caprolactone acrylate, methoxypolyethylene glycol acrylate, methoxypolypropylene glycol acrylate, 2-methoxyethyl acrylate, ethylcarbitol acrylate, 2-ethylhexyl acrylate, and these Acrylate with various modifications such as alkoxy modification and caprolactone modification may be mentioned, but is not limited to these.

Examples of polyfunctional polymerizable compounds include 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, and 2-vinyloxy (meth)acrylate. Propyl, 4-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 1-vinyloxymethylpropyl (meth)acrylate, 2-methyl-3-vinyl(meth)acrylate Roxypropyl, 1,1-dimethyl-2-vinyloxyethyl (meth)acrylate, 3-vinyloxybutyl (meth)acrylate, 1-methyl-2-vinyloxypropyl (meth)acrylate, 2-vinyloxybutyl (meth)acrylate , 6-vinyloxyhexyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, m-vinyloxymethylphenylmethyl (meth)acrylate, o-vinyloxymethylphenylmethyl (meth)acrylate , 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxy)propyl (meth)acrylate, (meth)acrylic acid 2 -(vinyloxyethoxy)isopropyl, 2-(vinyloxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxy (meth)acrylate ) ethyl (meth)acrylate, 2-(vinyloxyethoxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy) (meth)acrylate Ethyl, 2-(vinyloxyethoxyethoxy)propyl (meth)acrylate, 2-(vinyloxyethoxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyisopropoxyethoxy)propyl (meth)acrylate, ( 2-(vinyloxyisopropoxyisopropoxy)propyl meth)acrylate, 2-(vinyloxyethoxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyisopropoxy)isopropyl (meth)acrylate, (meth)acrylate 2-(vinyloxyisopropoxyethoxy)isopropyl acrylate, 2-(vinyloxyisopropoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, (meth)acrylic Acid 2-(vinyloxyethoxyethoxyethoxyethoxy)ethyl, (meth)acrylic acid 2-(isopropenoxyethoxy)ethyl, (meth)acrylic acid 2-(isopropenoxyethoxyethoxy)ethyl, (meth)acrylic acid 2 -(isopropenoxyethoxyethoxyethoxy)ethyl, 2-(isopropenoxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, polyethylene glycol monovinyl ether (meth)acrylate, polypropylene glycol monovinyl ether (meth)acrylate, 1 , 6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, polyalkylene glycol diacrylate, alkoxylated bisphenol A diacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, tetraethylene glycol diacrylate, dimethyloltricyclodecane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, glycerin triacrylate, and these (Meth)acrylates with different numbers of modifications, different types of modification, and different structures can be mentioned.

(Active energy ray polymerization initiator)
The active energy ray-curable ink composition may contain an active energy ray polymerization initiator, if necessary. Active energy rays are energy rays that can trigger a polymerization reaction of radicals, cations, anions, etc., and include light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X rays and γ rays, and electron rays. , proton beams, neutron beams, etc., but curing by ultraviolet irradiation is preferable from the viewpoints of curing speed, availability of irradiation equipment, price, and the like. The active energy ray polymerization initiator is not particularly limited as long as it accelerates the polymerization reaction of the compound having an ethylenically unsaturated double bond in the active energy ray-curable ink composition by irradiation with an active energy ray. A conventionally known active energy ray polymerization initiator can be used. Specific examples of active energy ray polymerization initiators include aromatic ketones including thioxanthone, α-aminoalkylphenones, α-hydroxyketones, acylphosphine oxides, aromatic onium salts, and organic peroxides. , thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

The amount of the active energy ray polymerization initiator may be an amount capable of appropriately initiating the polymerization reaction of the active energy ray polymerizable compound, and is preferably 1.0 parts by mass or more in 100 parts by mass of the ink composition. 0 parts by mass or more is more preferable. Also, it is preferably 20.0 parts by mass or less in 100 parts by mass of the ink composition. In addition, in the ink composition according to the present embodiment, the active energy ray polymerization initiator is not necessarily essential. For example, when an electron beam is used as the active energy ray, the active energy ray polymerization initiator may not be used. .

(dispersant)
The active energy ray-curable ink composition may contain a dispersant if necessary. Dispersants include, for example, polymeric dispersants. The main chain of this polymer dispersant is polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and the polymer dispersant has side chains such as amino groups, carboxyl groups, sulfone groups, hydroxyl groups, etc. or a salt thereof.

Preferred polymer dispersants are polyester-based dispersants, and specific examples include "Solsperse 33000", "Solsperse 32000", and "Solsperse 24000" manufactured by Nippon Lubrizol; "Disperbyk168" manufactured by BYK Chemie; "Ajisper PB821", "TEGO Dispers685" manufactured by Evonik Japan Co., Ltd., and the like.

(Other additives)
The active energy ray-curable ink composition may contain various additives such as plasticizers, polymerization inhibitors, light stabilizers, and antioxidants. The active energy ray-curable ink composition may contain water or an organic solvent, but preferably does not contain water or an organic solvent. An active energy ray-curable ink composition that does not contain water or an organic solvent can form a decorative layer without changing the shape transferred to the surface of the substrate.

(Method for producing active energy ray-curable ink composition)
The method for producing the active energy ray-curable ink composition is not particularly limited, and conventionally known methods can be used. The active energy ray-curable ink composition is dispersed with an active energy ray polymerizable compound, a dispersant, etc. using a disperser, and then, if necessary, an active energy ray polymerization initiator, a leveling agent, etc. are added. The mixture is uniformly stirred to obtain a mixture, and then an organic resin filler is added and the mixture is filtered through a filter to obtain an ink composition.

<3. Laminate>
A laminate formed with a decorative layer, which is a coating film of the ink set according to the above embodiment, will be described. This laminate is a laminate obtained by laminating at least a base material and a decorative layer.

As such a laminate, for example, there is a decorative board that laminates an ink set coating film in order to impart a design appearance and surface durability to the surface of various substrates that are left standing indoors or outdoors (decorative). mentioned. The surfaces of various base materials include interior wall surfaces, floor surfaces, and ceiling surfaces of buildings, surfaces such as exterior walls and roofs of buildings, surfaces of furniture such as desks, chests of drawers, cupboards, doors, windows, etc. Door frames, window frames, sills, lintels, handrails, rims and other fittings and fixtures; home appliances such as television receivers, refrigerators and air conditioners; surfaces of office equipment such as copiers; Surfaces of interiors or exteriors of vehicles such as vehicles, railroad vehicles, ships, and aircraft can be used.

In addition to the above-mentioned decorative board, the laminated body mainly includes books such as magazines, books, and publications that have a decorative layer containing images such as letters, numbers, drawings, and photographs on various substrates. , various containers such as bottles, cans, packaging materials, commercial printed materials such as advertisements, signboards, leaflets, catalogs, sample books, instruction manuals, posters, forms, passbooks, slips, office entry forms, etc. It may be a so-called business form, a menu, a menu, a price tag, a product label, or the like.

[Base material]
The substrate is not particularly limited, and either an absorbent substrate or a non-absorbent substrate can be used. Specifically, flat objects such as films, sheets, or plates containing paper, resin, woven or non-woven fabric (fabric), metal, wood, leather, non-metallic inorganic materials, etc., or three-dimensional objects of various shapes etc. can be used.

As paper, paper such as fine paper, medium quality paper, tissue paper, titanium paper, kraft paper, linter paper, parchment paper, glassine paper, parchment paper, glassine paper, parchment paper, coated paper, art paper, and cast paper, which are used for various known applications. , lightweight coated paper, coated paper coated with various coating films such as lightly coated paper, or mixed paper made by mixing these papers with glass fiber or resin fiber, resins such as rubber latex and acrylic resin are added to these papers. Impregnated resin-impregnated paper or the like can be used. Paper having a basis weight of about 20 g/m ² or more and 200 g/m ² or less can be used.

As the woven fabric or non-woven fabric (fabric), for example, natural fibers such as cotton, hemp, and silk, synthetic resins such as polyester resins, polyamide resins and acrylic resins, or fibers containing inorganic materials such as glass and carbon are used. can use things.

Examples of resins include olefin resins such as polyethylene, polypropylene, ethylene-propylene-butene copolymers and olefin thermoplastic elastomers, and acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and methyl methacrylate-butyl methacrylate copolymers. Resins, vinyl chloride resins such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, polyvinylidene chloride, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid- Isophthalic acid copolymer, terephthalic acid-ethylene glycol-1,4 cyclohexanedimethanol copolymer, polyester resins such as various polyester thermoplastic elastomers, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer Styrene resins such as coalescence (ABS), polyisoprene, natural rubber, synthetic rubbers such as ethylene propylene rubber (EPR) and chloroprene rubber, urethane resins, cellulose resins, polycarbonate resins, polyamide resins, polyimide resins etc. can be used.

Examples of metals that can be used include aluminum, iron, copper, tin, titanium, and alloys containing these metals (eg, brass, bronze, duralumin, carbon steel, stainless steel).

As the wood, for example, a veneer of wood such as cedar, pine, cypress, oak, oak, zelkova, teak, lauan, plywood, laminated wood, particle board, medium density fiber board (MDF), etc. can be used. can.

Natural stone materials such as granite and limestone, ceramics such as cement, calcium silicate, gypsum, glass and ceramics can be used as the non-metallic inorganic material.

The base materials of the various materials listed above may be configured as a single layer body made of only one kind of material, or two or more different materials, as required, regardless of whether they are flat objects or three-dimensional objects. It may be configured as a laminated body of each other, and may be appropriately selected in consideration of various viewpoints such as usage, required performance, and product price. Examples of laminates include a laminate of a polyvinyl chloride sheet and an acrylic resin sheet, a laminate of an aluminum plate and an acrylic resin sheet, and a vinyl chloride resin on the surface of an iron or iron alloy plate. , a laminate with a layer of melamine resin or polyester resin, a laminate with the surface of a three-dimensional wood object covered with a urethane resin sheet, and a three-dimensional object surface of acrylonitrile-butadiene-styrene copolymer covered with a polycarbonate resin sheet and a laminate obtained by coating the surface of paper with a vinyl chloride resin or an olefin resin.

In the case of a flat substrate, the thickness can be usually about 20 μm or more and 10000 μm (1 cm) or less. In the case of three-dimensional objects, various three-dimensional shapes can be selected and applied according to the application.

In this specification, words such as film, sheet, and plate are used as flat objects, but these are generally used to mean, among objects having a flat surface, plate, plate They are used in the order of sheet and film, and are used in this specification as well. However, in the present specification, such proper usage has no technical meaning, so these terms can be used by replacing shall be interpreted in the same way.

Moreover, the various substrates listed above may be appropriately colored in accordance with the design to be expressed. Coloring refers to applying a desired color to at least the surface of the base material on which the decorative layer is formed. When coloring the base material, a coloring agent such as a pigment or a dye is added and/or dyed to the base material itself by a known method, or the surface of the base material is coated, solidly printed, vapor-deposited, plated, or the like. It can be carried out by a method such as laminating a colored layer by a method.

When obtaining a decorative board as a laminate, as a representative example, titanium paper used as a recording base material for thermosetting resin decorative boards can be used as the base material. A decorative board is a surface of various adherends such as buildings, furniture, fixtures, and fixtures, which is exposed to the outside during use and is visible to the public. It is a laminate. The desired design appearance is, for example, the design of the same wood grain design as that of the surface of the natural wooden board.

When titanium paper is used as the base material, it is preferable to use an aqueous ink composition containing water as the main component of the solvent. In the case of an ink composition containing water as a main component, in the step of impregnating titanium paper on which a decorative layer is laminated with an uncured composition of a liquid thermosetting resin, More of the air present will be replaced by the liquid composition. As a result, during the molding of the thermosetting resin decorative board and the heating process after molding, it is possible to effectively remove the small spot-like swellings and dents (blister) caused by the thermal expansion of the residual air between the fibers. can be suppressed. In particular, when the uncured composition contains water as a solvent or dispersion medium, blistering can be more effectively suppressed.

Furthermore, since the ink composition containing water as the main component has low permeability to the recording base material for the decorative board (printing base material for the decorative board), the ink composition can The permeation to the surface (surface opposite to the side) is suppressed, and strike-through can be suppressed more effectively.

Here, examples of the thermosetting resin used for the thermosetting resin decorative board include melamine resin, diallyl phthalate resin, unsaturated polyester resin, epoxy resin, urethane resin, and the like.

Although the decorative laminate has been described as an example of the laminate, the ink set according to the above-described embodiment is not limited to the use for forming the decorative layer of the decorative laminate.

[Decoration layer]
The decorative layer is formed by volatilizing water or an organic solvent from at least one ink composition containing magenta or yellow ink contained in the above ink set, or by polymerizing an active energy ray-polymerizable compound. It is a layer made of a coating film of an ink set.

The decorative layer has a desired design appearance when viewed from above, that is, when the laminate is observed from the thickness direction (which is also the normal direction of the decorative layer). Such design appearances include, for example, patterns on the surface of natural wood boards such as cedar, pine, and zelkova, i.e., wood grain patterns, patterns on the surface of natural stone materials such as granite and marble, i.e., stone patterns, and threads of various fibers. Patterns on the surface of woven fabrics woven or knitted from empty, dyed or embroidered in various colors and patterns as necessary, i.e. texture patterns, patterns on the surface of natural leather, i.e. leather grains So-called abstract patterns such as a (leather tie) pattern, floral pattern, polka dot pattern, checkered pattern, striped pattern, thunder pattern, arabesque pattern, and various geometric patterns can be mentioned.

By using an ink set in which the hue distance D and the hue angle H are specified, the decorative layer has a wide range of color expressiveness. In addition, since the two types of ink compositions, magenta ink and yellow ink, broaden the color expression, it is possible to suppress a decrease in chroma.

Moreover, when the laminate is a decorative board, the decorative layer may be required to have weather resistance because it may be left standing indoors or outdoors for a long time. When this laminate is a decorative board, from the viewpoint of imparting weather resistance to the decorative layer, the magenta ink and yellow ink of the ink set forming the decorative layer are C.I. I. C.I. Pigment Violet 19 was used as a yellow colorant contained in the yellow ink. I. Pigment Yellow 110 is particularly preferred.

Although the layer thickness (dry state) of the decorative layer is not particularly limited, it is preferably 0.5 μm or more, more preferably 3 μm or more. Although the upper limit of the layer thickness of the decorative layer is not particularly limited, it is preferably 100 μm or less, more preferably 50 μm or less, from the viewpoint of productivity.

The decorative layer may contain coloring pigments, coloring dyes, light stabilizers, ultraviolet absorbers, radical scavengers and the like. Examples of the coloring pigment include organic pigments and inorganic pigments, and inorganic pigments may be included from the viewpoint of weather resistance in the decorative layer.

[Surface protective layer]
In this laminate, a transparent surface protective layer may be further laminated on the surface of the decorative layer, if necessary. The surface protective layer can be formed by laminating a resin layer, applying a coating film, or laminating a resin layer and applying a coating film. In any case, the surface protective layer may have transparency to the extent that the decorative layer can be seen through the layer, and may be either colorless transparent or colored transparent. .

The resin layer used for the surface protective layer can be appropriately selected from the resins exemplified above in the examples of the base material.

In the case of coating of a coating film, for example, known thermosetting resins (one-component curing type or two-component curing type) such as thermosetting urethane resin, thermosetting polyester resin, epoxy resin, melamine resin, etc. , known ionizing radiation-curable resins such as acrylates, epoxies, and unsaturated polyesters that are crosslinked or polymerized by irradiation with ionizing radiation such as ultraviolet rays and electron beams. The thickness of the coating film can usually be about 1 μm or more and 100 μm or less (film thickness after curing).

In addition, in combination with the base material and the decorative layer, further coating on the decorative layer, lamination with other base materials, shaping by embossing, etc., resin impregnation, heat treatment, It can also be used for various purposes after being subjected to processing and treatment such as pressure treatment, cutting or cutting into desired shapes and sizes, and formation of pressure-sensitive adhesive or adhesive layers. Applications include various laminates such as the above-described decorative board.

<4. Recording method>

Examples of the recording method for transferring the ink composition contained in the ink set to the surface of the substrate include an inkjet method, an offset method, a gravure method, a spray method, a brush coating method, and the like. A recording method in which ink is transferred (discharged) by an ink jet method is preferable in that it can be applied to a small lot of various products. In this specification, the term "on the base material" includes both the mode of forming directly on the surface of the base material and the mode of forming on the surface of the base material via another layer such as a primer layer.

There are no particular restrictions on the recording method for ejecting ink by an ink jet system, but conventionally known systems such as a piezo system, a thermal system, and an electrostatic system can be mentioned. The inkjet head provided in the printing apparatus is not particularly limited, and may be a serial head or a line head.

<5. Method for producing laminate (printed matter)>
A laminate (printed matter) can be produced using the ink composition of the present embodiment. For example, a method for producing a laminate (printed matter) including a step of discharging onto the surface of a base material by the inkjet method described above can be mentioned.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these descriptions.

<Production of ink composition>
Each material (pigment (3 parts by mass or 8 parts by mass), resin (dispersant (0.5 parts by mass or 1.5 parts by mass), binder resin (5 parts by mass)), 1,3-pentanediol (35 parts by mass) parts), Dynol 604 (0.5 parts by mass), water (56 parts by mass or 50 parts by mass so that the total ink composition is 100 parts by mass))), and 1 at room temperature (20 to 25 ° C.) Stirred for an hour. After that, it was confirmed that there was no undissolved residue. Thereafter, filtration was performed using a membrane filter to prepare yellow ink and magenta ink.

<Measurement of single perceptual chromaticity index>
The perceptual chromaticity index was measured for the yellow ink and magenta ink prepared as described above. Specifically, yellow ink and magenta ink are ejected onto a substrate (Photofinish Glossy Premium, manufactured by FUJIFILM) by an inkjet method (600 x 600 dpi, 12 pl, recording pattern (printing pattern) of 100% ink composition). A coating film (decorative layer) was formed by , and the coating film (decorative layer) was measured using X-Rite eXact (manufactured by X-Rite Co., Ltd.) under the conditions of a D50 light source and a 2° viewing angle. Table 1 shows the measurement results.

<Weather resistance test>
A weather resistance test was performed on the printed matter (laminate) produced as described above. Specifically, a test was conducted in accordance with JIS K 7350-2, and evaluation was made based on changes in appearance after exposure to a xenon arc weatherometer for 500 hours. Table 1 shows the evaluation results.

Specifically, the L ^* a ^* b ^* values of the cured film before and after the weather resistance test were measured in the same manner as the measurement of the perceptual color index. When the difference in L ^* before and after the test is ΔL ^* , the difference in a ^* before and after the test is Δa ^* , and the difference in b ^* before and after the test is Δb ^* , ΔE = [(ΔL ^* )2+(Δa ^* )2+ Evaluation was made by ΔE calculated by (Δb ^* )2] 1/2.

(Evaluation criteria)
○: ΔE after 500h exposure is less than 5 △: ΔE after 500h exposure is 5 or more and less than 10 ×: ΔE after 500h exposure is 10 or more

In Table 1, "PY110" means C.I. I. Pigment Yellow 110.

In Table 1, "PY83" means C.I. I. Pigment Yellow 83.

In Table 1, "PY155" means C.I. I. Pigment Yellow 155.

In Table 1, "PY138" means C.I. I. Pigment Yellow 138.

In Table 1, "PV19" means C.I. I. Pigment Violet 19.

In Table 1, "PR122" means C.I. I. Pigment Red 122.

In Table 1, "PR177" means C.I. I. Pigment Red 177.

From Table 1, the hue distance D of the coating film prepared with the yellow inks 1-1, 1-2, 2-1, and 2-2 is 105 or more, the hue angle H is 70° or more and 85° or less, and magenta It can be seen that the hue distance D of the coating films produced from the inks 1-1, 1-2, 2-1, and 2-2 is 73 or more and the hue angle H is -20° or more and 25° or less.

<Measurement of mixed perceptual chromaticity index>
A mixed color coating film was prepared using each of the yellow ink, magenta ink and cyan ink (C.I. Pigment Blue 15:3, cyan ink with a pigment concentration of 4.5%) prepared above, and similarly the perceptual chromaticity index was measured.

Specifically, (1) yellow ink: magenta ink = 1:1, (2) yellow ink: cyan ink = 1:1, (3) magenta ink: cyan ink = 1:1. Seed coatings were prepared and the perceptual color indices a ^* and b ^* were determined. Then, a ^* and b ^* of a total of six points of yellow, magenta, cyan, and the three mixed colors were connected in the CIELAB space, and the area in the range of 0≦a ^* and 0≦b ^* was obtained. Table 2 shows the measurement results. It should be noted that the larger the area, the wider the range of 0≦a ^* and 0≦b ^* , the wider the color representation of the ink set.

Furthermore, the printed matter (laminate) produced as described above was subjected to a weather resistance test in the same manner as described above. Table 2 shows the evaluation results.

From Table 2, yellow inks 1-1, 1-2, 2-1, 2-2, magenta inks 1-1, 1-2, 2-1, 1-1, 1-2, 2-1 and The area in the range of 0 ≤ a ^* and 0 ≤ b ^* obtained from three types of coating films prepared using the ink sets of Examples 1 to 8 containing 2-2 is the area of Comparative Examples 1 to 10. It can be seen that it is wider than the ink set. As a result, it was confirmed that the ink set of the present invention has a wide range of color expression, particularly within the range of 0≦a ^* and 0≦b ^* .

Claims (7)

a yellow ink containing a yellow pigment;
a magenta ink containing a magenta pigment;
contains
The yellow pigment is C.I. I. Contains pigment yellow 110,
The magenta pigment is C.I. I. Contains Pigment Violet 19,
Hue distance D = √(a ^* ^2+b ^* ^ calculated from perceptual chromaticity indices a ^* and b ^* defined in CIELAB space in a yellow coating film formed by applying the yellow ink to a substrate 2) is 105 or more, and the hue angle H=tan ⁻¹ (b ^* /a ^* ) calculated from the perceptual chromaticity indices a ^* and b ^* is 70° or more and 85° or less;
Hue distance D = √(a ^* ^2+b ^* ^ calculated from perceptual chromaticity indices a ^* and b ^* defined in CIELAB space in a magenta-based coating film formed by applying the magenta ink to a substrate 2) is 73 or more, and the hue angle H = tan ^-1 (b ^* / a ^* ) calculated from the perceptual chromaticity indices a ^* and b * is -20 ° or more ^and 25 ° or less , An ink set used in manufacturing . 2. The ink set according to claim 1, wherein the yellow pigment contained in the yellow ink is an isoindolinone pigment. The content of the yellow pigment contained in the yellow ink is 2.0 parts by mass or more and 15.0 parts by mass or less per 100 parts by mass of the yellow ink, and the content of the magenta pigment contained in the magenta ink is magenta ink. 3. The ink set according to claim 1, wherein the amount is 2.0 parts by mass or more and 15.0 parts by mass or less in 100 parts by mass. 4. The ink set according to any one of claims 1 to 3, which is used in an inkjet system. 5. A laminate having a decorative layer, which is a coating film containing at least one of yellow ink and magenta ink contained in the ink set according to claim 1 or 4, formed on a base material. 5. A method for producing a laminate, wherein at least one of the yellow ink and the magenta ink contained in the ink set according to claim 1 is ejected onto the surface of a substrate by an inkjet method. A recording method comprising ejecting at least one of a yellow ink and a magenta ink contained in the ink set according to claim 1 onto the surface of a substrate by an inkjet method.