WO2019103088A1 - Nonaqueous inkjet ink, printed material and method for producing printed material - Google Patents

Abstract

A nonaqueous inkjet ink which contains a colorant, a resin and an organic solvent, and which is configured such that: the colorant contains a dye and a pigment; the content of the dye is 3.0-9.0% by mass; the content of the pigment is 1.0-8.0% by mass; and water is not contained therein, or in cases where water is contained therein, the water content is less than 10% by mass.

Description

Non-aqueous inkjet ink, printed matter and method of producing printed matter

The present invention relates to a non-aqueous inkjet ink, a print, and a method of producing the print. More specifically, the present invention is a non-water-based inkjet ink, printed matter and printed matter which are excellent in ejection stability at the time of ink jet printing, and can provide prints excellent in abrasion resistance, water resistance and weather resistance. The manufacturing method of

Conventionally, there is known a technique for performing ink jet printing using an ink containing a pigment on a non-water absorbing substrate. However, the pigment does not have sufficient fixability to the substrate, and may peel off due to friction. Therefore, inks have been proposed for improving the friction resistance of printed matter (for example, Patent Documents 1 to 3).

JP, 2016-163986, A JP 2015-124458 A JP 7-109430 A

In the ink set described in Patent Document 1, after the reaction liquid is fixed to the substrate, a pigment is applied to form an image. However, this ink set is still insufficient in abrasion resistance. Therefore, in the printed matter obtained by this ink set, the image formed by the pigment peels off, the substrate is exposed, and the appearance is likely to be significantly impaired. Further, the ink described in Patent Document 2 contains a dye. However, this ink set tends to have poor weatherability and water resistance of the resulting printed matter. In addition, Patent Document 2 does not disclose that a non-water-absorptive substrate is used to produce a print. Furthermore, it is preferable to add water to the recording liquid described in Patent Document 3, and the resulting printed matter tends to have poor weatherability and water resistance. Also, the printed matter is not sufficiently resistant to friction.

The present invention has been made to solve the above-mentioned problems, and is a non-water-based material which is excellent in ejection stability at the time of ink jet printing and which is excellent in abrasion resistance, water resistance and weather resistance. An object of the present invention is to provide a method for producing an inkjet ink, a print and a print.

As a result of intensive investigations on the method of improving the water resistance and the weather resistance while improving the abrasion resistance of the printed matter obtained, the present inventor combined use of a specific amount of dye and pigment together with the addition of water. It was found that by suppressing the amount and blending the resin and the organic solvent, it is possible to improve the abrasion resistance of the obtained printed matter while improving the water resistance and the weather resistance, and completed the present invention. .

A non-aqueous ink jet ink according to one aspect of the present invention for solving the above problems comprises a coloring material, a resin and an organic solvent, wherein the coloring material contains a dye and a pigment, and the content of the dye is 3. 0 to 9.0% by mass, the content of the pigment is 1.0 to 8.0% by mass, or the content of water is less than 10% by mass when it contains no water or contains water It is a non-aqueous ink jet ink.

Further, the printed matter according to one aspect of the present invention for solving the above-mentioned problems comprises: a non-water-absorptive substrate; and an inkjet layer formed on the substrate by a non-aqueous inkjet ink containing a coloring material containing a dye and a pigment. And the ink jet layer is provided on the substrate and is a printed matter including a dye layer containing the dye and a pigment layer covering the dye layer and containing the pigment.

Furthermore, the printed matter according to one aspect of the present invention for solving the above-mentioned problems is a printed matter including a non-water-absorptive substrate and an inkjet layer formed on the substrate by the non-aqueous inkjet ink.

Further, a method for producing a printed matter according to one aspect of the present invention for solving the above problems is a method for producing a printed matter, including the step of applying the non-aqueous ink jet ink to a non-water-absorptive substrate by an inkjet method. is there.

<Non-aqueous inkjet ink>
A non-aqueous ink jet ink (hereinafter also referred to as an ink) according to an embodiment of the present invention contains a coloring material, a resin, and an organic solvent. Color materials include dyes and pigments. The content of the dye is 3.0 to 9.0% by mass, and the content of the pigment is 1.0 to 8.0% by mass. The ink does not contain water or has a water content of less than 10% by mass when it contains water. Such an ink is excellent in ejection stability, and a print having excellent abrasion resistance, water resistance and weather resistance can be obtained. Each of these will be described below.

(Color material)
Color materials include dyes and pigments. An appropriate combination of dye and pigment is selected according to the desired ink color (yellow, magenta, cyan, black, etc.). The color of the dye and the pigment is preferably similar so that the exposed surface is less noticeable when the substrate dyed with the dye is exposed by peeling off a part of the pigment in the obtained printed matter .

Dye The dye may be blended with various oil-soluble dyes, disperse dyes, acid dyes, reactive dyes, cationic dyes, direct dyes and the like. These may be used in combination. Among these, the dye preferably contains an oil-soluble dye or a disperse dye, and more preferably an oil-soluble dye or a disperse dye that dissolves in an organic solvent described later, from the viewpoint of excellent water resistance of the printed matter obtained. .

The oil-soluble dyes are, for example, azos, anthraquinones, indigoids, phthalocyanines, carboniums, quinone imines, methines, xanthenes, nitros, nitroso and the like. The disperse dyes are, for example, azo dyes, benzene azo dyes, disazo dyes, anthraquinone dyes, coumarin dyes, quinoline dyes, nitro dyes and the like. The acid dyes are, for example, benzene azo type, pyrazolone azo type, acetoacetic acid anilide azo type, naphthalene derivative azo type, j acid azo type, γ acid azo type, H acid azo type, H acid azo type, K acid azo type, anthraquinone type, quinizarin type, metal It is a complex salt type etc. The reactive dye is, for example, azo type, metal-containing azo type, anthraquinone type, phthalocyanine type, formazalin type, oxazine type, and the like. The direct dyes are, for example, diaminodiphenylamine azo type, stilbenzoazo type, dij acid azo type, polyazo type, benzidine type, tolidine type, dianisidine azo type and the like. These may be used in combination.

The content of the dye in the ink may be 3.0% by mass or more, and preferably 3.5% by mass or more. The content of the dye in the ink may be 9.0% by mass or less, and preferably 8.0% by mass or less. When the content of the dye is less than 3.0% by mass, the printed material obtained is likely to have a poor appearance when the substrate is not sufficiently dyed and the pigment is peeled off. On the other hand, when the content of the dye exceeds 9.0% by mass, the dye may be difficult to dissolve in the solvent. In this case, the substrate is not sufficiently dyed, the water resistance is poor, and bleeding easily occurs.

Pigment The pigment may be blended with various inorganic pigments or organic pigments. Inorganic pigments include oxides, composite oxides, hydroxides, sulfides, ferrocyanides, chromates, carbonates, silicates, phosphates, carbons (carbon black), metals Powders etc. are illustrated. Organic pigments include nitroso, dyed lakes, azo lakes, insoluble azos, monoazos, disazos, condensed azos, benzimidazolones, phthalocyanines, anthraquinones, perylenes, quinacridones, dioxazines, and iso Indolines, azomethines, pyrrolopyrroles and the like are exemplified. These may be used in combination.

The pigment of the present embodiment is preferably an organic pigment from the viewpoint of excellent color developability of the resulting printed matter. Moreover, an inorganic pigment may be used as a pigment, in order to further improve the weather resistance of the obtained printed matter.

The pigment may also be dispersed in various dispersants. The pigment of the present embodiment is more preferably a pigment dispersed by a polymer dispersant, from the viewpoint that the water repellency of the resulting printed matter is more excellent.

The polymeric dispersant is not particularly limited. As an example, the polymer dispersant is polyoxyalkylene polyalkylene polyamine, vinyl polymer or copolymer, acrylic polymer or copolymer, polyester, polyamide, polyimide, polyurethane, amino polymer and the like. Polymeric dispersants may be used in combination.

The acid value of the polymer dispersant is preferably 5 mg KOH / g or more, and more preferably 15 mg KOH / g or more. The amine value of the polymer dispersant is preferably 15 mg KOH / g or more, more preferably 25 mg KOH / g or more. These polymer dispersants having an acid value and an amine value have excellent adsorptivity to pigments. In the present embodiment, the acid value represents the acid value per 1 g of the solid content of the dispersant, and can be calculated by potentiometric titration according to JIS K 0070. In addition, the amine value represents the amine value per 1 g of solid content of the dispersant, and by using a 0.1 mol / L aqueous hydrochloric acid solution, the value calculated by the potentiometric titration method is converted to the equivalent of potassium hydroxide. It can be calculated.

The content of the pigment in the ink may be 1.0% by mass or more, preferably 1.5% by mass or more, and more preferably 2.0% by mass or more. The content of the pigment in the ink may be 8.0% by mass or less, and preferably 6.0% by mass or less. When the content of the pigment is less than 1.0% by mass, sufficient coloring tends not to be given. On the other hand, when the content of the pigment exceeds 8.0% by mass, the printed matter obtained tends to have inferior ejection stability.

With respect to the proportions of dye and pigment, the dye / pigment is preferably 0.3 or more, and more preferably 1.0 or more. The dye / pigment is preferably 9.0 or less, more preferably 6.0 or less, and still more preferably 5.0 or less. If the dye / pigment is less than 0.3, the resulting print is likely to have poor abrasion resistance. Moreover, the printed matter obtained is difficult to be sufficiently dyed by the dye and the appearance of the printed matter is likely to be inferior when the pigment is peeled off. On the other hand, when the dye / pigment exceeds 9.0, the resulting printed matter is apt to bleed and the water resistance of the printed matter tends to be reduced.

(resin)
The resin is blended to adjust the viscosity of the ink to properly hold the pigment, or to adjust the ejection stability of the ink during ink jet printing.

The type of resin is not particularly limited. As an example, the resin is a urethane resin, an acrylic resin, an acrylic urethane resin, a vinyl chloride-vinyl acetate copolymer resin, a polyvinyl acetal resin or the like. These resins may be used in combination.

The urethane resin is, for example, a polycarbonate polyurethane resin, a polyether polyurethane resin, a polyester polyurethane resin and the like.

The acrylic resin is a polymer of acrylic ester (acrylate) or methacrylic ester (methacrylate), for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethyl acrylate Alkyl acrylates such as hexyl; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, methacrylic acid alkyl esters such as 2-ethylhexyl methacrylate; 2-hydroxyethyl acrylate 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate and other hydroxy group-containing acrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylate It is a hydroxy group-containing polymer like methacrylic acid esters such as Le acid 4-hydroxybutyl.

The acrylic urethane resin may, for example, be an acrylic urethane resin obtained by reacting a methacrylic acid ester (for example, methyl methacrylate), a hydroxyethyl methacrylate copolymer and a polyisocyanate. Examples of the polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and the like.

Examples of the vinyl chloride-vinyl acetate copolymer resin include those having a vinyl chloride component content of 79 to 97% by mass. The vinyl chloride-vinyl acetate copolymer resin may contain other copolymerization components (eg, vinyl alcohol, maleic acid, etc.) within the range that does not inhibit the effects of the ink of the present embodiment.

The content of the resin in the ink is preferably 1% by mass or more, and more preferably 2% by mass or more. Further, the content of the resin in the ink is preferably 10% by mass or less, and more preferably 8% by mass or less. When the content of the resin is less than 1% by mass, the pigment is hardly retained sufficiently in the ink. As a result, the resulting printed matter tends to have poor abrasion resistance. On the other hand, when the content of the resin exceeds 10% by mass, the viscosity of the ink becomes high, and the ejection stability at the time of inkjet printing tends to be reduced.

(Organic solvent)
The organic solvent is a liquid component for appropriately dispersing or dissolving the above components in the ink. The organic solvent is not particularly limited. As an example, the organic solvent is a lactone type organic solvent, a ketone type organic solvent, a glycol ether type organic solvent, an acetate type organic solvent, a carbonate type organic solvent or the like. Among these, the organic solvent preferably contains a glycol ether-based organic solvent, an acetate-based organic solvent or a carbonate-based organic solvent. Both glycol ether organic solvents and acetate organic solvents have low viscosity and relatively high boiling point. Therefore, the drying property of the ink containing these as a solvent is further improved, and the ejection stability at the time of inkjet printing is more excellent. Moreover, the said dye is easy to be melt | dissolved in the organic solvent by containing such an organic solvent. As a result, the resulting printed matter is such that the substrate is easily dyed by the dye and the appearance is less likely to be impaired. In addition, these organic solvents are more attacking to the ink jet head material (the property of dissolving materials such as an adhesive used in the head; also referred to as solubility, permeability, and swelling), so It can be used stably for a long time.

Examples of lactone organic solvents include γ-butyrolactone, γ-valerolactone, δ-valerolactone and the like. Examples of ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl isoamyl ketone, diisobutyyl ketone, methyl hexyl ketone, isophorone and the like.

Examples of glycol ether organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono (iso) propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- n-butyl ether, triethylene glycol monomer Ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene glycol mono-n-butyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono- n-Butyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether Triethylene glycol butyl methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether and the like.

Acetate-based organic solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-sec-butyl ether acetate Ethylene glycol monoisobutyl ether acetate, ethylene glycol mono-tert-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol Glycol mono-n-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono-tert-butyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-ethoxy Butyl acetate, 3-methyl-3-propoxybutyl acetate, 3-methyl-3-isopropoxybutyl acetate, 3-methyl-3-n-butoxyethyl acetate, 3-methyl-3-isobutoxybutyl acetate, 3- Alkylene glycol monoalkyl ether acetates such as methyl 3-sec-butoxycyclohexyl acetate, 3-methyl-3-tert-butoxycyclohexyl acetate, ethylene glycol Call diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, tripropylene glycol diacetate, and the like.

Among the above, the organic solvent preferably has a boiling point of 155 ° C. or more, more preferably 170 ° C. or more. The boiling point of the organic solvent is preferably 300 ° C. or less, more preferably 250 ° C. or less. When the boiling point is in the above range, the ink is more improved in the drying property, and the ejection stability at the time of ink jet printing is more excellent. Further, by using an ink containing such an organic solvent, it is easy to obtain a clear printed matter with less bleeding. When the boiling point of the solvent is less than 150 ° C., the ink tends to be dried in the vicinity of the head nozzle, and the ejection stability tends to be lowered. On the other hand, when the boiling point of the solvent exceeds 300 ° C., the ink is difficult to dry, and the drying process at the time of formation of a print tends to take a long time. Also, the printed matter obtained tends to blur the image.

The organic solvents may be used alone or in combination. In the case where an organic solvent is used in combination, for example, when a solvent having a strong attack property and a solvent having a weak attack property are used in combination with the substrate, the ink is excellent in the dyeability of the substrate and damages the inkjet head. It is difficult to make prints stably for a long time.

The content of the organic solvent is not particularly limited. If an example is given, it is preferable in an ink that it is 75 mass% or more, and it is more preferable that it is 80 mass% or more. The organic solvent is preferably 95% by mass or less, and more preferably 90% by mass or less in the ink. When the content of the organic solvent is less than 75% by mass, the viscosity of the ink tends to be high, and the discharge stability at the time of ink jet printing tends to be lowered. On the other hand, when the content of the organic solvent exceeds 95% by mass, the proportion of each component that can be added to the ink is low, and it may be difficult to obtain desired performance.

(Others)
The ink of the present embodiment is a non-aqueous ink. That is, the ink has a low water content, which is less than 10% by mass. The content of water may be less than 10% by mass, preferably less than 5% by mass, and more preferably less than 1% by mass. Also, water may not be included. Thereby, the printed matter obtained is excellent in water resistance.

(Optional ingredient)
The ink of the present embodiment may optionally contain optional components in addition to the components described above. Examples of optional components include crosslinking agents, wax agents, antifoaming agents, light resistance improvers, light stabilizers and the like.

· Crosslinking agent (hardening agent)
A crosslinking agent (curing agent) can be formulated to cure the ink. The curing agent is not particularly limited. Examples of the curing agent include isocyanate curing agents, blocked isocyanate curing agents, amine curing agents, acid anhydride curing agents, carbodiimide curing agents and the like. These may be used in combination. Among these, the curing agent preferably contains an isocyanate resin. Thereby, the printed matter obtained is more excellent in weather resistance.

As the isocyanate resin, any compound having two or more isocyanate groups in one molecule may be used, and any of general-purpose type, light yellowing type, non-yellowing type and the like can be used. Examples of the general-purpose type include tolylene diisocyanate (TDI), isocyanurate which is a trimer of TDI, 4,4-diphenylmethane diisocyanate (MDI), and polymeric diphenylmethane diisocyanate (polymeric MDI). Xylylenediamine (XDI) etc. are illustrated as a non-yellowing type. Examples of the non-yellowing type include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI and the like. Among these, the curing agent preferably contains a non-yellowing blocked isocyanate, and more preferably a non-yellowing blocked isocyanate having an isocyanurate structure. By blending such a curing agent, the ink is more excellent in curability. Moreover, the printed matter obtained by using such an ink is further excellent in a weather resistance. Therefore, the printed matter tends to exhibit the desired color for a longer period of time.

When the curing agent is contained, the content of the curing agent is not uniquely determined because it varies depending on the addition amount of the resin and the hydroxyl value. As an example, the content of the curing agent in the ink is preferably 0.1% by mass or more, and more preferably 1% by mass or more. The content of the curing agent in the ink is preferably 20% by mass or less, and more preferably 10% by mass or less. When the content of the curing agent is less than 0.1% by mass, the resin does not react sufficiently, and the desired performance tends to be not obtained. On the other hand, when the content of the curing agent exceeds 20% by mass, excessive addition to the resin may occur, and the weather resistance of the resulting printed matter tends to decrease.

Waxing agent The waxing agent is appropriately blended to improve the slipperiness by reducing the surface resistance of the ink film to friction. The wax agent is not particularly limited. For example, the wax agent is a hydrocarbon such as paraffin wax, a higher alcohol such as cetyl alcohol, a higher fatty acid such as myristic acid, an animal wax such as beeswax, a vegetable wax such as carnauba, etc. Fatty acid alcohol esters and the like. These may be used in combination.

When the wax agent is contained, the content of the wax agent in the ink is preferably 0.5% by mass or more, and more preferably 2.0% by mass or more. The content of the wax agent is preferably 8.0% by mass or less in the ink. When the content of the wax agent is less than 0.5% by mass, the frictional property tends to be inferior because the slipperiness is inferior. On the other hand, when the content of the wax agent exceeds 8.0% by mass, when the coating layer is provided on the printing surface, the adhesion of the ink tends to decrease.

Antifoaming Agent The antifoaming agent is suitably blended to improve the ejection stability of the ink at the time of ink jet printing. Examples of the antifoaming agent include silicone antifoaming agents and polyether antifoaming agents. These may be used in combination. Among these, the antifoaming agent is preferably a silicone antifoaming agent from the viewpoint of easy diffusion and easily exhibiting an excellent antifoaming effect.

Examples of the silicone antifoaming agent include dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethyl polysiloxane), fluorosilicone oil and the like.

Examples of polyether antifoaming agents include di-t-amylphenoxyethanol, 3-heptyl cellosolve, nonyl cellosolve, 3-heptyl carbitol and the like.

When the antifoaming agent is blended, the content of the antifoaming agent is preferably 0.01% by mass or more in the ink, and more preferably 0.1% by mass or more. The content of the antifoaming agent in the ink is preferably 5% by mass or less, and more preferably 1% by mass or less. When the content of the antifoaming agent is less than 0.01% by mass, the effect as the antifoaming agent tends not to be sufficiently exhibited. On the other hand, when the content of the antifoaming agent exceeds 5% by mass, the ink tends to be expensive as well as the effect beyond this can not be obtained.

-Light resistance improver The light resistance improver is appropriately blended in order to delay the color fading. The light resistance improver is not particularly limited. For example, the light resistance improver is benzotriazole light resistance improver, benzophenone light resistance improver, triazine light resistance improver, cyanoacrylate light resistance improver, oxanilide light resistance improver, salicylate light resistance improver, formamidine These are various light resistance improvers such as a light resistance improver, a carbazide light resistance improver, a benzoate light resistance improver, a nickel complex light resistance improver, a hindered amine light resistance improver, and a cinnamate light resistance improver. These may be used in combination.

When the light resistance improver is contained, the content of the light resistance improver in the ink is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more. The content of the light resistance improver is preferably 2.0% by mass or less in the ink. When the content of the light resistance improver is less than 0.5% by mass, there is a tendency that a sufficient improvement in light resistance can not be obtained. On the other hand, when the content of the light resistance improver exceeds 2.0% by mass, the cost of the ink tends to increase.

Returning to the description of the entire ink, the viscosity of the ink is not particularly limited. The viscosity of the ink at 30 ° C. is preferably 5.0 mPa · s or more, more preferably 6.0 mPa · s or more. The viscosity of the ink is preferably 15.0 mPa · s or less at 30 ° C., and more preferably 12.0 mPa · s or less. When the viscosity is in the above range, the ink is excellent in ejection stability. When the viscosity is less than 5.0 mPa · s, the ink tends to have a reduced ejection stability at the time of ink jet printing. On the other hand, when the viscosity exceeds 15.0 mPa · s, the ink is not properly ejected from the head nozzle, and the ejection stability at the time of ink jet printing tends to be lowered. In the present embodiment, the viscosity can be measured using a B-type viscometer (TVB-20LT, manufactured by Toki Sangyo Co., Ltd.).

In addition, the method of adjusting a viscosity in the said range is not specifically limited. For example, the viscosity can be adjusted by the type and content of the resin used. The viscosity may be adjusted using a viscosity modifier such as a thickener, if necessary.

As described above, in the ink of the present embodiment, the substrate of the obtained printed matter is dyed with the dye by using the above-mentioned specific amounts of the dye and the pigment in combination, and then the pigment may be fixed on the substrate. Such printed matter is excellent in abrasion resistance, and even when a part of the pigment is peeled off, the substrate is simply exposed by exposing the substrate dyed with the dye. In comparison, the appearance is less likely to be lost. Further, the ink contains a resin and an organic solvent in addition to a coloring material containing a specific amount of the above-mentioned pigment and dye, and the amount of water is suppressed. As a result, the printed matter obtained is excellent in water resistance and weather resistance.

<Production method of printed matter>
The method for producing a printed matter according to an embodiment of the present invention includes the step of applying the above-described ink to a non-water-absorptive substrate by an inkjet method. In addition, the other process may be a process widely used when manufacturing the conventional printed matter.

The method for applying the ink to the substrate by the inkjet recording method is not particularly limited. Such methods include charge modulation method, micro dot method, charge injection control method, continuous method such as ink mist method, piezo method, pulse jet method, bubble jet (registered trademark) method, electrostatic suction method and the like. The demand system etc. are illustrated.

The substrate to which the ink has been applied is then dried. The drying conditions are not particularly limited. In one example, drying may be heat-treated at 50 to 250 ° C. for 1 to 60 minutes. Such drying can remove the organic solvent (and water, if water is included) in the ink. Drying is preferably performed at the same time or immediately after the ink is applied to the substrate in order to prevent ink bleeding.

According to the method for producing a print of the present embodiment, the substrate is dyed with a dye in the resulting print, and then the pigment is fixed on the substrate. As a result, the printed matter obtained is excellent in abrasion resistance, and even if some of the pigments are peeled off, the substrate is simply exposed by exposing the substrate dyed by the dye. Compared to the case, the appearance is less likely to be lost. Further, the non-aqueous ink jet ink to be used contains a resin and an organic solvent in addition to a coloring material containing a specific amount of the above-mentioned pigment and dye, and the amount of water is suppressed. As a result, the printed matter obtained is excellent in water resistance and weather resistance.

<Printed material>
First Embodiment
The printed matter according to one embodiment of the present invention includes a non-water-absorptive substrate, and an inkjet layer formed on the substrate by a non-aqueous inkjet ink containing a coloring material containing a dye and a pigment. The inkjet layer is provided on the substrate, and includes a dye layer containing a dye, and a pigment layer covering the dye layer and containing a pigment.

According to such a configuration, in the resulting print, the substrate is dyed with a dye, and then the pigment is fixed on the substrate. Such printed matter is excellent in abrasion resistance, and even when a part of the pigment is peeled off, the substrate is simply exposed by exposing the substrate dyed with the dye. In comparison, the appearance is less likely to be lost. Moreover, the compounding quantity of water is suppressed in the non-aqueous inkjet ink used. As a result, the printed matter is excellent in water resistance and weather resistance.

The non-water absorbing base is not particularly limited. In addition, such a non-water-absorptive substrate is imparted with non-water-absorptivity by treating the surface of the water-absorptive substrate (for example, by forming a resin layer described later on the substrate surface) It may be For example, the substrate is a steel plate, a metal plate such as aluminum or stainless steel, a plastic plate or film such as acrylic, polycarbonate, ABS, polypropylene, polyester, vinyl chloride or the like, a ceramic plate, concrete, wood, glass or the like. In addition, the base material includes cationic dyeable polyester (CDP) fiber, polyethylene terephthalate (PET) fiber, polybutylene terephthalate (PBT) fiber, polytrimethylene terephthalate (PTT) fiber, wholly aromatic polyester fiber, polylactic acid fiber, etc. Polyester fibers, acetate fibers, triacetate fibers, polyurethane fibers, nylon fibers, etc. or fabrics made of these composite fibers may be used. These may be suitably selected according to a use. When the substrate is a fabric, the fabric is preferably treated with a pretreatment agent before printing. As the pretreatment agent, water-soluble polymers, water-insoluble inert organic compounds, flame retardants, UV absorbers, reduction inhibitors, antioxidants, pH adjusters, hydrotropes, antifoaming agents, penetrants, microporous A forming agent etc. are illustrated. Examples of methods for applying these pretreatment agents to the fabric include a pad method, a spray method, an immersion method, a coating method, a laminating method, a gravure method, an inkjet method and the like.

In the present embodiment, “non-water-absorptive substrate” means that the substrate of 40 mm × 40 mm is immersed in normal temperature water for 3 days, and then the water absorptivity of the substrate is 15% or less. The base material which is

Moreover, the base material may have a resin layer on the surface. The resin layer is not particularly limited. As an example, the resin layer is a urethane resin, an acrylic resin, an acrylic urethane resin, a vinyl chloride resin or the like. As the urethane resin, acrylic resin, acrylic urethane resin and vinyl chloride resin, those described above in the embodiment of the ink may be used. By the resin layer being comprised by these resin, the ink is excellent in the dyeability of the surface of a base material.

In the printed matter of the present embodiment, the substrate is dyed with a dye by applying the above-described ink, and then the pigment is fixed on the substrate. Such printed matter is excellent in abrasion resistance, and even when a part of the pigment is peeled off, the substrate is simply exposed by exposing the substrate dyed with the dye. In comparison, the appearance is less likely to be lost. In addition, the amount of water used in the ink is reduced. As a result, the printed matter is excellent in water resistance and weather resistance.

More specifically, the printed matter of the present embodiment can achieve a color difference (ΔE) of less than 6.0 before and after a friction test described later. That is, the printed matter is excellent in adhesion between the substrate and the ink, and is excellent in abrasion resistance as well as water resistance and weather resistance. Therefore, the printed matter can be used in various applications using the above-mentioned substrate, and in the application, the desired color or image can be held for a long time.

Second Embodiment
The printed matter according to one embodiment of the present invention includes an ink jet layer formed on the non-water absorbing substrate by the above-described ink.

The non-water absorbing base is not particularly limited. As the non-water-absorptive substrate, the same one as described above in the first embodiment can be used.

In the printed matter of the present embodiment, the substrate is dyed with a dye by applying the above-described ink, and then the pigment is fixed on the substrate. Such printed matter is excellent in abrasion resistance, and even when a part of the pigment is peeled off, the substrate is simply exposed by exposing the substrate dyed with the dye. In comparison, the appearance is less likely to be lost. Further, the ink to be used contains a resin and an organic solvent in addition to a coloring material containing a specific amount of the above-mentioned pigment and dye, and the amount of water is suppressed. As a result, the printed matter is excellent in water resistance and weather resistance.

More specifically, the printed matter of the present embodiment can achieve a color difference (ΔE) of less than 6.0 before and after a friction test described later. That is, the printed matter is excellent in adhesion between the substrate and the ink, and is excellent in abrasion resistance as well as water resistance and weather resistance. Therefore, the printed matter can be used in various applications using the above-mentioned substrate, and in the application, the desired color or image can be held for a long time.

Heretofore, an embodiment of the present invention has been described. The present invention is not particularly limited to the above embodiment. The above-described embodiment mainly describes the invention having the following configuration.

(1) A coloring material, a resin, and an organic solvent, wherein the coloring material includes a dye and a pigment, the content of the dye is 3.0 to 9.0% by mass, and the content of the pigment is A non-aqueous inkjet ink, wherein the amount is 1.0 to 8.0% by mass, and the content of water when it does not contain water or when it contains water is less than 10% by mass.

According to such a configuration, in the non-aqueous ink jet ink, the substrate of the resulting printed matter is dyed with the dye, and then the pigment is fixed on the substrate, by using a specific amount of the dye and the pigment in combination. obtain. Such printed matter is excellent in abrasion resistance, and even when a part of the pigment is peeled off, the substrate is simply exposed by exposing the substrate dyed with the dye. In comparison, the appearance is less likely to be lost. Moreover, in addition to the coloring material containing the said pigment and dye of a specific amount, resin and the organic solvent are contained in the non-aqueous inkjet ink, and the compounding quantity of water is suppressed. As a result, the printed matter obtained is excellent in water resistance and weather resistance.

(2) The non-aqueous inkjet ink according to (1), wherein the dye contains an oil-soluble dye or a disperse dye and is soluble in the organic solvent.

According to such a configuration, the printed matter obtained is more excellent in water resistance.

(3) The non-aqueous inkjet ink according to (1) or (2), wherein the organic solvent has a boiling point of 155 ° C. or higher and contains a glycol ether organic solvent or a carbonate organic solvent.

According to such a configuration, the dye is easily dissolved in the organic solvent. As a result, the resulting printed matter is such that the substrate is easily dyed by the dye and the appearance is less likely to be impaired.

(4) The content of the resin is 1 to 10% by mass, and the resin is selected from the group consisting of a urethane resin, an acrylic resin, an acrylic urethane resin, a vinyl chloride-vinyl acetate copolymer resin and a polyvinyl acetal resin. The non-aqueous inkjet ink according to any one of (1) to (3), which comprises at least one selected from the group consisting of

According to such a configuration, the viscosity of the non-aqueous ink jet ink is appropriately adjusted, the pigment is easily held, and the ejection stability at the time of ink jet printing is more excellent.

(5) The non-aqueous inkjet ink according to any one of (1) to (4), wherein the content of the organic solvent is 75% by mass or more.

According to such a configuration, by containing 75% by mass or more of the organic solvent, the dye is sufficiently dissolved in the solvent, and the substrate is more easily dyed.

(6) A non-water absorbing substrate and an inkjet layer formed on the substrate by a non-aqueous inkjet ink containing a coloring material containing a dye and a pigment, the inkjet layer being provided on the substrate A printed matter comprising: a dye layer containing the dye; and a pigment layer covering the dye layer and containing the pigment.

According to such a configuration, in the resulting print, the substrate is dyed with a dye, and then the pigment is fixed on the substrate. Such printed matter is excellent in abrasion resistance, and even when a part of the pigment is peeled off, the substrate is simply exposed by exposing the substrate dyed with the dye. In comparison, the appearance is less likely to be lost. Moreover, the compounding quantity of water is suppressed in the non-aqueous inkjet ink used. As a result, the printed matter is excellent in water resistance and weather resistance.

(7) A printed matter comprising a non-water-absorptive substrate, and an inkjet layer formed on the substrate by the non-aqueous inkjet ink according to any one of (1) to (5).

According to such a configuration, in the resulting print, the substrate is dyed with a dye, and then the pigment is fixed on the substrate. Such printed matter is excellent in abrasion resistance, and even when a part of the pigment is peeled off, the substrate is simply exposed by exposing the substrate dyed with the dye. In comparison, the appearance is less likely to be lost. Further, the non-aqueous ink jet ink to be used contains a resin and an organic solvent in addition to a coloring material containing a specific amount of the above-mentioned pigment and dye, and the amount of water is suppressed. As a result, the printed matter is excellent in water resistance and weather resistance.

(8) The base material has a resin layer on the surface, and the resin layer is made of at least one selected from the group consisting of urethane resin, acrylic resin, acrylic urethane resin and vinyl chloride resin, (7) Printed matter described.

According to such a configuration, the organic solvent can swell the resin layer. As a result, the surface of the substrate is more susceptible to staining.

(9) A method for producing a printed matter, comprising the step of applying the non-aqueous ink jet ink according to any one of (1) to (5) to a non-water-absorptive substrate by an ink jet method.

According to such a configuration, the substrate is dyed with a dye in the resulting print, and then the pigment is fixed on the substrate. As a result, the printed matter obtained is excellent in abrasion resistance, and even if some of the pigments are peeled off, the substrate is simply exposed by exposing the substrate dyed by the dye. Compared to the case, the appearance is less likely to be lost. Further, the non-aqueous ink jet ink to be used contains a resin and an organic solvent in addition to a coloring material containing a specific amount of the above-mentioned pigment and dye, and the amount of water is suppressed. As a result, the printed matter obtained is excellent in water resistance and weather resistance.

Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited to these examples.

The raw materials used are shown below.
<Colorant>
(dye)
Product Name: NEO SUPER BLACK C-832: SOL. BLACK 27, Sold by Chuo Synthetic Chemical Industry Co., Ltd. Product name: NEO SUPER BLUE C-555: SOL. BLUE 44, Seller: Chuo Synthetic Chemical Industry Co., Ltd. Product name: NEO SUPER RED C-431: SOL. RED 132, seller: made by Chuo Synthetic Chemical Co., Ltd. Product name: NEO SUPER YELLOW C-131: SOL. YELLOW 21, Sold by Chuo Synthetic Chemical Co., Ltd. (pigment)
Brand name: NIPEX 35: Carbon black pigment, seller: Made by Degussa Brand name: CHROMOFINE BLUE: Phthalocyanine pigment, seller: Dainichi Seika Kogyo Co., Ltd. Brand name: SEIKAFAST RED: Azo pigment, Seller: Large Product name: SEIKAFAST YELLOW: Azo-based pigment, seller: Dainichi Seika Kogyo Co., Ltd. <Resin>
Resin 1: 5.0 parts by mass of Solvain TA5R (PVC / VPA copolymer, sold by Nisshin Chemical Industry Co., Ltd., features: OH group-containing) 15.0 parts by mass of solvent (IPDM) Solution dissolved in
Resin 2: DF407 (polyester-based polyurethane resin, sold by DIC Corporation, characteristics: nonvolatile 25.0%, solvent: methyl ethyl ketone, cyclohexanone, methyl cellosolve).
<Organic solvent>
Solvent 1: IPDM: diethylene glycol isopropyl methyl ether, glycol ether type organic solvent, seller: Toho Chemical Industry Co., Ltd., boiling point: 179 ° C.
Solvent 2: Propylene carbonate: Carbonate organic solvent, Seller: Tokyo Chemical Industry Co., Ltd., Boiling point: 242 ° C.
Solvent 3: DPMA: Dipropylene glycol methyl ether acetate, acetate-based organic solvent, seller: Made by Daicel Co., Ltd., boiling point: 209 ° C.

Preparation of Ink
The preparation method of the ink is shown below.
Each pigment was dispersed according to the following composition to prepare a master batch.
(K master batch)
Pigment 15 parts by mass Dispersant SOLSPERSE 33000 (manufactured by Lubrysol Co., Ltd.) 4.5 parts by mass Solvent DEDG (diethylene glycol diethyl ether, manufactured by Nippon Emulsifier Co., Ltd.) 80.5 parts by mass (C, M, Y master batch)
Pigment 15 parts by mass Dispersant SOLSPERSE 36000 (manufactured by Lubrisol Corporation) 3.75 parts by mass Solvent DEDG (diethylene glycol diethyl ether, manufactured by Japan Emulsifier Co., Ltd.) 81.25 parts by mass

Example 1
Mixing 10 parts by weight of Y masterbatch, 3.0 parts by weight of a yellow dye in 67.0 parts by weight of a solvent (IPDM), 20.0 parts by weight of a solution of resin 1 with a mixer and filtering Thus, a yellow ink (Y) was prepared. Similarly, as described in Table 1, each color ink (K, C, M) was prepared. Using the obtained ink (ink set), inkjet printing was performed on a non-water-absorptive substrate (see below for the preparation method) under the following inkjet conditions. The resulting inkjet image was subjected to a drying process under the following drying conditions to produce a printed matter.

<Ink jet conditions>
Ink jet recording device: Piezo method Nozzle diameter: 40 μm
Driving voltage: 70V
Frequency: 12kHz
Resolution: 400 x 800 dpi
Substrate temperature: 60 ° C (warming)
(Production method of non-water absorbent base material)
40 parts by mass of dimethylformamide was added to 100 parts by mass of the polycarbonate-based polyurethane resin, and the viscosity was adjusted to about 2,000 mPa · s (B-type viscometer, rotor: No. 3, 10 rpm, 23 ° C.) The resin composition was applied to a release paper by a comma coater to a coating thickness of 200 μm, and treated with a dryer at 130 ° C. for 2 minutes to produce a skin layer. Subsequently, 50 parts by mass of dimethylformamide is added to 100 parts by mass of the polycarbonate-based polyurethane resin to obtain a viscosity of about 4,500 mPa · s (B-type viscometer, rotor: No. 3, 10 rpm, 23 ° C.) To prepare an adhesive solution. The prepared adhesive solution was applied to the above skin layer with a comma coater to a coating thickness of 200 μm, and treated with a dryer at 100 ° C. for 1 minute. The adhesive coated surface and the surface of the polyester fabric of the fibrous base material were combined and press-bonded at 392.3 kPa for 4 seconds, and then the release paper was peeled off to prepare a non-water absorbent base material.

<Drying conditions>
Heat drying (1 minute at 150 ° C)

(Examples 2 to 14, Comparative Examples 1 to 11)
Inkjet printing was performed by the same method as in Example 1 except that the type and composition of the used raw materials were changed as described in Tables 1 to 4, and printed matter was produced.

The inks and prints obtained by Examples 1 to 14 and Comparative Examples 1 to 11 were evaluated based on the following evaluation methods and evaluation criteria. The results are shown in Tables 1 to 4.

<Anti-friction>
Using a Gakushin friction tester (model number: G-II, sold by Orihara Seisakusho Co., Ltd.), a weight with a load of 200 g was installed, and the printed matter was rubbed 200 times back and forth using a sandpaper # 200. For the appearance, before and after the friction test was measured with a colorimeter, and evaluated according to the following evaluation criteria.
(Evaluation criteria)
◎: The color difference ΔE was within 3.0.
○: The color difference Δ was more than 3.0 and less than 6.0.
X: The color difference Δ was 6.0 or more.

<Water resistance>
The prints stored at room temperature for 2 weeks after immersion in normal temperature water were evaluated according to the following evaluation criteria.
○: Bleeding width of the ink was 1 mm or less.
X: Bleeding width of ink exceeded 1 mm.

<Weatherability (light resistance)>
Color difference ΔE after implementation of ultraviolet irradiation for 6 hours (UV condition 100 mW / cm ² , temperature 63 ° C., humidity 50%) using a super UV tester (SUV-W161 manufactured by Iwasaki Electric Co., Ltd.) Were measured using a color difference meter (CM-2600 d, manufactured by Konica Minolta Co., Ltd.), and evaluated according to the following evaluation criteria.
(Evaluation criteria)
◎: ΔE <1.
○: 1 ≦ ΔE ≦ 2.
X: ΔE> 2.

<Discharge stability>
The nozzle clogging was confirmed when the ink was continuously discharged for 60 minutes and after being left after discharging, and evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: No clogging of the nozzle occurred ×: A clogging of the nozzle occurred after continuous discharge or standing for 10 minutes

As shown in Tables 1 to 4, according to Examples 1 to 14 using the ink of the present invention, the resulting printed matter is excellent in all of the abrasion resistance, water resistance and light resistance, and The ejection stability of each ink was also excellent. On the other hand, in Comparative Examples 1 and 4 and Comparative Examples 7 and 9 in which the dye was not contained or contained in a small amount, the abrasion resistance of the obtained printed matter was inferior. In Comparative Examples 2 and 8 in which the ink containing no pigment or having a small content was used, the light fastness of the obtained printed matter was inferior. The comparative example 3 using the ink containing a large amount of pigment was inferior in ejection stability. In Comparative Examples 5 and 10 using the ink containing a large amount of dye, the water resistance of the obtained printed matter was inferior. In Comparative Example 6 and Comparative Example 11 in which the ink containing a large amount of water was used, the abrasion resistance of the obtained printed matter and the ejection stability of the ink were inferior.

Claims (9)

Contains coloring material, resin, and organic solvent,
The colorant contains a dye and a pigment,
The content of the dye is 3.0 to 9.0% by mass,
The content of the pigment is 1.0 to 8.0% by mass,
Non-water-based inkjet ink which does not contain water or whose water content in the case of containing water is less than 10 mass%. The non-aqueous inkjet ink according to claim 1, wherein the dye comprises an oil-soluble dye or a disperse dye and is soluble in the organic solvent. The non-aqueous inkjet ink according to claim 1, wherein the organic solvent has a boiling point of 155 ° C. or more and contains a glycol ether solvent or a carbonate solvent. The content of the resin is 1 to 10% by mass,
The resin according to any one of claims 1 to 3, wherein the resin comprises at least one selected from the group consisting of a urethane resin, an acrylic resin, an acrylic urethane resin, a vinyl chloride-vinyl acetate copolymer resin, and a polyvinyl acetal resin. Non-aqueous inkjet ink as described in. The non-aqueous inkjet ink according to any one of claims 1 to 4, wherein the content of the organic solvent is 75% by mass or more. A non-water-absorptive substrate, and an inkjet layer formed on the substrate by a non-aqueous inkjet ink containing a coloring material containing a dye and a pigment,
The inkjet layer is
A dye layer provided on the substrate and containing the dye;
A printed matter which covers the dye layer and includes a pigment layer containing the pigment. A printed matter comprising: a non-water-absorptive substrate; and an inkjet layer formed on the substrate by the non-aqueous inkjet ink according to any one of claims 1 to 5. The substrate has a resin layer on the surface,
The printed matter according to claim 7, wherein the resin layer comprises at least one selected from the group consisting of a urethane resin, an acrylic resin, an acrylic urethane resin, and a vinyl chloride resin. A method for producing a printed matter, comprising the step of applying the non-aqueous ink jet ink according to any one of claims 1 to 5 to a non-water absorbing substrate by an ink jet method.