JP2001288386A - Active energy ray curable inkjet ink stock solution, active energy ray curable inkjet ink using the same, and recording method - Google Patents

Abstract

(57) [Summary] [Problem] An active energy-curable inkjet ink stock solution which can be diluted with an aqueous or hydrocarbon-based solvent depending on the material of a printing medium, and can be applied to any printing medium without any material. Provided is a method for inkjet recording on a printing medium. An active energy ray-curable inkjet ink stock solution having compatibility with both water and / or a water-soluble solvent and a hydrocarbon solvent, and the total amount of the stock solution and monomers and oligomers in the stock solution 0.2 to 2
An ink-jet ink containing 0% by weight of water and / or a water-soluble solvent, or a hydrocarbon solvent, and water and / or a water-soluble solvent and a hydrocarbon solvent are prepared. A recording method in which the water and / or a water-soluble solvent or a hydrocarbon solvent is added to the ink jet stock solution, an image is formed on a printing medium by an ink jet method using the obtained ink, and active energy rays are irradiated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable inkjet ink stock solution which can be diluted with water and / or a water-soluble solvent or a hydrocarbon solvent depending on the material of a printing medium, and an activity using the same. The present invention relates to an energy ray-curable inkjet ink and an inkjet recording method.

[0002]

2. Description of the Related Art Ink used for ink-jet recording is an aqueous type containing water as a main component, a solvent type using an alcohol or a ketone solvent, and the like. Solid type. In the case of the aqueous type, there is no particular problem when the printing medium has permeability such as paper,
When it is impermeable like a film, the fixability and drying property of the ink are poor, and it is necessary to provide an ink receiving layer on the side of the printing medium. Therefore, the applicable range of the printing medium is limited,
There is a problem that printing cost increases.

[0003] In the case of the solvent type, if a volatile solvent such as alcohol or ketone is used, the drying property of the ink is fast. be able to. However, there is a problem in that the solvent in the ink is volatilized at the nozzle portion, the solid content of the ink is increased, and as a result, nozzle clogging is likely to occur. In the case of the solid type, the ink is in a molten state until the ink is jetted from the nozzle, but is cooled by the ambient temperature from the moment the droplet flies, so that the solidification of the ink starts. Therefore, there is a problem that the fixing property of the ink depends on the environmental temperature and the temperature of the printing medium. Further, since the ink does not substantially penetrate into the printing medium, there is a disadvantage that the fixing strength, particularly the friction resistance, is weak.

As described above, there is a problem depending on the type of ink used for ink jet recording, and therefore, each type of ink has been put to practical use under limited applications, conditions and environments. In addition, in order to solve the problems of each type of ink, an ink jet ink containing a component that is cured by irradiation with ultraviolet light has been invented. Ultraviolet-curable ink jet (hereinafter abbreviated as UVIJ) ink includes a solvent containing 50% by weight or more of the ink component as disclosed in JP-A-7-224241 and disclosed in JP-A-9-183927. And those that do not use a diluting solvent as described above.

[0005]

A UVIJ ink containing about 50% by weight of a diluting solvent is disclosed in JP-A-7-41712.
As disclosed in Japanese Patent Application Laid-Open Publication No. H10-187, regardless of whether the diluting solvent is water or an organic solvent, the ink is cured on a non-permeable printing medium, and water resistance and rub resistance are imparted. . As a result, the range of applicable printing media has been widened. However, in a general ultraviolet irradiation apparatus, the curing time takes several seconds to several tens of seconds, and thus, in high-speed printing that requires instantaneous drying, the length of the drying time becomes a problem.

On the other hand, if a UVIJ ink that does not use a diluting solvent is used, the ink is cured immediately after irradiation with ultraviolet rays, and it is possible to cope with high-speed printing. However, there is a new problem that the selection range of monomers and oligomers that can be used for UVIJ inks that do not use a diluting solvent is very narrow.
The reason is that there is a range in the appropriate viscosity of the IJ ink, and the desirable upper limit is 50 mPa · s at room temperature. Therefore, it is necessary to select a monomer or oligomer having a low viscosity at the expense of other properties, or to lower the viscosity to an appropriate range by heating the ink itself as described in JP-A-2-311569. Was. However, such measures do not lead to an essential solution.

Accordingly, the present invention provides an active energy curing method which can be diluted with water and / or a water-soluble solvent or a hydrocarbon solvent depending on the material of the printing medium to be used, and which can be applied to any printing medium material. It is an object of the present invention to provide a method for performing an inkjet recording on an ink-jet undiluted solution and a printing medium of any material.

[0008]

Means for Solving the Problems The inventor of the present invention has proposed water and / or water.
Alternatively, an active energy ray-curable inkjet ink stock solution that is compatible with both a water-soluble solvent and a hydrocarbon solvent is diluted with water and / or a water-soluble solvent or a hydrocarbon solvent to form an inkjet ink. They found that they could be prepared, leading to the present invention. In addition, the present inventor adds water and / or a water-soluble solvent or a hydrocarbon solvent to the ink-jet ink stock solution according to the material of the printing medium, and uses the obtained ink-jet ink to obtain a printing medium. The present inventors have found that an image having good adhesion and water resistance can be formed on any printing medium by using a method of forming an image thereon and irradiating with an active energy ray.

That is, the present invention is an active energy ray-curable inkjet ink stock solution having compatibility with both water and / or a water-soluble solvent and a hydrocarbon solvent. Further, the present invention provides that the ink-jet stock solution contains water and / or a water-soluble solvent or a hydrocarbon-based solvent in an amount of 0.2 to 20% by weight based on the total amount of monomers and oligomers in the stock solution. It is an active energy ray-curable inkjet ink characterized by the following. Further, according to the present invention, water and / or a water-soluble solvent and a hydrocarbon solvent are prepared, and the water and / or the water-soluble solvent or the hydrocarbon solvent is added to the ink jet stock solution according to the material of the printing medium. , An image is formed on an object to be printed by an ink-jet method using the obtained ink-jet ink, and irradiation with active energy rays is performed.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The ink-jet ink stock solution of the present invention is compatible with both water and / or a water-soluble solvent and a hydrocarbon solvent, and is exposed to active energy rays such as ultraviolet rays and electron beams. It has the property of curing, and can be diluted with water and / or a water-soluble solvent or a hydrocarbon solvent selected according to the material of the printing medium, the curing device, the environment, and the like. Specifically, the ink-jet ink stock solution of the present invention contains two or more types of active energy ray-curable monomers or oligomers, at least one of which is composed of water and / or a water-soluble solvent and a hydrocarbon-based solvent. One that is compatible with both solvents with the solvent, or at least one monomer or oligomer thereof is compatible only with water and / or a water-soluble solvent, and at least one other monomer or oligomer is hydrocarbon-based It has compatibility only with the solvent.

The stock ink for ink jet ink of the present invention needs to be compatible with water and / or a water-soluble solvent as a diluting solvent or a hydrocarbon solvent. Further, 2 contained in the stock solution of the inkjet ink of the present invention.
It is necessary that at least one kind of active energy curable monomer and oligomer have compatibility with each other. In the present invention, having compatibility means that when liquids are mixed and left to stand, phase separation cannot be visually confirmed. In addition, even if it is a mixed system of a monomer and / or an oligomer and a diluting solvent, if the mixing ratio of the diluting solvent is small, the two-phase is immediately separated into two phases when mixed at almost the same ratio. It does not immediately separate, but shows a state in which the diluent solvent is emulsified in the monomer or oligomer. However, in a system showing such an emulsified state, the performance of the ink-jet IJ ink such as the aging stability of the ink and the bleeding of an image at the time of printing is insufficient. It does not fall under the “have” state.

The meaning of compatibility in the present invention will be explained more clearly. Compatibility is an abbreviation of mutual solubility, and depends on the ratio of substances to be mixed and the temperature during mixing as shown in the conceptual diagram of the mutual solubility curve in FIG. In the conceptual diagram of the mutual solubility curve in FIG. 1, the vertical axis represents temperature, and the horizontal axis represents the mixing ratio of monomers and / or oligomers and diluent solvents. The conceptual diagram shows that when the temperature is T1, a state in which all monomers and / or oligomers and a diluting solvent are mutually dissolved can be achieved, and it is easy to separate into two phases in the order of T2 and T3. ing. In general, a two-component liquid-
In order for the liquid equilibrium, that is, different substances to dissolve in each other, it is possible to cite that the solubility parameters of the respective substances are close to each other. The concept of the solubility parameter can be applied to nonpolar substances and small polar substances.However, in the case of water and substances having polar groups as in the present invention, hydrogen bonds, ionic interactions, ion-dipole interactions, etc. The application of solubility parameters is difficult because they are expected to interact. Further, it is not practical to determine the solubility parameter of a system in which a plurality of active energy-curable monomers and oligomers are mixed.

[0013] A system having compatibility with both strong and weak polar solvents such as water and / or a water-soluble solvent and a hydrocarbon solvent (stock solution of the ink-jet ink of the present invention) is limited. It cannot be realized without prescription. That is, in FIG. 1, a combination in which the temperature at which the inkjet recording is performed is close to T2 is a desirable mode for the inkjet ink stock solution of the present invention. A combination in which the temperature at which ink jet recording is performed reaches T1 cannot be expected to have compatibility with both water and / or a water-soluble solvent and a hydrocarbon solvent. Further, in the case of a combination in which the temperature at which the ink jet recording is performed is close to T3, the amount of the solvent that can be diluted is very small and is not useful for adjusting the viscosity of the ink or improving the wettability to the printing medium. is there.

Monomers compatible with both water and / or a water-soluble solvent and a hydrocarbon solvent include:
N-vinylpyrrolidone, N-vinylformamide, acryloylmorpholine and the like can be mentioned. Above all, N
-Vinylformamide is preferred because of its high compatibility with both water and hydrocarbon solvents. In addition, monomers that are compatible only with water and / or a water-soluble solvent include butanediol monoacrylate, N, N-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, -Methoxyethyl acrylate, N-vinylcaprolactam, tripropylene glycol diacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate and the like.

Examples of monomers having compatibility only with hydrocarbon solvents include dicyclopentanyl acrylate, tetrahydrofurfuryl acrylate, and isobornyl acrylate. By properly combining the above monomers or oligomers, it is possible to control the hardness and flexibility of a recorded image after irradiation with active energy rays, and the adhesiveness to a printing medium.

When at least one of the two or more monomers or oligomers contained in the ink-jet ink stock solution of the present invention is compatible with water and / or both a water-soluble solvent and a hydrocarbon solvent, the other Monomers and oligomers include those that are compatible only with water and / or water-soluble solvents, those that are compatible only with hydrocarbon solvents, and those that are compatible with water, water-soluble solvents, and hydrocarbon solvents. Those that do not show solubility can be used. Other monomers and oligomers can be selected arbitrarily in consideration of the easiness of curing and the properties of the ink film after curing.

The weight ratio of a monomer or oligomer compatible with water and / or a water-soluble solvent and a hydrocarbon solvent to another monomer or oligomer is in the range of 90:10 to 10:90. Is preferred. If the ratio of the other monomer or oligomer is more than the above range, the amount of water, water-soluble solvent, and hydrocarbon solvent that can be added as a diluent decreases, and it is difficult to achieve the object of the present invention. On the other hand, if the ratio of the other monomer or oligomer is less than the above range, the effect expected by adding the other monomer or oligomer is not sufficiently exhibited, and the meaning of the addition becomes sparse.

The weight ratio of the monomer or oligomer compatible only with water and / or the water-soluble solvent to the monomer or oligomer compatible only with the hydrocarbon solvent is 90:10 to 10:90. It is preferably within the range. If the ratio of the monomer or oligomer having compatibility only with water and / or the water-soluble solvent is less than the above range, the resulting inkjet ink stock solution will have insufficient compatibility with water and / or the water-soluble solvent. Further, when the ratio of the monomer or oligomer having compatibility only with the hydrocarbon solvent is less than the above range,
The resulting inkjet ink stock solution has insufficient compatibility with hydrocarbon solvents.

The stock solution of the inkjet ink of the present invention includes:
For the purpose of coloring, a coloring agent such as a pigment or a dye can be contained. Because sufficient recording density, light resistance, and stability when used as an inkjet ink are required,
Pigments include achromatic pigments such as carbon black and titanium oxide, and quinacridone, phthalocyanine, benzimidazolone, perylene, isoindolinone, quinophthalone, condensed azo, insoluble azo, and soluble azo pigments. It can be arbitrarily selected from chromatic organic pigments such as dye derivative derivatives.

It is preferable that the organic pigment is finely divided by the following method. That is, a mixture containing the organic pigment (A), the water-soluble inorganic salt (B) and the water-soluble solvent (C) in an amount of 3 to 20 times the weight of the organic pigment (A) is mixed, kneaded and fined by a kneader or the like. Thereafter, the mixture is put into water and stirred by a high-speed mixer or the like to form a slurry.
Water-soluble inorganic salt (B) by repeating filtration and washing of the slurry
And the water-soluble solvent (C) are removed. The hydrated pigment obtained by the above procedure may be used as it is in an ink-jet ink stock solution, or may be dried by heating and used as a powder.

The water-soluble inorganic salt (B) functions as a grinding agent for an organic pigment, and for example, sodium chloride is used. The water-soluble solvent (C) is used for forming an appropriate clay state between the organic pigment (A) and the water-soluble inorganic salt (B) and effectively performing grinding. Therefore, the solvent is not particularly limited as long as it dissolves in water. However, since the temperature of the system increases during milling, a solvent having a boiling point within the range of 120 to 250 ° C. is suitably used from the viewpoint of safety. Specific examples of the water-soluble solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. , Triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low And molecular weight polypropylene glycol.

The stock solution of the inkjet ink of the present invention includes:
In order to stably disperse the pigment in the monomer or oligomer, it is desirable to include a dispersant in the range of 0.1 to 10% by weight based on the total amount of the ink jet ink stock solution. Examples of the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide and a high-molecular-weight acid ester, a salt of a high-molecular-weight polycarboxylic acid, a salt of a long-chain polyaminoamide and a polar acid ester, a high-molecular-weight unsaturated ester, Molecular copolymer, modified polyurethane, modified polyacrylate, polyetherester type anionic surfactant, naphthalenesulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate, polyoxyethylene nonylphenyl Ether, stearylamine acetate, pigment derivatives and the like can be used.

As a specific example of the dispersant, BYK Chem
ie, "Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terraa-203"
/ 204 (high molecular weight polycarboxylate) "," Disp
erbyk-101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165,
166, 170 (respectively, high molecular weight copolymers) "," 40
0 "," Bykumen "(high molecular weight unsaturated ester)," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," P104S, 240S (high molecular weight unsaturated polycarboxylic acid and silicon type) "," Lac
timon (long-chain amine, unsaturated polycarboxylic acid and silicon) ".

Further, “Efka 44, 46, 47, 48, 49, 54, 6” manufactured by Efka Chemicals, Inc.
3, 64, 65, 66, 71, 701, 764, 76
6 "," Efka polymer 100 (modified polyacrylate), 150 (aliphatic modified polymer), 400, 40
1, 402, 403, 450, 451, 452, 453
(Modified polyacrylate), 745 (copper phthalocyanine-based) ", Kyoeisha Chemical" Floren TG-710 (urethane oligomer), "Flonon SH-290, SP-1
000 "," Polyflow No. 50E, No. 300 "
(Acrylic copolymer), "Dispalon KS860, 873SN, 874 (polymer dispersant), manufactured by Kusumoto Chemicals, #
2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester type) "and the like.

Further, "Demol RN, N (sodium salt of formalin condensate of naphthalenesulfonic acid)" manufactured by Kao, M
S, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP "," Homogenol L-18 (polycarboxylic acid type polymer), "Emulgen 920, 93
0, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether), "acetamine 24 (coconut acetate), 86 (stearylamine acetate)", Zeneca Corp. "SOLSPERS 5000, 132"
40, 13940, 17000, 22000, 2400
0 ", Nikko Chemical's" Nikkor T106 (polyoxyethylene monostearate), Hexagline
4-0 (hexaglyceryltetraolate) "and the like.

If necessary, a photopolymerization initiator may be appropriately added to the stock ink-jet ink and / or ink-jet ink of the present invention. When ultraviolet rays are used as the active energy ray for curing the ink-jet ink of the present invention, radicals are generated by molecular chain scission of the photopolymerization initiator to cause a polymerization reaction of monomers and oligomers in the ink. It is common to add agents. However, when using an electron beam,
Radicals are generated by the molecular chain cleavage of monomers and oligomers in the ink, causing a polymerization reaction. Therefore, a photopolymerization initiator is not particularly required. Whether or not to use a photopolymerization initiator is a difference derived from the principle of radical generation, and is not an essential problem in the present invention.

As the photopolymerization initiator, benzophenones such as benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, hydroxybenzophenone,
4-diethylaminobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-benzoyl-
4′-methyldiphenyl sulfide and the like as thioxanthones, thioxanthone, 2-chlorooxanthone, 2,4-diethylthioxanthone, 2-methyl-1
-(4-methylthio) phenyl-2-morpholinopropan-1-one, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone and the like, as acetophenones, 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 1 -[4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one or the like is a benzoin-based compound.
Benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.
4,6-trimethylbenzyl-diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-
(Morpholinophenyl) -butan-1-one, bis-
2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide and the like are used.

A sensitizer (photopolymerization aid) which promotes the initiation reaction in combination with a photopolymerization initiator can be used although it is not activated by ultraviolet light by itself. Examples of the sensitizer include aliphatic or aromatic compounds such as triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, and ethyl 4-dimethylaminobenzoate (n-butoxy). Group amines.

Further, in order to further ensure the stability over time of the ink-jet ink of the present invention and the on-machine stability in a recording apparatus, the stock solution of the ink-jet ink of the present invention and / or
Alternatively, a thermal polymerization inhibitor may be added to the inkjet ink. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone,
2,6-t-butyl-p-cresol, 2,3-dimethyl-6-t-butylphenol, anthraquinone and the like. The thermal polymerization inhibitor can be added in the range of 0.01 to 5% by weight based on the total amount of the ink.

The ink-jet ink stock solution and / or the ink-jet ink of the present invention may be added to the ink-jet ink stock of the present invention for the purpose of improving the adhesion of the ink-jet ink to a printing medium, improving the abrasion resistance of a printed matter, and adjusting the spread of dots. A resin soluble in the active energy ray-curable monomer and / or oligomer therein can also be added. Specific examples of the resin include polyvinyl chloride, poly (meth) acrylate, epoxy resin, polyurethane, cellulose derivative, vinyl chloride-vinyl acetate copolymer, polyamide, polyvinyl acetal, diallyl phthalate resin, and butadiene-acrylonitrile copolymer. Coalescing, acrylic resin, styrene-acrylic resin, styrene-maleic acid resin, rosin, rosin ester, ethylene-vinyl acetate copolymer, petroleum resin, coumarone indene resin, terpene phenol resin, phenol resin, melamine resin, urea resin, Xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, silicone resin, maleic acid resin, fumaric acid resin, and the like.

The stock solution of the inkjet ink of the present invention comprises two or more monomers or oligomers as essential components, a pigment, and if necessary, a pigment dispersant, a photopolymerization initiator, a sensitizer, a thermal polymerization inhibitor, a resin and the like. Into a normal dispersing machine,
The pigment can be manufactured by performing dispersion until the pigment has a desired average dispersed particle size and particle size distribution. These materials may be mixed and dispersed at once, or may be separately mixed and dispersed in consideration of the characteristics and economy of each material. As a dispersing machine, a sand mill, a bead mill, an agitator mill, a dyno mill, a Kobol mill and the like are suitable.
In each disperser, when there is an appropriate viscosity range for pigment dispersion, it is desirable to adjust the ratio of the monomer or the oligomer to the pigment. After the dispersion, it is desirable to carry out filtration by a filter or a centrifugal method for the purpose of removing coarse particles and foreign matters.

The ink-jet ink stock solution of the present invention is added in an amount of 0.2 to the total amount of monomers and oligomers in the stock solution.
Preparation of an active energy ray-curable inkjet ink by adding water and / or a water-soluble solvent or a hydrocarbon-based solvent in an amount of from 20 to 20% by weight, preferably from 0.5 to 15% by weight, and stirring uniformly. Can be. The obtained ink-jet ink has a proper viscosity (about 50 mPa · s or less at the time of recording). Also,
By diluting with water, a water-soluble solvent, or a hydrocarbon-based solvent, the wettability is adjusted so as to be compatible with various printing materials, and as a result, the selection range of the printing material to be applied is widened, and paper It can be recorded on various printing materials such as paper, plastic film, metal and glass. Further, since the amount of the diluting solvent is small, the energy required for curing the ink is small, and the time required for curing the ink is reduced to a range where there is no problem, and high-speed printing is possible. When the content of the solvent is less than 0.2% by weight, the viscosity of the ink-jet ink cannot be adjusted to an appropriate range, and the wettability of the ink-jet ink to a printing medium becomes insufficient. On the other hand, when the content exceeds 20% by weight, the curing of the ink becomes insufficient with the capability of generally available ultraviolet rays and electron beams, and a device for irradiating ultraviolet rays and electron beams with higher output is required, making it difficult to cope with high-speed printing. .

As the water added to the ink-jet stock solution of the present invention, ion-exchanged water or distilled water is preferably used in view of the stability of the ink. Examples of the water-soluble solvent include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone (MEK), amides such as dimethylformamide and dimethylacetamide, and glycols. Water and a water-soluble solvent can be used as a mixture, or two or more water-soluble solvents can be used as a mixture. As the hydrocarbon-based solvent, a linear hydrocarbon, a chain hydrocarbon of a branched hydrocarbon, an alicyclic hydrocarbon, or the like is used alone or in combination.

[0034]

Next, the present invention will be described in more detail with reference to examples. Parts and% in the examples are parts by weight and% by weight.
Are respectively shown. [Examples 1 to 8] Examples of UV curable inkjet ink stock solutions A pigment and a dispersant having the composition shown in Table 1 were placed in a sand mill together with 90 parts of the monomer having the composition of (1), and dispersed for 4 hours. A curable inkjet ink stock solution was obtained. Next, 10.0 parts of the photopolymerization initiator having the composition of (2) and the diluting solvent shown in Table 1 were added to the ink stock solution, and the mixture was gently mixed until the photoinitiator was dissolved. An ink jet ink was obtained. Using the obtained ink, printing was performed on a printing medium shown in Table 1 by an ink jet printer having a piezo head, and then a UV irradiation device (one high-pressure mercury lamp: output 120 W) was used to transport the printing medium at a speed of 20 m /. The printed matter was cured by irradiating ultraviolet rays under the conditions of minutes. (1) Monomer composition Trimethylolpropane triacrylate 50 parts N-vinylformamide 40 parts (2) Photopolymerization initiator composition 2-methyl-1- (4-methylthio) phenyl-2-morpholinopropan-1-one 6.5 Parts 3.5 parts isopropylthioxanthone

[Examples 9 to 16] Examples of electron beam-curable ink-jet ink stock solutions Among the compositions shown in Table 2, pigments, monomers and dispersants were dispersed in a sand mill for 4 hours and then applied to a 1-micron filter. And filtered to prepare a stock solution of an electron beam-curable inkjet ink. Thereafter, a diluting solvent shown in Table 2 was added to the ink stock solution and mixed to obtain an electron beam-curable inkjet ink. After printing with an ink jet printer having a piezo head using the obtained ink, an EB irradiator (acceleration voltage: 50 KV, output density: 150 W / cm ² ) is used at a transport speed of a printing medium of 30 m / min. Irradiate an electron beam,
The printed matter was cured.

[Comparative Examples 1 to 4] Comparative examples of UV curable ink-jet ink stock solutions Among the compositions shown in Table 3, pigments, monomers and dispersants were placed in a sand mill and dispersed for 4 hours. A stock solution was obtained. Next, 10.0 parts of a photopolymerization initiator having the same composition as in Examples 1 to 8 and a diluting solvent shown in Table 3 were added to the ink stock solution, and the mixture was gently mixed until the photoinitiator was dissolved. After that, an ultraviolet curable inkjet ink was obtained. Using the obtained ink,
After printing in the same manner as in Examples 1 to 8, the printed matter was cured.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

The abbreviations in the table indicate the following. Also,
The numbers indicate the number of copies. Pigment ・ P1 Crude copper phthalocyanine (“Copper phthalocyanine” manufactured by Toyo Ink Mfg.): 250 parts, sodium chloride: 25
00 parts and 160 parts of polyethylene glycol (“Polyethylene Glycol 300” manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, the mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and then filtered and washed with water five times to repeat sodium chloride and solvent. , And then spray-dried to obtain a dried treated pigment.

P2 quinacridone red pigment (CibaG)
Eigy “Sincacia Magenta RT-355-D”):
250 parts, 2500 parts of sodium chloride, and 160 parts of "polyethylene glycol 300" were charged into a 1-gallon kneader made of stainless steel, and a treated pigment was obtained in the same manner as in P1. -P3 Benzimidazolone yellow pigment ("Hostapalm Yellow H3G" manufactured by Hoechst): 250 parts, sodium chloride: 2500 parts, and "polyethylene glycol 3"
00 ": 160 parts were placed in a stainless steel 1 gallon kneader, and a treated pigment was obtained in the same manner as in P1.・ P4 carbon black pigment (Degussa “Print”
ex 150T ")

Monomers · NVF N-vinylformamide · NVP N-vinylpyrrolidone · TPGDA tripropylene glycol diacrylate · TMPTA trimethylolpropane triacrylate · HDDA 1,6-hexanediol diacrylate · ACMO acryloylmorpholine · DCPA dicyclo Pentanyl diacrylate ・ IBX Isobornyl acrylate

Dispersant ・ 13940 Dispersant “SOLSPERS 144000” manufactured by Zeneca Corporation ・ 24000 Dispersant “SOLSPERS 24000” manufactured by Zeneca Corporation ・ 5000 Dispersant “SOLSPERS5000” manufactured by Zeneca Corporation ・ 22000 Dispersant “SOLSPERS 22000” manufactured by Zeneca Corporation L-18 polycarboxylic acid type polymer dispersant (“Homogenol L-18” manufactured by Kao Corporation) ・ Efka 49 modified polyacrylate dispersant (Efka CHE)
MICALS “Fuka 49”) Diluent solvent ・ IsoparL aliphatic hydrocarbon solvent (Exxon “IsoparL”) ・ EXXSOL D110 Aliphatic hydrocarbon solvent (Exxon “EXXSOL D110”)

The inks obtained in Examples 1 to 16 and Comparative Examples 1 to 4 and the printed matter after curing were evaluated as follows. Table 4 shows the results. [Adhesion] The printed matter was peeled off after a cellophane tape was applied thereto, and the presence or absence of peeling of the ink film was visually checked (o: no peeling off, x: peeling off). [Water resistance] The printed matter was immersed in water for 1 minute, and the presence or absence of ink bleeding and ink bleeding was visually evaluated (○: bleeding, no bleeding out, ×: bleeding, bleeding out). [Curability] The tackiness of the ink film surface of the printed matter was confirmed by touch with a finger (（: no tackiness, ×: tackiness).

[D50] The particle size distribution of the ink was measured using a laser light scattering type particle size distribution meter (“Microtrac UPA-100” manufactured by Nikkiso Co., Ltd.).
") And the average particle diameter was shown. The unit is nm. [Ejection] Printing was performed with an ink jet printer having a piezo-type head performing a frequency change of 4 to 10 KHz using the ink, and the printed state of the printed matter was visually evaluated (○:
Continuous printing can be performed accurately at a predetermined position. ×: Defects occurred on the way, or not printed at predetermined positions. ). [Stability over time] The state of dispersion of the ink after storage at 25 ° C. for one month was evaluated visually and by a change in viscosity (◎: no precipitate was observed, and no change was observed in the dispersion particle size and viscosity).
：: No generation of precipitate was observed, and there was no change in viscosity. ×:
Precipitation is observed. ).

[Viscosity] The viscosity of the ink was measured at 25 ° C. using a B-type viscometer. The unit is mPa · s. [Transparency] The transparency when the ink was spread on an OHP sheet for ink jet with a 1.5 mm applicator was visually evaluated (A: very good; B: good; X: bad). [Filterability] 25 ml of ink is 25 mm in diameter and the pore size is 3.
It was evaluated whether or not filtration was possible with a 0 μm membrane filter (○: filtration possible. Δ: slight filtration possible. ×:
No filtration at all. ). [Resolubility] The cleaning property when the nozzle tip to which the dried ink adhered was immersed in the ink was visually evaluated (目:
Completely washable. ：: Almost washable. X: Washing impossible. ).

Table 4 Evaluation Results Adhesion Waterproof curing D50 Discharge Aging Viscosity Transparent filtration Re-dissolution Stable Example 1 ○ ○ ○ 136 ○ ○ 20.9 ○ ○ ◎ Example 2 ○ ○ ○ 123 ○ ○ 28.8 ○ ○ ◎ Example 3 ○ ○ ○ 103 ○ ○ 18.6 ○ ○ ◎ Example 4 ○ ○ ○ 122 ○ ○ 19.8 ○ ○ ◎ Example 5 ○ ○ ○ 113 ○ ○ 23.9 ○ ○ ◎ Example 6 ○ ○ ○ 95 ○ ○ 24.6 ○ ○ ◎ Example 7 ○ ○ ○ 168 ○ ○ 20.5 ○ ○ ◎ Example 8 ○ ○ ○ 102 ○ ○ 22.2 ○ ○ ◎ Example 9 ○ ○ ○ 142 ○ ○ 21.0 ○ ○ ◎ Example 10 ○ ○ ○ 128 ○ ○ 19.9 ○ ○ ◎ Example 11 ○ ○ ○ 133 ○ ○ 19.0 ○ ○ ◎ Example 12 ○ ○ ○ 128 ○ ○ 23.3 ○ ○ ◎ Example 13 ○ ○ ○ 106 ○ ○ 20.0 ○ ○ ◎ Example 14 ○ ○ ○ 127 ○ ○ 21.3 ○ ○ ◎ Example 15 ○ ○ ○ 108 ○ ○ 20.6 ○ ○ ◎ Example 16 ○ ○ ○ 138 ○ ○ 24.1 ○ ○ ◎ Comparative Example 1 ○ ○ ○ 178 △ × 19.5 ○ △ × Comparative Example 2 ○ ○ ○ 168 △ × 20.1 ○ △ × Comparative Example 3 ○ ○ ○ 258 × × 40.8 ○ × × Comparative Example 4 ○ ○ ○ 221 × × 32.9 ○ × ×

[0048]

The ink-jet stock solution of the present invention comprises:
Depending on the material of the printing medium, it can be diluted with water and / or a water-soluble solvent or a hydrocarbon-based solvent. Thus, an ink-jet ink in which is adjusted was obtained. as a result,
The range of choices of the printing medium that can be applied without forming a special receiving layer has been expanded, and active energy ray-curable inkjet inks can be developed for a wide range of applications.

[0049]

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing a mutual solubility curve.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA13 FA04 FB01 FB02 FC02 HA44 2H086 BA02 BA52 BA53 BA54 BA55 BA59 BA62 4J039 AD21 BC02 BC07 BC09 BC12 BC13 BE12 BE27 CA03 CA04 EA04 EA06 EA36 EA38 GA24

Claims (10)

[Claims] 1. An active energy ray-curable inkjet ink stock solution having compatibility with both water and / or a water-soluble solvent and a hydrocarbon solvent. 2. An active energy ray-curable monomer or oligomer, wherein at least one monomer or oligomer is compatible with water and / or both a water-soluble solvent and a hydrocarbon-based solvent. 2. The active energy ray-curable inkjet ink stock solution according to claim 1, which has solubility. 3. An active energy ray-curable monomer or oligomer comprising at least one monomer or oligomer, wherein at least one monomer or oligomer is compatible with water and / or a water-soluble solvent, and at least one other monomer or oligomer. 2. The active energy ray-curable inkjet ink stock solution according to claim 1, wherein the oligomer is compatible with a hydrocarbon solvent. 4. The weight ratio of a monomer or oligomer compatible with both water and / or a water-soluble solvent and a hydrocarbon solvent to another monomer or oligomer is 90:10 to 10:90. The active energy ray-curable inkjet ink stock solution according to claim 2, wherein 5. The weight ratio of a monomer or an oligomer compatible with water and / or a water-soluble solvent to a monomer or an oligomer compatible with a hydrocarbon solvent is 9%.
4. The active energy ray-curable inkjet ink stock solution according to claim 3, wherein the concentration is in the range of 0:10 to 10:90. 6. The active energy ray according to claim 2, wherein the monomer compatible with water and / or both the water-soluble solvent and the hydrocarbon solvent is N-vinylformamide. Curable inkjet ink stock solution. 7. An ink-jet stock solution according to claim 1, comprising 0.2 to 20% by weight of water and / or a water-soluble solvent based on the total amount of monomers and oligomers in the stock solution. An active energy ray-curable inkjet ink characterized by the following. 8. An ink-jet stock solution according to claim 1, comprising 0.2 to 20% by weight of a hydrocarbon solvent based on the total amount of monomers and oligomers in the stock solution. Active energy ray curable inkjet ink. 9. The hydrocarbon solvent is a chain hydrocarbon and / or
Or an alicyclic hydrocarbon.
The active energy ray-curable inkjet ink according to the above. 10. A method according to claim 1, wherein water and / or a water-soluble solvent and a hydrocarbon-based solvent are prepared, and depending on the material of the printing medium.
7. The above-mentioned water and / or water-soluble solvent or hydrocarbon-based solvent is added to the ink-jet stock solution described in any one of 6 to 6, and an image is formed on a printing medium by an ink-jet method using the obtained ink-jet ink; An inkjet recording method comprising irradiating a line.