JP2003012971A - Inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet recording method which comprises imparting a polymerizable resin to a recording medium with the use of two liquids of an ink composition and a reactant solution, and excels in quick drying characteristics and bleeding, and has adaptability to many materials to be recorded. SOLUTION: The injet recording method comprises attaching an ink composition and a reactant solution on to a recording medium to effect printing, and the above ink composition contains a polymerizable compound and a coloring material and, simultaneously, has a content of the polymerizable compound therein of 30-98 mass%, and the above reactant solution contains a polymerizable compound and a polymerization initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording method capable of excellent printing by using a polymerizable resin as a recording medium by using two liquids of an ink composition and a reaction liquid.

[0002]

2. Description of the Related Art Ink jet recording methods are of high resolution,
It has the feature that high-quality images can be printed at high speed. The ink composition used in the ink jet recording method generally contains an aqueous solvent as a main component and a coloring component and a wetting agent such as glycerin for the purpose of preventing clogging.

On the other hand, paper which is difficult for the aqueous ink composition to penetrate,
When printing on a recording medium such as cloth or a material such as metal or plastic that does not penetrate, for example, a resin such as phenol, melamine, vinyl chloride, acryl, or polycarbonate, a recording medium such as a film, an ink composition or a reaction liquid is used. Is required that the colorant can be stably fixed to the recording medium.

In response to such a demand, an ink composition containing a component which is polymerized by application of ultraviolet rays has been disclosed (for example, JP-A-3-216379).
Further, an ultraviolet curable inkjet ink containing a colorant, an ultraviolet curing agent, a polymerization initiator and the like has been disclosed (for example, US Pat. No. 5,623,001). According to these ink compositions and inkjet recording methods, it is said that the ink can be prevented from bleeding into the recording medium and the image quality can be improved.

Further, an ink composition containing a coloring agent is used for the purpose of preventing the separation of dye which is a coloring agent, improving the abrasion resistance to improve printing reliability, preventing bleeding after printing and improving the drying property of the ink. Using two liquids of a reaction product containing a substance and a polymerization initiator,
Ink jet recording methods for printing on a recording medium have been disclosed (for example, JP-A-5-186725, JP-A-8-218018, and JP-A-2000-119574).

In the ink jet recording method using such two liquids, when the ink composition and the reaction liquid containing the polymerization initiator are brought into contact with each other on the recording medium and irradiated with ultraviolet rays, the polymerization initiator in the reaction liquid is Generate radicals and the like, and the oligomers and monomers start polymerization to fix the colorant in the ink composition onto the recording medium. It is considered that this fixation can realize printing with high color density and less blurring and unevenness. Further, by separating the ink composition and the reaction liquid, the storage stability of the ink composition and the reaction liquid is improved.

In recent years, particularly, required quality such as high speed, large size, and high image quality is increasing, and quick drying property and bleeding reduction are desired. There is also an increasing demand for recording on various recording materials as well as recording papers and recording films.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide an ink jet recording method which is excellent in quick drying and bleeding and is adaptable to many recording materials. It is in.

[0009]

The above object of the present invention can be achieved by the following constitutions.

1. In an inkjet recording method for printing by adhering an ink composition and a reaction liquid to a recording medium, the ink composition contains a polymerizable compound and a colorant,
In addition, the content of the polymerizable compound in the ink composition is 30.
To 98% by mass, and the reaction liquid contains a polymerizable compound and a polymerization initiator.

2. In an inkjet recording method for printing by adhering an ink composition and a reaction liquid to a recording medium, water or a boiling point of 300 in the ink composition is used.
An ink jet recording method, characterized in that the content of the solvent at 60 ° C. or less is 60% by mass or less.

3. 3. The ink jet recording method according to 1 or 2, wherein the polymerization initiator of the reaction liquid is a photopolymerization initiator.

4. 4. The inkjet recording method according to any one of 1 to 3, wherein the colorant is a pigment.

The present invention will be described in detail below. One of the inkjet recording methods according to the present invention is to perform printing on a recording medium using two liquids of an ink composition and a reaction liquid. The ink composition contains a polymerizable compound and a colorant, and the reaction liquid contains a polymerizable compound and a polymerization initiator.
The content of the polymerizable compound in the ink composition is 30.
Is about 98% by mass.

In the present invention, the ink composition containing a colorant and the reaction liquid containing a polymerization initiator are divided into two liquids, and the two liquids are used to print on a recording medium. Therefore, the polymerization efficiency, the film strength, the storage stability and the life stability of the ink composition or the reaction liquid, and the ejection stability can be significantly improved.

That is, in the present invention, the colorant and the polymerization initiator are separately contained in the ink composition and the polymerization initiator is separately contained in the reaction liquid without mixing them into one solution. When both are printed and brought into contact with each other, the curing reaction can be efficiently performed, and the storage stability of the ink composition can be improved. Further, by setting the content of the polymerizable compound to be large, it is possible to obtain an image excellent in quick-drying property and bleeding prevention.

From the above, according to the ink jet recording method of the present invention, it is possible to suppress bleeding and uneven printing on the recording medium. Further, it is possible to effectively prevent uneven color mixing, that is, color bleeding, in a boundary region of different colors, which is often a problem in the color ink jet recording method. Therefore, it is possible to obtain a high-quality print excellent in color developability and a recorded matter excellent in abrasion resistance.

Further, in the ink jet recording method of the present invention, it is preferable that the recording medium is irradiated with ultraviolet rays and / or heated during or after recording. As a result, it is possible to obtain a printed material that is clear and has excellent abrasion resistance even on the surface of a medium that cannot penetrate an aqueous medium such as metal or plastic.

According to a preferred embodiment of the present invention, it is preferable to carry out the curing reaction after bringing the ink composition and the reaction liquid into contact with each other. Examples of methods for this purpose include light irradiation and heating.

The light irradiation may be visible light irradiation or ultraviolet irradiation, and ultraviolet irradiation is particularly preferable. When UV irradiation is performed, the UV irradiation amount is 100 mJ / cm ² or more, preferably 500 mJ / cm ² or more, and 10,000
mJ / cm ² or less, preferably performed at 5,000 mJ / cm ² or less. An ultraviolet irradiation amount within such a range is advantageous because the curing reaction can be sufficiently carried out, and the colorant can be prevented from fading due to ultraviolet irradiation. Examples of the ultraviolet irradiation include lamps such as metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, low pressure mercury lamps, and high pressure mercury lamps. For example, commercially available lamps such as H lamps, D lamps, and V lamps manufactured by Fusion System can be used. The metal halide lamp has a continuous spectrum as compared with a high-pressure mercury lamp (main wavelength is 365 nm), has a high luminous efficiency in the range of 200 to 450 nm, and is abundant in the long wavelength region. Therefore, when a pigment is used as in the ink composition of the present invention, a metal halide lamp is suitable.

The heating is carried out by bringing a heat source into contact with the recording medium to heat the medium, infrared rays or microwaves (2,450 Mh).
For example, a method of irradiating an electromagnetic wave having a maximum wavelength of about z) or blowing hot air without heating the recording medium may be used.

In the present invention, the ink composition and the reaction liquid are contacted on the recording medium. According to an aspect of the invention,
The step of depositing the ink composition on the recording medium may be performed after the step of depositing the reaction liquid on the recording medium or before the step of depositing the reaction liquid on the recording medium.

In the present invention, it is preferable to use the piezoelectric action of a piezoelectric material, which has a wide range of application to ink, as the driving force for ink ejection of an ink jet printer. Specifically, as described in, for example, Japanese Patent Publication No. 4-48622, an electrode film is formed inside a fine groove formed on a piezoelectric substrate and further covered with an insulating film to form an ink flow path. Inkjet head method.

Next, the reaction liquid and the ink composition will be described in this order. (Reaction Liquid) The reaction liquid in the present invention is characterized by containing a polymerizable compound and a polymerization initiator.

Examples of the polymerizable compound include photopolymerizable compounds, and radical polymerizable compounds such as JP-A-7-15.
No. 9983, No. 8-224982, No. 10-863.
No. 7, Japanese Patent Publication No. 7-31399, Japanese Patent Application No. 7-231444
Photo-curable material using a photo-polymerizable composition described in No., and a cationic polymerization-based photo-curable resin are known,
Recently, a photo-cationic photocurable resin of a photo-cationic polymerization type sensitized to a longer wavelength region than visible light is also disclosed in, for example, JP-A-6-43633.
Issue No. 8-324137, etc. 1) Radical-polymerizable compound What is a radical-polymerizable compound is a compound having a radical-polymerizable ethylenically unsaturated bond, as long as it is a compound having at least one radical-polymerizable ethylenically unsaturated bond in the molecule. Any of these may be used, including those having a chemical form such as a monomer, an oligomer and a polymer. Only one radical polymerizable compound may be used, or two or more radical polymerizable compounds may be used in combination at an arbitrary ratio in order to improve desired properties. In addition, it has 2 more functional groups than monofunctional compounds.
A polyfunctional compound having three or more is more preferable. More preferably, two or more polyfunctional compounds are used in combination,
It is preferable in controlling the performance such as reactivity and physical properties.

Examples of the radically polymerizable compound having an ethylenically unsaturated bond include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, and salts and esters thereof.
Radical-polymerizable compounds such as urethane, amide and anhydride, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides and unsaturated urethanes can be mentioned. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane,
Neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate. , Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, acrylic acid derivatives such as N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n- Butylme Acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,
6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxy) Methacrylic derivatives such as polyethoxyphenyl) propane, and derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be mentioned, and more specifically, Shinzo Yamashita "Crosslinking Agent Handbook" (1981). Taiseisha); “UV / EB curing handbook (raw materials)” edited by Kiyomi Kato (19)
1985, Kobunshi Kogyokai); RadTech Study Group "UV ・
Application and Market of EB Curing Technology ", p. 79, (1989,
CMC); commercial products described in "Polyester Resin Handbook" by Eiichiro Takiyama (1988, Nikkan Kogyo Shimbun) and the like, or radically polymerizable or crosslinkable monomers, oligomers and polymers known in the art can be used. The amount of the radically polymerizable compound added is preferably 1 to 97% by mass, more preferably 30 to 95% by mass. 2) Cationic polymerization type photo-curable resin UV curable prepolymer of a type (mainly epoxy type) in which polymerization is caused by cationic polymerization, and monomers include prepolymers containing two or more epoxy groups in one molecule. You can Examples of such prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, and polyglycidyl aromatic polyols. Examples thereof include ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds and epoxidized polybutadienes. These prepolymers may be used alone or in a mixture of two or more.

Other cationically polymerizable compounds contained in the cationically polymerizable composition include, for example, the following (1) styrene derivatives, (2) vinylnaphthalene derivatives, and (3).
Examples thereof include vinyl ethers and (4) N-vinyl compounds. (1) Styrene derivative For example, styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-
Methylstyrene etc. (2) Vinylnaphthalene derivative, for example, 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, 4
-Methyl-1-vinylnaphthalene, 4-methoxy-1-
(3) Vinyl ethers such as vinyl naphthalene, for example, isobutyl vinyl ether, ethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-methoxyphenyl vinyl ether,
α-Methylphenyl vinyl ether, β-methyl isobutyl vinyl ether, β-chloroisobutyl vinyl ether, etc. (4) N-vinyl compounds such as N-vinylcarbazole, N-vinylpyrrolidone, N-vinylindole, N-vinylpyrrole, N-
Vinylphenothiazine, N-vinylacetanilide, N
-Vinylethylacetamide, N-vinylsuccinimide, N-vinylphthalimide, N-vinylcaprolactam, N-vinylimidazole and the like.

The content of the above cationically polymerizable compound in the cationically polymerizable composition is preferably 1 to 97% by mass, more preferably 30 to 95% by mass.

Examples of the polymerization initiator include radical polymerization initiators, for example, Japanese Examined Patent Publication Nos. 59-1281 and 61-9.
621 and the triazine derivatives described in JP-A-60-60104 and the like, JP-A-59-1504 and JP-A-61-104.
Organic peroxides described in No. 243807, Japanese Examined Patent Publication No. 43-
No. 23684, No. 44-6413, No. 44-6413
No. 47-1604 and U.S. Pat. No. 3,56.
No. 7,453, diazonium compounds, U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853, organic azide compounds, JP-B-36-22062, No. 37-13109, No. 3
8-18015, 45-9610 and the like, ortho-quinonediazides, 55-39162, JP-A-59-14023 and the like, and "Macromolecular (Ma).
various types of onium compounds described in pp. 1307 (1977).
Azo compounds described in JP-A 9-142205, JP-A 1-5
No. 4440, European Patent Nos. 109,851, 126,712, etc., "Journal of Imaging Science" (J.Imag.Sci.) ", No. 3
0, page 174 (1986), metal allene complexes, Japanese Patent Application Nos. 4-56831 and 4-89535, (oxo) sulfonium organoboron complexes, JP-A-61-151197. Titanocenes, "Coordination Chemistry Review (Coordi
Nation Chemistry Review
w) ", Vol. 84, 85-277 (1988).
And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701, and JP-A-3-209477.
2,4,5-triarylimidazole dimer, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344. These polymerization initiators are preferably contained in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the compound having a radically polymerizable ethylenic unsaturated bond.

As the polymerization initiator for the cationic polymerization type photocurable resin (also referred to as a cationic polymerization initiator), an aromatic onium salt can be mentioned. As the aromatic onium salt, a salt of a Group Va element of the periodic table, for example, a phosphonium salt (for example, triphenylphenacylphosphonium hexafluorophosphate), a salt of a Group VIa element, for example, a sulfonium salt (for example, triphenyl tetrafluoroborate) Sulfonium, triphenylsulfonium hexafluorophosphate, tris (4-thiomethoxyphenyl) hexafluorophosphate, sulfonium and triphenylsulfonium hexafluoroantimonate), and salts of Group VIIa elements, such as iodonium salts (eg, diphenyl chloride) Iodonium and the like).

The use of such an aromatic onium salt as a cationic polymerization initiator in the polymerization of an epoxy compound is disclosed in US Pat. Nos. 4,058,401 and 4,058.
69,055, 4,101,513 and 4,161,478.

The preferred cationic polymerization initiator is
Examples thereof include sulfonium salts of Group VIa elements. Among them, from the viewpoint of ultraviolet curability and storage stability of the composition, triarylsulfonium hexafluoroantimonate is preferable. 3 of Photopolymer Handbook (Published by Industrial Research Society, Photopolymer Society 1989)
Known photopolymerization initiators described on pages 9 to 56, JP-A-64-
The compounds described in JP-A No. 13142 and JP-A No. 2-4804 can be optionally used.

In the present invention, of the above-mentioned polymerization initiators, photopolymerization initiators are preferable in terms of the effects of the present invention.

The reaction solution in the present invention may contain an aqueous solvent, and may further contain a polyvalent metal salt, polyallylamine or a derivative thereof, a wetting agent, a pH adjusting agent, an antifungal agent and the like. (Ink Composition) The ink composition of the present invention is characterized by containing a polymerizable compound and a colorant, and the content of the polymerizable compound in the ink composition is 30 to 98% by mass.

As the colorant in this ink composition,
Conventionally known dyes and pigments can be used. A pigment is more preferable as the colorant in the invention.

Among the dyes, examples of water-soluble dyes include:
C. I. Direct Black-2, -4, -9, -1
1, -17, -19, -22, -32, -80, -15
1, -154, -168, -171, -194; C.I.
I. Direct Blue-1, -2, -6, -8, -2
2, -34, -70, -71, -76, -78, -8
6, -112, -142, -165, -199, -20
0, -201, -202, -203, -207, -21
8, -236, -287; C.I. I. Direct Red-
1, -2, -4, -8, -9, -11, -13, -1
5, -20, -28, -31, -33, -37, -3
9, -51, -59, -62, -63, -73, -7
5, -80, -81, -83, -87, -90, -9
4, -95, -99, -101, -110, -189;
C. I. Direct Yellow-1, -2, -4, -8,
-11, -12, -26, -27, -28, -33,-
34, -41, -44, -48, -58, -86, -8
7, -88, -135, -142, -144; C.I. I.
Food Black-1, -2; C.I. I. Acid Black-1, -2, -7, -16, -24, -26, -28,
-31, -48, -52, -63, -107, -11
2, -118, -119, -121, -156, -17
2, -194, -208; C.I. I. Acid Blue-
1, -7, -9, -15, -22, -23, -27,-
29, -40, -43, -55, -59, -62, -7
8, -80, -81, -83, -90, -102, -1
04, -111, -185, -249, -254; C.I.
I. Acid Red-1, -4, -8, -13, -1
4, -15, -18, -21, -26, -35, -3
7, -110, -144, -180, -249, -25
7; C.I. I. Acid Yellow-1, -3, -4,-
7, -11, -12, -13, -14, -18, -1
9, -23, -25, -34, -38, -41, -4
2, -44, -53, -55, -61, -71, -7
6, -78, -79, -122 and the like.

As the oil-soluble dye, azo dye, metal complex salt dye, naphthol dye, anthraquinone dye, indigo dye, carbonium dye, quinoimine dye, cyanine dye, quinoline dye, nitro dye, nitroso dye, benzoquinone dye, naphthoquinone dye, Examples thereof include naphthalimide dye, perinone dye, phthalocyanine dye, and the like, but are not limited to these.

The water-insoluble dyes and pigments include, but are not limited to, organic pigments, inorganic pigments, colored polymer particles, water-insoluble dyes, disperse dyes and oil-soluble dyes. As the black pigment, furnace black,
Lamp black, acetylene black, carbon black pigments such as channel black and the like, and the like, for example,
Raven7000, Raven5750, Raven
5250, Raven5000 ULTRA II, Ra
ven3500, Raven2000, Raven15
00, Raven1250, Raven1200, Ra
ven1190ULTRA II, Raven1170,
Raven1255, Raven1080, Raven
1060 (above, Colombian Carbon Co., Ltd.), Re
gal400R, Regal330R, Regal66
0R, Mogul L, Black Pearls
L, Monarch700, Monarch800, M
onarch, 880, Monarch900, Mon
arch1000, Monarch1100, Mona
rch1300, Monarch1400 (above made by Cabot), Color Black FW1, Col
or BlackFW2, Color Black F
W2V, Color Black 18, Color
Black FW200, Color Black S
150, Color Black S160, Colo
r Black S170, Pritex35, Pri
texU, Pritex Vrintex140U, P
rintex140V, Special Black
6, Special Black 5, Special
Black 4A, Special Black 4
(Above, manufactured by Degussa), No. 25, no. 33, N
o. 40, No. 47, No. 52, No. 900, N
o. 2300, MCF-88, MA600, MA7, M
A8, MA100 (above, manufactured by Mitsubishi Chemical Co., Ltd.) or the like can be used. Further, magnetic fine particles such as magnetite and ferrite, titanium black and the like can be used as the black pigment.

Cyan color pigments include C.I. I. Pigment Blue-1, C.I. I. Pigment Blue-2, C.I. I. Pigment Blue-3,
C. I. Pigment Blue-15, C.I. I. Pigment Blue-15: 1, C.I. I. Pigment Blue-
15: 3, C.I. I. Pigment Blue-15: 34,
C. I. Pigment Blue-16, C.I. I. Pigment Blue-22, C.I. I. Pigment Blue-60
Etc.

Examples of magenta pigments include C.I. I. Pigment Red-5, C.I. I. Pigment Red-7,
C. I. Pigment Red-12, C.I. I. Pigment Red-48, C.I. I. Pigment Red-4
8: 1, C.I. I. Pigment Red-57, C.I. I.
Pigment Red-112, C.I. I. Pigment Red-122, C.I. I. Pigment Red-123,
C. I. Pigment Red-146, C.I. I. Pigment Red-168, C.I. I. Pigment Red-
184, C.I. I. Pigment Red-202 and the like.

Examples of the yellow pigment include C.I. I. Pigment
Yellow-1, C.I. I. Pigment Yellow-2,
C. I. Pigment Yellow-3, C.I. I. Pigment yellow-12, C.I. I. Pigment Yellow-
13, C.I. I. Pigment Yellow-14, C.I. I.
Pigment yellow-16, C.I. I. Pigment Yellow-17, C.I. I. Pigment Yellow-73,
C. I. Pigment Yellow-74, C.I. I. Pigment Yellow-75, C.I. I. Pigment Yellow-83, C.I. I. Pigment Yellow-93, C.I.
I. Pigment Yellow-95, C.I. I. Pigment Yellow-97, C.I. I. Pigment Yellow-9
8, C.I. I. Pigment Yellow-114, C.I. I.
Pigment Yellow-128, C.I. I. Pigment
Yellow-129, C.I. I. Pigment Yellow-1
51, C.I. I. Pigment Yellow-154 and the like.

In addition to the above three primary color pigments of black and cyan, magenta and yellow, specific color pigments such as red, green, blue, brown and white, metallic luster pigments such as gold and silver, colorless extender pigments and plastic pigments. Etc. can also be used. In addition to the above, a newly synthesized pigment may be used. Further, these pigments may be surface-treated. As the surface treatment method, for example, alcohol, acid,
Examples include treatment with a coupling agent such as a base and a silane compound, polymer grafting treatment, and plasma treatment.
The colorant used in the present invention preferably has a small content of organic and inorganic impurities. Generally, commercially available coloring agents have a high content of impurities, so it is desirable to use a purified product thereof. The colorant used in the ink composition of the present invention is preferably 0.1 to 20% by mass, and particularly preferably 0.4 to 10% by mass with respect to the mass of the ink.

According to a preferred embodiment of the present invention, these pigments are preferably added to the ink composition as a pigment dispersion obtained by dispersing them in an aqueous medium with a dispersant or a surfactant. As a preferable dispersant, a dispersant which is commonly used for preparing a pigment dispersion, for example, a polymer dispersant can be used. It will be apparent to those skilled in the art that the dispersant and surfactant contained in this pigment dispersion also function as the dispersant and surfactant of the ink composition.

The polymerizable compound contained in the ink composition is
The compound equivalent to the polymerizable compound mentioned in the reaction solution is used. The content of the polymerizable compound in the ink composition is 30
To about 98% by mass, preferably 60 to 98% by mass
It is a range of degrees.

A water-soluble organic solvent may be used in the above reaction liquid and ink composition. Examples of the water-soluble organic solvent include alcohols (eg, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (eg, ethylene glycol, diethylene glycol). , Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), polyhydric alcohol alkyl ethers (eg ethylene glycol) Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Lumpur dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monoethyl ether, triethylene glycol monomethyl ether,
Triethylene glycol monobutyl ether, triethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, etc.), amine Kinds (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine,
N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc., amides (for example, formamide, N, N-). Dimethylformamide, N, N-dimethylacetamide, etc., heterocycles (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone,
1,3-dimethyl-2-imidazolidinone etc.), sulfoxides (eg dimethyl sulfoxide etc.), sulfones (eg sulfolane etc.) and the like. Of these, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether are preferable.

In another one of the ink jet recording methods according to the present invention, water or a boiling point of 30 in the ink composition is used.
The content of the solvent at 0 ° C. or lower is 60% by mass or less. Among the ink compositions, water or a boiling point of 3
The content of the solvent at 00 ° C or lower is preferably as small as possible, and may be 0% by mass.

The solvent having a boiling point of 300 ° C. or lower means a substance which does not participate in the polymerization reaction and has a boiling point of 300 ° C. or lower.
Specific examples include alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and iso-butyl alcohol; Amides such as dimethylformamide and dimethylacetamide; ketones or keto alcohols such as diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, Alkylene such as triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol Alkylene glycols having 2 to 6 carbon atoms; glycerin: lower alkyl of polyhydric alcohol such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether Ethers; N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, acetone, acetonitrile, N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), etc. Can be mentioned.

Water or boiling point of the ink composition is 300 ° C.
When the content of the following solvent exceeds 60% by mass, it is inferior in quick-drying property and bleeding and lacks adaptability to many recording materials. <Other additives> As additives to the ink of the present invention, other additives such as a viscosity modifier, a reaction diluent, a filler, a flow aid, a thixotropic agent, a wetting agent, a defoaming agent, and a plasticizer. Can be included. In addition, stabilizers such as light stabilizers, ultraviolet absorbers, antioxidants, polymerization inhibitors, and corrosion inhibitors, or Si compounds, waxes, etc. may be added.

[0049]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to the forms in these examples. (Preparation of Ink Composition) C.I. I. pigment Black 7 5.0% by mass C.I. I. Pigment Blue 15: 3 2.5 mass% C.I. I. pigment Red 122 3.0 mass% C.I. I. Pigment Yellow 93 2.5% by mass The compounds shown in Table 1 were added to each of the above colorants to prepare an ink composition.

[0050]

[Table 1]

Photopolymerizable compound 1: Shin-Nakamura Chemical Co., Ltd. EA-1020 Photopolymerizable compound 2: Shin-Nakamura Chemical Co., Ltd. A-9300 Photopolymerizable compound 3: 1,6-hexanediol diacrylate Photopolymerizable compound 4 : 2-phenoxyethyl acrylate polymerization initiator: Irgacure 18 manufactured by Ciba-Geigy Japan
4 * Remaining mass (unit: mass%) (Preparation of reaction solution) A reaction solution as shown in Table 2 below was prepared. The photopolymerizable compound, the polymerization initiator and * are in accordance with Table 1.

[0052]

[Table 2]

(Production of Recording Medium) The recording medium has a thickness of 60.
A μm PET sheet was used, and the PET sheet was kept at room temperature (25 ° C.). (Inkjet recording) An inkjet head was filled with the obtained ink and a reaction liquid, and was ejected onto a PET sheet under the following conditions. The temperature of the ink and head was adjusted so that the viscosity was 7 mPa · s. When evaluating the storage stability of the ink, output was performed under the same temperature conditions as before the ink was stored.

After printing on a PET sheet, it was irradiated with ultraviolet rays under the following conditions. The irradiation lamp used was a metal halide type having a wavelength of 365 nm, and ultraviolet irradiation was performed at an ultraviolet irradiation amount of 1,000 mJ / cm ² .

Density measurement and color measurement are carried out by a colorimeter (manufactured by Gretag Macbeth Co .; spectorino, keywiza).
rd) was performed under the following conditions.

Light source: D50 visual field; 2 ° visual field density; ANSI T white standard; abs filter; No-filter (evaluation) After inkjet recording, the following evaluation was performed.
The results obtained are shown in Table 3 below. [Bleeding] An image pattern in which 8-point characters were arranged on a solid density of magenta and 1 dot of each color were output, and the quality after 10 minutes was magnified with a loupe and visually evaluated.

∘: a dot shape is a perfect circle without shakiness ○: a slight shading can be seen, but a dot shape is a perfect circle Δ: a shakyness is visible, and the dot shape is slightly disturbed ×: a shakyness is visible , Dot shape is also poor [ink storability] After being left at room temperature for 10 days, the same was filled in an inkjet head and discharged.

○: Stable ejection △: Ejected but partially clogged ×: Not ejected [Drying property] Rubbing the recording portion with a finger immediately after irradiation with ultraviolet rays, the following points were evaluated. went.

[0059] ○: No ink stickiness and no stain △: No ink stains, but sticky ×: Ink stains your fingers

[0060]

[Table 3]

As is clear from Table 3, ink composition 1
4 to 4 and the reaction liquids 1 to 4 are excellent in drying property and bleeding, and ink storage property is also good. However, the ink composition 5 containing the polymerization initiator
Not only is the ink storability poor when only used,
It can be seen that neither the bleeding nor the drying property is sufficient, and when the ink composition 6 containing the photopolymerizable compound in an amount of less than 30% is used, neither the bleeding nor the drying property is practical.

[0062]

According to the present invention, there is provided an ink jet recording method in which a polymerizable resin is applied to a recording medium to print by using two liquids of an ink composition and a reaction liquid. It has a remarkably excellent effect that it can provide an inkjet recording method which is excellent and adaptable to many recording materials.

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Claims (4)

[Claims] 1. An inkjet recording method for printing by depositing an ink composition and a reaction liquid on a recording medium,
The ink composition contains a polymerizable compound and a colorant, and the content of the polymerizable compound in the ink composition is 30 to 9
It is 8% by mass, and the reaction liquid contains a polymerizable compound and a polymerization initiator, wherein the inkjet recording method is characterized. 2. An inkjet recording method for printing by adhering an ink composition and a reaction liquid to a recording medium,
An ink jet recording method, wherein the content of water or a solvent having a boiling point of 300 ° C. or less in the ink composition is 60% by mass or less. 3. The ink jet recording method according to claim 1, wherein the polymerization initiator of the reaction liquid is a photopolymerization initiator. 4. The ink jet recording method according to claim 1, wherein the colorant is a pigment.