JP2001322349A - Active energy ray-curable composition for forming ink receiving layer, printing method and printed matter - Google Patents

Abstract

[PROBLEMS] To improve the water resistance of an ink receiving layer itself formed on the label side of an optical information medium, the adhesion between an ink receiving layer and a synthetic resin substrate, and the image quality. It is an object of the present invention to provide a composition for forming an ink receiving layer that can be formed. An active energy ray-curable composition for forming an ink receiving layer comprising a liquid compound containing an ethylenic double bond (excluding an organic silane compound) and an organic silane compound. A printing method in which a cured product of the above composition is formed on a synthetic resin substrate, an active energy ray-curable ink is printed on the cured product by an inkjet method, and the composition is cured by irradiation with active energy rays.

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 composition for forming an ink receiving layer, a printing method for recording an ink receiving layer obtained therefrom by an ink jet method, and a printed material.

[0002]

2. Description of the Related Art At present, the CD system is widely used among information recording media using condensed laser light. As a practical example of the optical information medium of the CD system, a CD (compact disk) for music, a CD-ROM for data of a computer, and a CD-ROM such as a game machine are well known as reproduction-only ones. On the other hand, CD-Rs and the like have become widespread as optical information media capable of optical recording as well as reproduction. These are configured to be capable of accommodating a large variety of small amounts of information or, as the ultimate form thereof, accommodating different information for each optical information medium. In addition, since the amount of information will increase in the future, DVDs, DVD-Rs, DVD-RAMs, and the like that can record a large amount of information have begun to spread gradually.

In such an optical information recording medium, the content of the recorded optical information is specified on a surface (hereinafter, referred to as a label surface) opposite to a surface on which the optical information is reproduced and / or recorded. (Hereinafter, referred to as labeling) for displaying characters, pictures, and the like. The mass-produced music CDs, computer CD-ROMs,
In the case of a game machine CD-ROM or the like, labeling is generally performed on the label surface by printing means such as screen printing or offset printing. But for self-published music
In the case of CDs and small-volume music CDs, it is wasteful to create a printing plate to create a label surface. Further, in the case of an optical information medium for recording and reproducing different optical information for each medium, such as a CD-R, it is desired that the user can label the label surface by himself after recording the information.

[0004] Here, the simplest labeling method is a method of writing directly on the label surface with a writing instrument such as a felt pen, or a method of sticking a sheet-like material having an adhesive applied to the back surface to the label surface. However, in the former case, there is a problem that the degree of freedom of expression is limited and the appearance is deteriorated. On the other hand, in the case of the latter, the thickness of the label surface is partially changed by sticking a sheet-like material, which causes eccentricity or surface blur of the optical information medium when recording or reproducing optical information. However, none of these methods was satisfactory as a labeling method.

As one of the labeling methods for solving the above problems, an ink receiving layer is formed on the label side, and ink jet recording is performed on the receiving layer. For example, Japanese Patent Application Laid-Open No. 6-60432 discloses a coating agent for forming a receptor layer in which a water-soluble polymer is dissolved in an aqueous medium, and silica, alumina, aluminum hydroxide and the like are further added as a filler. I have. However, since these coating agents are generally coated on the entire surface of the base material and are coated relatively thickly, a long process is required to evaporate water in the coating agent. Therefore, it is not suitable for printing only a necessary portion of the base material in addition to coating the entire surface of the base material.

Japanese Patent Application Laid-Open No. 7-44888 discloses a radiation-curable ink containing a water-soluble monomer, a hydrophobic polymer, and an inorganic filler.
According to this technique, although the water resistance of the ink receiving layer itself is improved, the formed ink jet recorded image is inferior in water resistance, or when the recorded image is left for a long time in a high temperature and high humidity environment. In such an environment, the phenomenon that the ink absorbed in the ink receiving layer diffuses in the receiving layer and the entire image is contaminated, that is, in such an environment, Further, there is a defect that unevenness of a solid portion and boundary bleeding between different colors occur due to poor ink absorption in a recording portion having a high print duty.

[0007] JP-A-2000-34435 discloses a radiation-curable ink containing a water-soluble monomer, a hydrophobic monomer and an inorganic filler. According to this technique, although the ink receptivity and the drying property are improved, the dot shape of the formed ink jet recording image is dented in the shape of a donut at the center of the dot and becomes thin, resulting in discoloration of the image and uneven density. And also
There is a drawback when a phenomenon occurs in which the ink dot diameter changes depending on the state of the base material and affects the stability of image density.

[0008]

SUMMARY OF THE INVENTION The present invention is directed to improving the water resistance of the ink receiving layer itself formed on the label side of the optical information medium, improving the adhesion between the ink receiving layer and the synthetic resin substrate, and improving image quality. An object of the present invention is to provide a composition for forming an ink receiving layer which can be improved.

Further, the present invention provides an ink jet recording method comprising the steps of:
It has excellent drying properties, and even if the formed recorded image is left for a long time in a high-temperature and high-humidity environment, the image is not deteriorated and the optical information medium itself is hardly deteriorated. An object of the present invention is to provide a printed matter having an optimal label surface.

Further, the present invention provides a printing method for recording label information of an optical information medium or the like by an ink jet recording method using an active energy ray-curable ink jet ink excellent in water resistance, drying property and adhesion. Aim.

[0011]

SUMMARY OF THE INVENTION The present invention provides an active energy ray-curable composition for forming an ink receiving layer comprising a liquid compound containing an ethylenic double bond (excluding an organic silane compound) and an organic silane compound. About things. Furthermore, the present invention relates to the above composition further containing a resin (excluding an organic silane compound) inert to active energy rays. Furthermore, the present invention relates to a printing method in which a cured product of the above composition is formed on a synthetic resin substrate, an active energy ray-curable ink is printed on the cured product by an inkjet method, and the composition is irradiated with active energy rays and cured. . Furthermore, the present invention relates to the above printing method, wherein the active energy ray-curable ink contains a pigment, a compound containing two or more ethylenic double bonds, and N-vinylformamide. Furthermore, the present invention relates to a printed matter obtained by the above method. Further, the present invention relates to the printed matter, wherein the printed matter is an optical information recording medium such as a compact disk or a DVD.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid compound containing an ethylenic double bond to be incorporated in the composition for forming an ink receiving layer of the present invention includes those called monomers, prepolymers, oligomers and the like. Preferably, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tri (2-hydroxyethyl isocyanurate) There are triacrylate, propoxylate glyceryl triacrylate, urethane acrylate, epoxy acrylate, polyester acrylate and the like, and these may be used alone or in combination of two or more as needed.

The organic silane compound to be incorporated in the ink receiving layer forming composition of the present invention includes γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,
Silane coupling agents such as aminopropyltriethoxysilane, polyether-modified silicone, epoxy-modified silicone, amino-modified silicone, carboxyl-modified silicone, mercapto-modified silicone, methacryl-modified silicone, dimethylpolysiloxane, dimethylpolysiloxane-polyoxyalkylene Examples include polymers, modified silicone resins such as alcohol-modified silicone and alkoxy-modified silicone, and polyorganosiloxanes.

The organic silane compound of the present invention reduces the contact angle of the ink-jet ink, maintains the dot roundness, and improves the adhesion to the synthetic resin substrate and the friction resistance of the ink. The organic silane compound is 0.000001 per 100 parts by weight of the liquid compound having an ethylenic double bond.
0.5 parts by weight, preferably 0.00001 to 0.0 parts by weight.
5 parts by weight are used. If the addition amount of the organic silane compound is smaller than the above value, the dot roundness is not improved because the contact angle of the ink does not decrease, and if it is larger than the above value, the ink jet ink is repelled and the printing characteristics are deteriorated. .

The composition for forming an ink receiving layer of the present invention includes:
A thermoplastic resin or a thermosetting resin inert to the active energy ray can be blended. As the resin, for example, polyvinyl chloride, poly (meth) acrylate, epoxy resin, polyurethane resin, cellulose derivative (eg, ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl resin Acetal resin, diallyl phthalate resin, butadiene-acrylonitrile copolymer, acrylic resin, styrene-acrylic resin, styrene-maleic acid resin, rosin resin, rosin ester resin, ethylene-vinyl acetate resin, petroleum resin , Coumarone indene resin, terpene phenol resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin,
Cellulose-based resins, polyvinyl chloride-based resins, xylene resins, alkyd resins, aliphatic hydrocarbon resins, butyral resins, silicone resins, maleic acid resins, fumaric acid resins, and the like are included.

In order to improve suitability for silk screen printing and adhesion to a synthetic resin substrate, a resin inert to these active energy rays is used in an amount of 0 to 100 parts by weight of a liquid compound containing an ethylenic double bond. It is preferable to add 1 to 30 parts by weight.

The composition for forming an ink receiving layer of the present invention includes:
A compound that reduces the contact angle, such as a fluorine compound, may be added as necessary.

In the present invention, the active energy rays include electron beams, γ rays, ultraviolet rays, visible rays and the like. When an ultraviolet ray or a visible ray is used as the active energy ray, it is preferable to add a photopolymerization initiator. As a photopolymerization initiator, benzophenone, 4,4-diethylaminobenzophenone, diethylthioxanthone, 2-methyl-1-
(4-methylthio) phenyl-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenylsulfide, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 1-
Hydroxy-cyclohexyl-phenyl ketone, bis-
2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide, 1- [4- (2-
Hydroxyethoxy) -phenyl] -2-hydroxy-
2-methyl-1-propan-1-one, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6-trimethylbenzyl-diphenylphosphine oxide,
-Benzyl-2-dimethylamino-1- (morpholinophenyl) -butan-1-one and the like. In combination with a photopolymerization initiator, a photo-promoting agent such as ethyl p-dimethylaminobenzoate and pentyl 4-dimethylaminobenzoate may be used.

The composition for forming an ink receiving layer of the present invention may contain a leveling agent, an antifoaming agent, a dye, a pigment and the like, if necessary. The composition for forming an ink receiving layer of the present invention can be printed by a printing method such as gravure printing, flexographic printing, or screen printing, and irradiated with active energy rays to form a cured film. In order to give sufficient receiving performance to the ink jet ink, the thickness of the ink receiving layer must be 5
To 100 μm, preferably about 10 to 40 μm.
For this reason, screen printing in which the thickness of the ink receiving layer is easily adjusted to the above range is most preferable as the means for forming the ink receiving layer.

The composition for forming an ink receiving layer of the present invention can be applied to a base material such as a synthetic resin, a metal plate, and paper as in an optical information recording medium.

According to the printing method of the present invention, an active energy ray-curable inkjet ink is discharged from an orifice of a recording head into an ink receiving layer formed on a base material such as an optical information recording medium in accordance with a recording signal to record information. It is to cure by irradiation with energy rays.

The ink-jet ink of the present invention contains at least a pigment and a compound having two or more ethylenic double bonds.

As the pigment, achromatic pigments such as carbon black, titanium oxide and calcium carbonate or chromatic organic pigments can be used. Examples of the organic pigment include insoluble azo pigments such as toluidine red, toluidine maroon, hanza yellow, benzidine yellow, and pyrazolone red; soluble azo pigments such as litol red, helio bordeaux, pigment scarlet, and permanent red 2B; alizarin, indanthrone, and thioindigo. Derivatives from vat dyes such as maroon; phthalocyanine-based organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone-based organic pigments such as quinacridone red and quinacridone magenta; perylene-based organic pigments such as perylene red and perylene scarlet; isoindolinone yellow , Organic pigments such as isoindolinone orange, pyranthrone red and pyranthrone orange, Digo-based organic pigments, condensed azo-based organic pigments, benzimidazolone-based organic pigments, quinophthalone-based organic pigments such as quinophthalone yellow, isoindoline-based organic pigments such as isoindoline-yellow, and other pigments such as flavanthrone yellow and acylamide yellow , Nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine violet and the like.

Among the above pigments, quinacridone organic pigments, phthalocyanine organic pigments, benzimidazolone organic pigments, isoindolinone organic pigments, condensed azo organic pigments, quinophthalone organic pigments, isoindoline organic pigments, etc. Is preferred because of its excellent light resistance. The organic pigment has an average particle size of 10 to 150 n as measured by laser scattering.
It is preferably a fine pigment having a particle size of m. When the average particle size of the pigment is less than 10 nm, the light resistance is reduced due to the decrease in the particle size. When the average particle size is more than 150 nm, it is difficult to maintain a stable dispersion, and the pigment tends to precipitate.

The organic pigment can be made fine by the following method. That is, at least 3 parts by weight of an organic pigment, a water-soluble inorganic salt at least 3 times the weight of the organic pigment, and a water-soluble solvent.
The mixture composed of the two components is made into a clay-like mixture, kneaded strongly with a kneader or the like, pulverized and then poured into water, and stirred with a high-speed mixer or the like to form a slurry. Next, filtration and washing of the slurry are repeated to remove the water-soluble inorganic salt and the water-soluble solvent. In the miniaturization step, a resin, a pigment dispersant and the like may be added. Examples of the water-soluble inorganic salt include sodium chloride and potassium chloride. These inorganic salts are at least 3 times the weight of the organic pigment,
Preferably, it is used in a range of 20 weight times or less. When the amount of the inorganic salt is less than 3 times by weight, a treated pigment having a desired size cannot be obtained. On the other hand, when the amount is more than 20 times by weight, the washing process in the subsequent step is large, and the substantial processing amount of the organic pigment is reduced.

The water-soluble solvent is used for forming an appropriate clay state between the organic pigment and the water-soluble inorganic salt used as a crushing aid, and for efficiently performing sufficient crushing. Although there is no particular limitation, a high boiling solvent having a boiling point of 120 to 250 ° C. is preferred from the viewpoint of safety because the temperature rises during kneading and the solvent is easily evaporated. Examples of the water-soluble solvent include 2- (methoxymethoxy) ethanol, 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 molecular weight Polypropylene glycol and the like.

In the present invention, in order to obtain a sufficient concentration and a sufficient light resistance, the pigment is used in the ink-jet ink.
Preferably, it is contained in the range of 15 to 15% by weight.

The compounds of the present invention having two or more ethylenically unsaturated double bonds include those called prepolymers and oligomers, and specifically include ethylene glycol diacrylate, diethylene glycol diacrylate, and the like. 1,6-hexanediol di (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, urethane acrylate, Epoxy acrylate, polyester acrylate and the like can be mentioned. One or more of these compounds may be used as needed. These compounds having two or more ethylenic double bonds are preferably used in an amount of 30 to 80% by weight in the ink because the curing rate and the crosslink density are increased, and the water resistance, hardness, gloss and the like are improved.

The inkjet ink of the present invention preferably contains N-vinylformamide. N-vinylformamide has excellent photopolymerizability, exhibits good curability and adhesion to a substrate, and has a very low viscosity, and is used in other inks such as prepolymers, pigment dispersants, and photopolymerization initiators. Since the component (1) is well dissolved, the pigment can be dispersed well and the viscosity can be kept low. N-vinylformamide is preferably used in an amount of 20 to 60% by weight in the ink.

Further, the ink-jet ink of the present invention includes:
A compound (monomer) having one ethylenic double bond such as 2-hydroxyethyl (meth) acrylate, tetrahydrofurfuryl acrylate, isoformyl acrylate, or 2- (2-ethoxyethoxy) ethyl acrylate may be contained. . These monomers preferably suppress the drying of the ink at room temperature, have a high curing speed in the recording medium, and have flow characteristics that follow a high-speed ejection head. Further, a monomer having a high boiling point is preferable because it acts as a dispersion medium for the pigment and functions to prevent the ink from sticking at the nozzle tip.

In the present invention, the compound containing one or more ethylenic double bonds is preferably 25 to 90% by weight in the ink including N-vinylformamide.

When an ultraviolet ray or a visible ray is used as the active energy ray in the present invention, the above-mentioned photopolymerization initiator is blended in the ink. In the ink-jet ink of the present invention, in order to enhance the stability of the ink over time and the on-machine stability in a recording device, an aromatic derivative such as hydroquinone, p-methoxyphenol, t-butylcatechol, or pyrogallol is used. It is preferable to mix 0.01 to 5% by weight in the ink.

Examples of the pigment dispersant of the present invention include a carboxylic acid ester having a hydroxyl group, 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, Molecular weight unsaturated acid ester, high molecular weight 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 mentioned.

Specific examples of the pigment dispersant include BYK C
"Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terra-20" manufactured by Hemie
3/204 (high molecular weight polycarboxylate) "," Dis
perbyk-101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl-containing carboxylate), 110 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165,
166, 170 (polymer copolymer) "," 400 ",
"Bykumen" (high molecular weight unsaturated acid ester),
"BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid)", "P104S, 240S (high molecular weight unsaturated acid polycarboxylic acid and silicon type)", "Lacti
mon (long-chain amine, unsaturated acid polycarboxylic acid, and silicon) ".

In addition, "Efka 44, 46, 47, 48, 49, 54, 63," manufactured by Efka Chemicals, Inc.
64, 65, 66, 71, 701, 764, 766 ",
"Efka polymer 100 (modified polyacrylate), 1
50 (aliphatic modified polymer), 400, 401, 40
2, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine) ",
Kyoeisha Chemical Co., Ltd. "Floren TG-710 (urethane oligomer)", "Flonon SH-290, SP-10"
00, "Polyflow No. 50E, No. 300 (acrylic copolymer)", "DISPARON" manufactured by Kusumoto Kasei Co., Ltd.
KS-860, 873SN, 874 (polymer dispersant),
# 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester type) ".

Further, “Demol RN, N (sodium salt of formalin condensate of naphthalenesulfonic acid)” manufactured by Kao Corporation,
MS, C, SN-B (sodium salt of aromatic sulfonic acid formalin condensate), EP "," Homogenol L-18
(Polycarboxylic acid type polymer), "Emulgen 920, 9
30, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether), "Acetamine 24
(Coconut amine acetate), 86 (stearylamine acetate) ", manufactured by Zeneca Corporation
0 (phthalocyanine ammonium salt), 13240,
13940 (polyesteramine-based), 17000 (fatty acid amine-based), 24000 ", Nikko Chemical's" Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 ( Hexaglyceryl tetraolate) "and the like.

As the pigment derivative, a functional group effective for dispersing a pigment, such as a phthalimidomethyl group, an amino group, or a triazine group, is introduced into the pigment molecular skeleton. Preferably,
A pigment derivative represented by the following general formula (1) is used. P- [XYZN (R1) R2] n General formula (1) (wherein P is an organic dye residue and X is S, C, N,
A divalent linking group consisting of a chemically rational combination composed of 2 to 15 atoms selected from O and H;
Is a direct bond, -NR- (where R is H or C 1
Z is an alkylene group having 1 to 6 carbon atoms, and R 1 and R 2 are each independently an alkyl group having 1 to 18 carbon atoms which may be substituted (is R1 and R2 may form a heterocyclic ring), and n represents an integer of 1 to 3. )

Specific examples of the organic dye residue P include azo, phthalocyanine, quinacridone, benzimidazole, anthraquinone, perylene, perinone, thioindigo, dioxazine, isoindolinone, quinophthalone, Dye residues such as triphenylmethane and metal complex salts are exemplified.

X is, for example, -SO _2- , -CO
_{-, - CH 2 -, -} CH 2 S -, - CR, H 2 O -, -
COO -, - NH -, - CH 2 NHCOCH-, or is a combination thereof, among others -SO ₂ -,
—CO— and —CH ₂ — are preferred. When a heterocyclic ring is formed by R1 and R2, N, O, and S may be mentioned as constituent elements other than carbon of the heterocyclic ring.

Although the molecular skeleton of the organic pigment and the molecular skeleton of P in the pigment derivative do not necessarily have to coincide with each other, usually, the same system is combined from the viewpoint of hue. It is preferable to combine a phthalocyanine-based residue, a quinacridone-based residue for a red pigment, and a benzimidazole-based residue for a yellow pigment.

Specific examples of the pigment derivative include compounds a to g represented by the following organic dye residues / substituents. a: CI Pigment Blue 15 / -SO2 NH (CH2) 2 N (C2 H5) 2 b: CI Pigment Yellow 24 / -SO2 NH (CH2) 2 N (C3 H7) 2 c: CI Pigment Violet 19 / -SO2 NH (CH2) 3 N (C4 H9) 2 d: CI Pigment Blue 15 / -CH2 S-CH2 N (C3 H7) 2 e: CI Pigment Yellow 83 / -SO2 NH (CH2) 3 N (C2 H5) 2 f: CI Pigment Yellow 108 / -CH2 O-CH2 N (C2 H5) 2 g: CI Pigment Violet 19-CH2 S-CH2 N (C4 H9) 2

The pigment dispersant of the present invention may contain 0.1 to
It is preferable to contain a dispersant in the range of 10% by weight. Further, these pigment dispersants may be added during the above-mentioned pigment refining step.

In the ink-jet ink of the present invention, an organic solvent can be used for the purpose of adjusting the amount of fixation. The organic solvent is a medium for dispersing the pigment together with the active energy ray-curable compound, and functions as a solubilizing agent for the resin, a viscosity regulator, and a drying regulator. However, in the present invention, it is preferable to use the non-permeable recording medium in order to reduce unevenness of an image. Among them, an organic solvent having a boiling point of 120 ° C. or lower serves as a dispersion medium for the pigment and functions as a good solvent for the fixing resin, so that it is preferably used. Further, in the non-permeable non-recording medium, a solvent having a low boiling point can be used to improve the drying speed.

As the organic solvent, alcohol solvents, aromatic hydrocarbon solvents, ketone solvents, ester solvents,
Examples thereof include aliphatic hydrocarbon solvents, higher fatty acid solvents, carbitol solvents, cellosolve solvents, higher fatty acid ester solvents, and the like. Examples of the alcohol solvent include methanol, ethanol, propanol, butanol and the like. As the aromatic hydrocarbon solvent, toluene,
Xylene and the like can be mentioned. Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Examples of the ester solvent include ethyl acetate and butyl acetate.

The organic solvent is preferably contained in the ink in the range of 0 to 30% by weight. These solvents can be used alone, but adjustment of viscosity, formation and drying of dots in a non-permeable medium, adjustment of penetration into paper,
Two or more types can be used in combination for adjusting the wettability with the ink contacting system of the head and the printer.

In order to improve the adhesion of the ink to the recording medium or to adjust the spread of the dots of the ink on the recording medium, the above-mentioned active energy ray-curable ink is used. Compound and / or
Alternatively, a resin having no ethylenic double bond that is soluble in an organic solvent can be contained, and a thermosetting or thermoplastic resin can be used as a part of the ink. For these, resins having excellent compatibility with the active energy ray-curable compound can be used. As the resin, those exemplified as resins that can be blended in the composition for forming an ink receiving layer can also be used here.

The ink-jet ink of the present invention is produced by well dispersing a pigment together with an active energy ray-curable compound and, if necessary, a resin, an organic solvent and a pigment dispersant using a conventional dispersing machine such as a sand mill. You. It is preferable that a concentrated solution having a high pigment concentration is prepared in advance and then diluted with an active energy ray-curable compound. Sufficient dispersion is possible even with a normal dispersing machine, so that excessive dispersing energy is not required and a large dispersing time is not required. An ink with excellent properties is prepared. The ink is preferably filtered with a filter having a pore size of 3 μm or less, more preferably 1 μm or less.

The inkjet ink of the present invention has a temperature of 25 ° C.
It is preferable to adjust the viscosity at 5 to 50 mPa · s. Inks having a viscosity of 5 to 50 mPa · s at 25 ° C. exhibit stable ejection characteristics, especially from a normal head having a frequency of 4 to 10 KHz to a high frequency head of 10 to 50 KHz. When the viscosity is less than 5 mPa · s, a decrease in the followability of discharge is observed in a high-frequency head, and when the viscosity exceeds 50 mPa · s, even if a mechanism for lowering the viscosity by heating is incorporated in the head, the discharge itself is not improved. As a result, the stability of the ejection becomes poor and the ejection becomes impossible.

The ink-jet ink of the present invention is
In the case of a piezo head, it is preferable to use an ink having an electric conductivity of 10 μS / cm or less and having no electrical corrosion inside the head. In the continuous type, it is necessary to adjust the electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mS / cm or more.

[0050]

The present invention will be described below with reference to examples. In the examples, “parts” means “parts by weight”. The performance of the ink receiving layer printed on the substrate was evaluated based on the presence or absence of image density unevenness and adhesion of the ink jet printed matter when the ink jet printing was performed on the receiving layer.

Examples 1 to 4 and Comparative Examples 1 to 3 (Preparation of compositions for forming active energy ray-curable receiving layer) Various raw materials were blended in the weight ratios shown in Table 1 below, and these were kneaded with three rolls. By fleshing, various active energy ray-curable receiving layer forming compositions were obtained.

[0052]

[Table 1]

The compounds in the table are as follows. B66: Copolymer of methyl methacrylate and butyl methacrylate ("Paraloid B66" (manufactured by Rohm and Haas) TPGDA: Tripropylene glycol diacrylate UV7000B: Urethane acrylate oligomer ("Shikou UV7000B" manufactured by Nippon Gosei Co., Ltd.) B3672- 40: Urethane acrylate oligomer ("Photoglaze B3672-40" manufactured by Road Corporation) I907: Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy) ITX: Photopolymerization initiator ("Kayacure ITX" manufactured by Nippon Kayaku) Tego: Polyether-modified silicone (“TegoRad2600” manufactured by Tego Chemi) FZ2123: Dimethylpolysiloxane-polyoxyalkylene copolymer (“FZ-2123” manufactured by Nippon Unicar) 330: Silane coupling agent (“Silaace S-330”) "Chisso Corporation) FZ3711: Alcohol Sex silicone ( "FZ-3722" manufactured by Nippon Unicar Co., Ltd.)

(Active Energy Ray-Curable Inkjet Ink) Parts and% in Examples are parts by weight and% by weight, respectively. The raw materials shown in Table 2 were placed in a sand mill and dispersed for 4 hours to prepare a concentrated liquid for inkjet.
Next, a mixture having the following composition was mixed and dispersed for 30 minutes using a stirrer having propeller type blades, and then pressure-filtered with a 3 μm membrane filter to obtain a CMYK inkjet ink.

The concentrate of Table 2 40 parts Trimethylolpropane triacrylate 27.7 parts N-vinylformamide 25.7 parts Irgacure 907 6 parts Isopropylthioxanthone 3 parts

This ink was printed by a printer having a piezo head, and dried and cured by a UV irradiation device (one high-pressure mercury lamp: output 120 W) at a conveyor speed of 20 m / m.
The test was performed under the conditions of “in”.

[0057]

[Table 2]

The compounds in the table are as follows. Pigment ・ P1 Crude copper phthalocyanine “copper phthalocyanine”: 2
50 parts, sodium chloride: 2500 parts, blue pigment dispersant (P- [CH2NH (CH2) 4N (CH3) 2] 3,
P is a copper phthalocyanine residue): 25 parts and "polyethylene glycol 300": 160 parts were charged into a 1-gallon kneader made of styrene, and a treated pigment was obtained in the same manner as in P1.

P2 quinacridone red pigment (Ciba)
Geigy's "Sincacia Magenta RT-355-
D "): 250 parts, sodium chloride: 2500 parts, red pigment dispersant (P- [CH2NH (CH2) 4N (CH
3) 2) 3, P: quinacridone residue): 25 parts and "polyethylene glycol 300": 160 parts were charged into a 1-gallon kneader made of styrene, and a treated pigment was obtained in the same manner as in P1.

P3 Benzimidazolone yellow pigment (Hostapalm Yellow manufactured by Hoechst): 250 parts, sodium chloride: 2500 parts, yellow pigment dispersant (P- [CH2
NH (CH2) 4N (CH3) 2] 3, P is a benzimidazole residue): 25 parts and "polyethylene glycol 300": 160 parts were charged into a 1-gallon kneader made of styrene, and a treated pigment was obtained in the same manner as in P1. .・ P4 carbon black pigment “Printex 150
T ”(made by Degussa)

Monomer • NVF N-vinylformamide (“Beam Set 77
0) Arakawa Chemical Co., Ltd. ・ TPGDA Tripropylene glycol diacrylate (“KS-TPGDA” manufactured by Nippon Kayaku) ・ TMPTA Trimethylolpropane triacrylate (“KS-TMPTA” manufactured by Nippon Kayaku) ・ U-acryl 3 Functional urethane acrylate ("Actilane2
51 "Akcros)

Resin ・ R1 rosin ester (“Super Ester 75” manufactured by Arakawa Chemical) ・ R2 hydrogenated rosin (“Ester gum HP” manufactured by Arakawa Chemical)

Dispersant ・ 13940 Polyesteramine-based dispersant (“Solspers® 24000” manufactured by Zeneca) ・ 24000 Aliphatic modified dispersant (“Solspers® 24000”)
・ Baene blue pigment dispersant

The compositions for forming the active energy ray-curable receiving layer obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were screen-printed on a compact disk using a 300-mesh screen, and irradiated with ultraviolet rays. Then, the mixture was cured to form a receiving layer having a thickness of 25 μm. Next, a full-color image is printed on the receiving layer using an active energy ray-curable inkjet ink using an inkjet printer,
The ink jet printing performance was examined. Table 3 shows the results.

[0065]

[Table 3]

Evaluation Method in Table [Substrate Adhesion] A cellophane tape was applied to the ink receiving layer formed on the compact disk, and the ink receiving layer was visually evaluated for changes in the ink receiving layer when peeled off. The adhesion of the layer to the compact disc was evaluated. ○: No peeling ×: Peeling

[Water resistance] After the printed matter was cured, the presence or absence of bleeding of the ink and the outflow of the ink when immersed in water for 1 minute were visually evaluated. ：: Bleeding, no outflow. ×: Bleeding, flow out.

[Ink Drying Property] After printing with an ink jet printer was irradiated with an ultraviolet ray irradiator, the presence or absence of adhesiveness of the ink on the surface was confirmed by finger touch. At 20m / min conveyor speed, evaluate the adhesiveness immediately after irradiation. ：: No tackiness. ×: Adhesive.

[Ink absorption capacity] Cyan, Magenta, Yellow,
A solid image was printed by an ink jet printer using each ink of Black, and after irradiating ultraviolet rays, the degree of bleeding of the adjacent solid images of two colors was visually evaluated. ○: No bleeding ×: Bleeding

[Image Quality] The presence or absence of density unevenness of an image printed by an ink jet printer was evaluated. ○: No density unevenness ×: Density unevenness

[Image Water Resistance] When an image printed by an ink jet printer was immersed in water for 1 minute, the presence or absence of ink bleeding and the flow of ink were visually evaluated. ：: Bleeding, no outflow. ×: Bleeding, flow out.

[Image Adhesion] A cellophane tape was adhered to an image printed by an ink jet printer, and then a change in the image when peeled off was visually evaluated. The adhesion to the hydrophilic ink was evaluated. ○: No peeling ×: Peeling

[0073]

The composition for forming an active energy ray-curable receiving layer according to the present invention can print not only the entire surface of the substrate but also only the necessary portions, and can be carried out quickly without a step of evaporating water. Printing can be completed. Further, the ink receiving layer of the present invention is excellent in dot forming property, dot roundness, ink absorption, ink fixing property, image rub resistance, water resistance of the ink itself, and the ink receiving layer and the synthetic resin base. Very good adhesion to materials. Further, the image formed by ink jet recording on the ink receiving layer is excellent in processability due to good quick-drying property, the dots are sharp and sharp, and the image quality is high. Also, the change in image performance is small. For this reason, the optical information recording medium on which an image is formed by the printing method of the present invention is stable against long-term storage in a high-temperature and high-humidity environment.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09D 11/10 G11B 7/24 534E G11B 7/24 534 571A 571 B41J 3/04 101Y (72) Inventor: Yasuharu Iida Tokyo 2-13-13 Kyobashi, Chuo-ku Toyo Ink Manufacturing Co., Ltd. F-term (reference) 2C056 EA04 EA13 FB01 FC02 FC06 2H086 BA05 BA15 BA19 BA34 BA59 4J039 AB02 AB08 AD01 AD03 AD05 AD07 AD08 AD10 AD11 AD14 AD15 AD18 AD19 AD21 AE02 AE03 AE04 AE05 AE06 AE08 AE11 BC57 EA04 EA05 EA06 EA08 EA10 EA36 EA38 EA42 EA43 EA44 GA02 GA03 GA10 GA24 5D029 PA01

Claims (6)

[Claims] An active energy ray-curable composition for forming an ink receiving layer comprising a liquid compound containing an ethylenic double bond (excluding an organic silane compound) and an organic silane compound. 2. The composition according to claim 1, further comprising a resin inert to active energy rays (excluding an organic silane compound). 3. A cured product of the composition according to claim 1 is formed on a synthetic resin substrate, and an active energy ray-curable ink is printed on the cured product by an ink jet method and irradiated with active energy rays. Printing method to cure. 4. An active energy ray-curable ink comprising a pigment,
Compound containing two or more ethylenic double bonds and N
The printing method according to claim 3, wherein the printing method contains vinyl formamide. 5. A printed matter obtained by the method according to claim 4. 6. The printed matter according to claim 5, wherein the printed matter is an optical information recording medium such as a compact disk or a DVD.