WO2006064748A1 - 活性光線硬化型インクジェットインク及びそれを用いた画像形成方法 - Google Patents
活性光線硬化型インクジェットインク及びそれを用いた画像形成方法 Download PDFInfo
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- WO2006064748A1 WO2006064748A1 PCT/JP2005/022744 JP2005022744W WO2006064748A1 WO 2006064748 A1 WO2006064748 A1 WO 2006064748A1 JP 2005022744 W JP2005022744 W JP 2005022744W WO 2006064748 A1 WO2006064748 A1 WO 2006064748A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
Definitions
- the present invention has good storage stability, light emission and curability after light emission, high density, no gloss unevenness, good color reproducibility, no wrinkles, and high definition.
- the present invention relates to an actinic ray curable inkjet ink capable of obtaining an image and an image forming method using the same.
- ink jet recording methods have been applied to various printing fields such as photographs, various printing, marking, special printing such as color filters, and the like because images can be easily and inexpensively created.
- ink jet recording devices that emit and control fine dots, and ink ink and ink jet ink with improved color reproduction gamut, durability, and emission suitability, coloring material coloring, and surface gloss are dramatically improved. It is now possible to obtain image quality comparable to silver halide photography using special paper.
- the improvement in image quality of today's ink jet recording systems is mainly achieved for the first time in all of ink jet recording devices, ink jet inks and special paper.
- the actinic ray curable inkjet method has a relatively low odor compared to the solvent-based inkjet method.
- JP-A-6-200204 and JP-A-2000-504778 disclose ultraviolet curing.
- Type ink-jet inks are disclosed.
- Image formation by an ultraviolet curable ink jet method is characterized in that a high-quality image can be obtained at low cost, and that an image can be formed on a recording material that does not absorb ink.
- it also has problems peculiar to this ultraviolet curable ink jet system. For example, in the case of forming an image on a recording material that does not absorb ink if ink curing performance is sufficient, image quality deterioration due to mixing of the landed dots with adjacent dots is significant. In particular, when high-definition image formation is required, dot mixing between landed colors becomes a major problem.
- actinic ray curable ink-jet inks using oxysilane compounds, buler ether compounds, and oxetane compounds as photopolymerizable compounds are disclosed (see Patent Documents 1 and 2).
- actinic ray curable inkjet inks using alicyclic epoxy compounds and oxetane compounds as photopolymerizable compounds are disclosed (see Patent Documents 3 and 4).
- each of the proposed methods described above has yet to solve the problem of simultaneously achieving a high-quality image that has good curability and projectability and is free of blurring. Is the current situation.
- ultraviolet curable inkjet inks are expected to be used for outdoor advertising because of their high water resistance. Visibility is important for outdoor advertising applications, and high saturation is required to reproduce vivid colors. In order to increase the saturation with conventional inks, it is necessary to increase the amount of ink attached or increase the pigment concentration in the ink. There were problems such as deterioration in discharge performance and inability to perform stable discharge.
- Isoindoline-based or isoindolinone-based pigments have high fastness such as light resistance and heat resistance and high color development properties, and are mainly used for color filters, with the purpose of improving brightness and light transmittance.
- Examples of use as a color pigment in a radical polymerization system are disclosed (see Patent Documents 5 and 6).
- an isoindoline-based or isoindolinone-based pigment was applied to a cation-polymerizable active light curable inkjet ink, and the cation-polymerizable monomer was
- dispersed inks there are no examples that satisfy storage stability, emission stability, and curability at the same time.Furthermore, when cured after ejection, the ink has high density and no gloss unevenness. I was not able to get high-definition image quality!
- Patent Document 1 Japanese Patent Laid-Open No. 2001-220526
- Patent Document 2 Japanese Patent Laid-Open No. 2002-188025
- Patent Document 3 Japanese Patent Laid-Open No. 2002-317139
- Patent Document 4 Japanese Patent Laid-Open No. 2003-55449
- Patent Document 5 Japanese Patent Application Laid-Open No. 2003-232913
- Patent Document 6 Japanese Patent Laid-Open No. 11-310716
- the present invention has been made in view of the above-mentioned problems, and its purpose is that the storage stability, the emission property and the curability after emission are good, and the color reproducibility without gloss unevenness at a high concentration. It is an object to provide an actinic ray curable inkjet ink that can provide a high-definition image that is favorable and free of wrinkles, and an image forming method using the same.
- actinic ray curable ink-jet ink as described in 1 above, further comprising a compound having an oxetane ring as the cationic polymerizable compound.
- R is an optionally substituted alkyl group having 1 to 10 carbon atoms, and may be substituted.
- ⁇ to ⁇ may have different hydrogen atoms, unsubstituted or substituted
- An image forming method wherein the actinic ray curable inkjet ink according to any one of 1 to 9 above is jetted onto a recording material from an inkjet recording head, and printing is performed on the recording material.
- An image forming method in which the actinic ray curable inkjet ink according to any one of 1 to 9 above is jetted onto a recording material from an inkjet recording head, and printing is performed on the recording material.
- An image forming method comprising irradiating an actinic ray for 0.001 to 1 second after an actinic ray curable inkjet ink has landed on the recording material.
- An image forming method in which the actinic ray curable inkjet ink according to any one of 1 to 9 above is jetted onto a recording material from an inkjet recording head, and printing is performed on the recording material.
- An image forming method comprising: irradiating actinic rays after the light-curable ink-jet ink has landed on the recording material; and a total ink film thickness after curing by irradiating with actinic rays is 2 to 25 111 .
- Image formation in which the actinic ray curable inkjet ink described in 1 to 9 above is shifted from the nozzles of the inkjet recording head onto the recording material, and printing is performed on the recording material.
- a method for forming an image wherein the amount of droplets of the actinic ray curable ink jet ink ejected from the nozzle is 2 to 20 pl.
- the ink jet recording head force is a line head type ink jet recording head. 14. The image forming method according to any one of items 10 to 13, wherein:
- the storage stability, the emission property, and the curability after emission are good, and the color reproducibility is high with high density and no gloss unevenness. It is possible to provide an actinic ray curable inkjet ink capable of obtaining a high-definition image and an image forming method using the same.
- FIG. 1 is a front view showing an example of a configuration of a main part of an ink jet recording apparatus.
- FIG. 2 is a top view showing another example of the configuration of the main part of the ink jet recording apparatus.
- the actinic ray curable inkjet ink is jetted onto the recording material and the actinic ray curable inkjet ink is landed on the recording material, the actinic ray is applied within 0.001 to 1 second.
- Image forming method for irradiating actinic light to curable inkjet ink, total film thickness after ink curable by irradiating actinic light after the actinic radiation curable inkjet ink has landed on the recording material is 2 to 25 / an image forming method that is zm, an image forming method in which the amount of droplets of the actinic radiation curable ink jet ejected from each nozzle of the ink jet recording head is 2 to 20 pl, and the ink jet recording head is a line head type ink jet recording head
- a certain image forming method has good storage stability, light emission and curability after light emission, high density and no uneven gloss, and good color reproducibility. It found that can be realized how the image height fine fine image free from occurrence of the resulting formation is completed the invention.
- the isoindoline-based pigment that can be used in the present invention is not particularly limited.
- CI pigment yellow 139, CI pigment yellow 185, CI pigment orange 66, CI pigment orange 69, CI pigment red There are no particular restrictions on the isoindolinone pigment having 260 isotropic powers, but CI pigment yellow 109, CI pigment yellow 110, CI pigment yellow 173, CI pigment orange 61 and the like can be mentioned.
- the average particle diameter of the pigment particles is preferably 0.05 to 0.5 ⁇ m.
- the maximum particle diameter is 0.5 to: ⁇ / ⁇ ⁇ , preferably 0.
- the pigment, dispersion medium, dispersion conditions, and filtration conditions are appropriately set so that the ratio is 3 to 3 / ⁇ ⁇ .
- the pigment concentration is preferably 1 to LO mass% of the entire ink.
- the dispersant used in the present invention is a polymer dispersant having a basic functional group with an amine value of 5 to 25 mg KOH / g.
- Enomoto Kasei Co., Ltd. A series of ED211, ED214, ED251, etc., and Ajinomoto Fine Technone Ajisu Peri series PB821, PB822, PB824, etc. are not limited to these.
- the amine value according to the present invention is particularly preferably 5 to 19 mg KOHZg from the viewpoint of strength and curability.
- the amine value according to the present invention is defined as follows.
- the surface of the pigment or dispersant has an acid amount and a base amount distribution. When the base amount is larger than the acid amount, the pigment is basic, and the size is called the amine value.
- the amine value of the dispersant was measured by dissolving the dispersant in methyl isobutyl ketone, performing potentiometric titration with 0.01N methyl isobutyl ketone perchlorate solution, and converting it to KOHmgZg as the ammine value.
- the potentiometric titration was measured using an automatic titrator COM-1500 manufactured by Hiranuma Sangyo Co., Ltd.
- These dispersants are preferably added at 10 to L00 parts by mass and more preferably at 10 to 60 parts by mass with respect to 100 parts by mass of the pigment. If the amount of the dispersant added is large, the dispersant traps the acid generated by the acid generator and inhibits the curing reaction by the cationic polymerizable monomer.
- the actinic ray curable inkjet ink of the present invention is preferably solvent-free because it reacts and cures immediately after ink landing. . If the solvent remains in the cured image, the solvent resistance deteriorates. Therefore, it is preferable for dispersion suitability to select a polymerizable monomer that is not a solvent as the dispersion medium, and a monomer having the lowest viscosity among them.
- Photopolymerizable compounds include radically polymerizable compounds and cationically polymerizable compounds.
- cationically polymerizable compounds are used, and the cationically polymerizable compounds are further used.
- the compound is characterized in that it is a compound having an oxysilane ring.
- the compound having an oxysilane ring is not particularly limited, but the compound represented by the general formula (1), the compound represented by the general formula (2), ⁇ -pinene oxide, 1, 2: 8, 9 Diepoxy limonene, vegetable oils having epoxy unsaturated bonds, the above general formula (
- a compound represented by A) is preferably used.
- R represents an optionally substituted alkyl group having 1 to 10 carbon atoms (for example,
- Substituted or substituted alkyl groups eg, methyl, ethyl, propyl, butyl, isopropyl, t-butyl, hexyl, 2-ethylhexyl, benzyl, etc.
- a carbonyl group having a substituent for example, acetyl group, benzoyl group, etc.
- alkoxy group or cycloalkoxy group e.g, methyl, ethyl, propyl, butyl, isopropyl, t-butyl, hexyl, 2-ethylhexyl, benzyl, etc.
- the bond formed by bonding to each other is a methylene bond or an ether bond.
- Preferable examples of the compound represented by the general formula (2) include compounds represented by the following general formulas (III) and (IV).
- R represents an aliphatic group other than the ⁇ and ⁇ positions of the oxysilane ring, and m3 represents 0 to 2.
- r3 represents 1-3.
- L is oxygen atom in the main chain
- R represents an aliphatic group other than the a and ⁇ positions of the oxosilane ring, and m4 represents 0 to 2.
- X represents — (CH 3) or one (O), and nl represents 0 or 1.
- p2 and q2 are each
- r4 represents 1-3.
- L is oxygen atom in the main chain
- R represents an aliphatic group
- the aliphatic group is an alkyl group having 1 to 6 carbon atoms.
- cycloalkyl group having 3 to 6 carbon atoms for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group,
- An alkenyl group having 1 to 6 carbon atoms for example, vinyl group, 1 probe group, 2 probe group, 2 butyr group, etc.
- an alkynyl group having 1 to 6 carbon atoms for example, an acetyl group, a 1 propyl group, a 2-propyl group, a 2-propyl group, and the like.
- it is a C1-C3 alkyl group, and a methyl group and an ethyl group are more preferable.
- m3 represents 0 to 2, and preferably 1 or more.
- X represents — (CH 2) — or — (O) —.
- ⁇ represents 0 or 1, and when ⁇ is 0, it means that X does not exist.
- m3 + n0 is 1 or more
- L has 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain
- R represents an aliphatic group
- the aliphatic group is an alkyl group having 1 to 6 carbon atoms.
- cycloalkyl group having 3 to 6 carbon atoms for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, ), Alkenyl groups having 1 to 6 carbon atoms (for example, vinyl group, 1 probe group, 2 probe group, 2 butyr group, etc.), alkynyl groups having 1 to 6 carbon atoms ( For example, an acetyl group, a 1 propyl group, a 2-propyl group, a 2-propyl group, and the like.
- it is a C1-C3 alkyl group, and a methyl group and an ethyl group are more preferable.
- m4 represents 0 to 2, preferably 1 or more.
- X represents one (CH 3) — or one (O) —.
- nl represents 0 or 1, and when nl is 0, it means that X does not exist.
- (M4 + nl) is preferably 1 or more.
- L has 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain
- the main chain in the general formula (III) or (IV) may contain an oxygen atom or a sulfur atom!
- Examples of the divalent linking group having 1 to 15 carbon atoms include the following groups and these groups: And a group formed by combining a plurality of —O groups, —S— groups, —CO groups, and —CS groups.
- Isopropylidenebis-p-phenylene group p—C H C (CH 2) p—C H —.
- Examples of the trivalent or higher linking group include the divalent linking basic forces listed above, a group formed by removing as many hydrogen atoms as necessary, and an —O group, —S group, —CO group, —CS— Listed by combining multiple groups.
- L 1 and L may have a substituent.
- substituents include halogen atoms (e.g. salt Elementary atom, bromine atom, fluorine atom, etc.), alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), alcohol having 1 to 6 carbon atoms.
- Xy group for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.
- acyl group for example, acetyl group, propiool group, trifluoroacetyl
- acyloxy group for example, acetooxy group, propionyloxy group, trifluoroacetoxy group, etc.
- alkoxy carb group methoxy methoxy group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.
- Etc is a halogen atom, an alkyl group, or an alkoxy group.
- Examples of the vegetable oil having an unsaturated bond which has been epoxidized include those obtained by epoxidizing vegetable oil having an unsaturated bond such as olive oil, safflower oil, sunflower oil, soybean oil, linseed oil and the like.
- Commercially available epoxy-oiled vegetable oils can also be used, for example, Sanso Sizer I-4030 manufactured by Shin Nippon Rika Co., Ltd., Vf7010, Vf9010, Vf9040 manufactured by ATOFINA Chemical, etc. ⁇ Compound represented by general formula (A)>
- R represents a substituent
- examples of the substituent include a halogen atom (for example, a chlorine atom,
- alkyl group having 1 to 6 carbon atoms for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.
- alkoxy group having 1 to 6 carbon atoms for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.
- isyl group for example, acetyl group, propiool group, trifluoroacetyl group, etc.
- An acyloxy group for example, an acetooxy group, a propionyloxy group, a trifluoroacetoxy group, etc.
- an alkoxy carbo group a methoxy carbo ol group, an ethoxy carbonyl group, a tert-butoxy carbo ol group, etc.
- Etc Preferred as a substituent are an alkyl group, an alkoxy group, and an alkoxycarbo group.
- mO represents 0 to 2, preferably 0 or 1.
- L is oxygen or sulfur atom in the main chain
- the compound having an oxysilane ring represented by the general formula (A) is preferably a compound represented by the following general formula (I) or general formula (II).
- R represents a substituent
- ml represents 0 to 2.
- rl represents 1 to 3.
- L represents oxygen in the main chain.
- R represents a substituent
- m2 represents 0 to 2.
- p2 and q2 each represents 0 or 1;
- L is carbon which may contain an oxygen atom or a sulfur atom in the main chain
- R 1 and R 2 represent a substituent.
- substituents include halogen atoms (eg, chlorine atoms, bromine atoms, fluorine atoms, etc.), alkyl groups having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl).
- halogen atoms eg, chlorine atoms, bromine atoms, fluorine atoms, etc.
- alkyl groups having 1 to 6 carbon atoms eg, methyl group, ethyl group, propyl group, isopropyl group, butyl.
- an alkoxy group having 1 to 6 carbon atoms for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert butoxy group
- acyl group for example, acetyl
- acyloxy group for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.
- alkoxycarbonyl group for example, methoxycarboro group
- Preferred as a substituent are an alkyl group, an alkoxy group, and an alkoxycarbo group.
- ml and m2 each represent 0 to 2, preferably 0 or 1.
- L is an (rl + 1) valent having 1 to 15 carbon atoms and may contain an oxygen atom or a sulfur atom in the main chain.
- a linking group or a single bond, L is carbon which may contain an oxygen atom or a sulfur atom in the main chain
- divalent linking groups having 1 to 15 carbon atoms that may contain an elemental atom or sulfur atom include the following groups and combinations of these groups with a plurality of —O, S, —CO, and CS groups. Can be mentioned.
- Methylene group one CH —
- Isopropylidene group > C (CH 2), 1, 2—ethylene group: —CH 2 CH—,
- Oxydiethylene group one CH CH OCH CH one,
- 3-Oxothiojetylene group One CH CH SOCH CH One,
- 1,3-cyclopentandyl group -1,3--C H
- 1,2-cyclohexanediyl group — 1, 2 -C H-
- 1,3-cyclohexanediyl group — 1, 3 -C H-
- 1,4-cyclohexanediyl group — 1, 4 -C H-
- Phenylene group m— C H —
- Furan 2,5 diyl bismethylene group 2,5-CH 2 -CH 2 O-CH—,
- trivalent or higher linking groups examples include divalent linking groups listed above, groups formed by removing as many hydrogen atoms as necessary, and —O, S, —CO, CS — A group formed by combining a plurality of groups can be mentioned.
- L 1, L 2, and L may have a substituent.
- substituents include halogen atoms (for example,
- Replace Preferred as the group are an al
- L, L, and L may contain an oxygen atom or a sulfur atom in the main chain! 2 having 1 to 8 carbon atoms
- a divalent linking group having 1 to 5 carbon atoms in which the main chain preferred by the valent linking group is only carbon is more preferred.
- the addition amount of the compound having an oxysilane ring is preferably 10 to 80% by mass from the viewpoint of curability and film physical properties after curing.
- one of the compounds having an oxysilane ring may be used alone, or two or more may be used in appropriate combination.
- the production method of these compounds having an oxysilane ring is not limited. For example, Maruzen KK Publishing, 4th Edition, Experimental Chemistry Course 20 Organic Synthesis ⁇ , 21 3 ⁇ , 1992, Ed.
- the cationically polymerizable compound further contains a compound having an oxetane ring together with a compound having an oxetane ring.
- any known oxetane compound as disclosed in JP-A-2001-220526 and JP-A-2001-310937 can be used.
- the compound having an oxetane ring used in the present invention is preferably a compound having 1 to 4 oxetane rings.
- the photoacid generator according to the present invention is a photopolymerization initiator that can harden a cationically polymerizable compound by irradiation with actinic rays.
- any known photoacid generator can be used.
- a chemical amplification type photoresist or a compound used for photopower thione polymerization is used (Organic Elect Port). -See Tas Materials Study Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187-192). Examples of compounds suitable for the present invention are listed below.
- B (CF)-, PF-, AsF-, SbF-, CF SO-- of aromatic onium compounds such as diazoum, ammonia, jordanum, snorehonum, phospho- um, etc. Salting
- halide that photo-generates halogen hydrogen can also be used, and specific compounds thereof are exemplified below.
- composition of the present invention a sulfo-salt salt compound represented by the following general formulas [1] to [4] that does not generate benzene by irradiation with actinic rays is preferred.
- the above condition is satisfied if there is a substituent on the benzene ring that is bonded to.
- R to R each represents a hydrogen atom or a substituent.
- R to R cannot simultaneously represent hydrogen atoms.
- R to R can simultaneously represent hydrogen atoms.
- R to R represent hydrogen atoms at the same time
- R to R represent hydrogen atoms at the same time
- the substituent represented by R to R is preferably a methyl group, an ethyl group, a propyl group,
- Alkyl groups such as isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, alkoxy groups such as methoxy group, ethoxy group, propyl group, butoxy group, hexyloxy group, decyloxy group, dodecyloxy group, Acetoxy group, propionyloxy group, decylcarboxoxy group, dodecylcarboxoxy group, methoxycarbon group, ethoxycarbol group, carboyl group, carboyl group, phenolthio group, fluorine, chlorine, bromine And halogen atoms such as iodine, cyan groups, nitro groups, hydroxy groups and the like.
- X represents a non-nucleophilic key-on residue, for example, a halogen atom such as F, Cl, Br, or I, B (CF 4), R COO, R SO, SbF, AsF, PF, BF and the like can be mentioned.
- a halogen atom such as F, Cl, Br, or I
- B CF 4
- R and R are alkyl groups such as methyl group, ethyl group, propyl group and butyl group, respectively.
- B (C F) and PF are preferable from the viewpoint of safety.
- the above compound is a photoacid generator described in THE CHEMICAL SOCIETY OF JAPAN Vol. 71 No. 11 (1998), edited by Organic Electronics Materials Research Group, "Organic Materials for Imaging", Bunshin Publishing (1993). Similarly to the above, it can be easily synthesized by a known method.
- sulfonium salt power represented by the above general formulas [1] to [4]
- the following general formula [5] to [13] power is at least one of the selected sulfonium salts. Power Especially preferred.
- X represents a non-nucleophilic key residue and is the same as described above.
- an isoindoline pigment or an isoindolinone pigment is a cationically polymerizable compound having an oxetane ring or an oxsilane ring, and a polymer dispersion having a basic functional group having an amine value of 5 mgKOHZg or more.
- the polymer dispersant in the constitution of the present invention has a basic functional group having an amine value of 5 to 25 mg KOHZg, it is good even after ink formation in which the adsorptive power between the polar part of the pigment and the dispersant functional group is strong It is considered that the storage stability over time is shown. Furthermore, good curability was exhibited even after ink ejection. This is because when the ammine value is less than 5 mgKOHZg, the adsorption of the pigment and the dispersant is not sufficient, and during storage after dispersion, the particle size and viscosity increase due to aggregation of the pigment. This is thought to be because the polar group of the dispersant traps the photogenerated acid during the curing reaction after discharging the water and lowers the curing sensitivity.
- actinic ray curable ink-jet ink of the present invention may contain any known basic compound for the purpose of improving the storage stability.
- Examples include metal compounds, basic alkaline earth metal compounds, and basic organic compounds such as amines.
- Examples of basic alkali metal compounds include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (lithium carbonate, sodium carbonate, potassium carbonate, etc.). And alkali metal alcoholates (sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, etc.).
- Basic alkaline earth metals include alkaline earth metal hydroxides (magnesium hydroxide, calcium hydroxide, etc.), alkali metal carbonates (magnesium carbonate, calcium carbonate, etc.). And alkali metal alcoholates (magnesium methoxide, etc.).
- Examples of basic organic compounds include amines and nitrogen-containing heterocyclic compounds such as quinoline and quinolidine. Among these, amines are also preferred for compatibility with photopolymerizable monomers. , Octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl 1,6-hexamethylenediamine Min, hexamethylenetetramine, triethanolamine and the like.
- the concentration of the basic compound is preferably 10 to: LOOO mass ppm, more preferably 20 to 500 mass ppm, based on the total amount of the photopolymerizable monomer.
- the basic compounds may be used alone or in combination.
- water can be added to suppress hardening in an ink state such as in an ink tank, a pipe, or a head.
- the amount of water added is preferably 0.1 to less than 8% by mass of the total composition.
- the viscosity at 25 ° C is 7 to 50 mPa's. Power Curing is stable from the inkjet head irrespective of the curing environment (temperature 'humidity), and good curability is obtained. Therefore, it is preferable.
- the average particle size of the pigment particles of the ink according to the constitution of the present invention is 50 to 220 nm, more preferably 80 to 200 nm.
- the ink of the present invention has a stable average particle diameter even after storage at 60 ° C for 1 week, and shows good storage stability.
- the ink of the present invention when the ink of the present invention was continuously ejected from the inkjet ejection head, it showed extremely good emission properties (continuous ejection properties). This is because there is no generation of free dispersant due to strong adsorption due to the interaction between the polar group of the pigment and the dispersant, and the emission from the nozzle (continuous discharge) that prevents the dispersant from adhering to the wall of the discharge nozzle. I guess it has improved.
- V various non-absorbable plastics used for soft packaging, and films thereof can be used in addition to ordinary uncoated paper and coated paper.
- the various plastic films include PET film, OPS film, OPP film, ONy film, PVC film, PE film, and TAC film.
- Other plastics that can be used include polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubbers. It can also be applied to metals and glass.
- the surface energies of these various plastic films differ greatly, and the dot diameter after ink landing varies depending on the recording material.
- good high-definition images can be formed on a wide range of recording materials with a surface energy of 35-60 mNZm, including OPP films with low surface energy, OPS films, relatively large surface energy, and even PET. .
- a long (web) recording material is used in terms of the cost of recording materials such as packaging costs and production costs, print production efficiency, and compatibility with various size prints. Is more advantageous.
- the ink of the present invention can be used as a set together with an ink having a multicolor pigment. At least a yellow inkjet ink, a magenta inkjet ink, a cyan ink jet ink, an inkjet ink set having a black inkjet ink, and a plurality of inks commonly used in so-called color inkjet printing It is preferred to be used in an ink set.
- the image forming method of the present invention is a method in which the ink is ejected and drawn on a recording material by an ink jet recording method, and then the ink is cured by irradiation with an actinic ray such as ultraviolet rays. [0116] (Total ink film thickness after ink landing)
- the total ink film thickness after the ink has landed on the recording material and cured by irradiation with actinic rays is preferably 2 to 25 ⁇ m.
- the total ink film thickness is currently over 25 m.
- the force recording material is thin and is often a plastic material.
- the problem of curling and wrinkling of the material is that it is difficult to discharge the ink with excessive film thickness because there is a problem if the texture and texture of the entire printed matter change.
- total ink film thickness means the maximum value of the film thickness of the ink drawn on the recording material. Even if it is a single color, the other two colors are superimposed (secondary color), three colors The meaning of the total ink film thickness is the same even when recording is performed by the ink-jet recording method of overlapping or four-color overlapping (white ink base).
- the recording head and ink are heated to 35 to 100 ° C. and ejected.
- Actinic radiation curable ink has a large viscosity fluctuation range due to temperature fluctuations. Viscosity fluctuations directly affect the droplet size and droplet ejection speed, causing image quality degradation. It is necessary to keep it at the same time.
- the control range of the ink temperature is set temperature ⁇ 5 ° C, preferably set temperature ⁇ 2 ° C, more preferably set temperature ⁇ 1 ° C.
- the appropriate amount of liquid discharged from each nozzle is preferably 2 to 20 pl.
- the amount of droplets it is necessary for the amount of droplets to be within this range. Force When discharging with this amount of droplets, the aforementioned discharge stability becomes particularly severe. According to the present invention, even when the ink is ejected with a small droplet amount such as 2 to 20 pl, the ejection stability is improved, and a high-definition image can be stably formed.
- the actinic ray is irradiated for 0.001 to 1 second after ink landing as the actinic ray irradiation condition, more preferably 0.001 to 0.5 second. It is. In order to form a high-definition image, it is particularly important that the irradiation timing is as early as possible.
- a basic method of actinic ray irradiation is disclosed in JP-A-60-132767. According to this, a light source is provided on both sides of the head unit, and the head and the light source are scanned by the shuttle method. Irradiation is performed after a certain period of time after ink landing.
- US Pat. No. 6,145,979 discloses a method of using an optical fiber as a method of irradiation and a method of irradiating a recording unit with UV light by applying a collimated light source to a mirror surface provided on the side of the head unit. It has been done. Any of these irradiation methods can be used in the image forming method of the present invention.
- irradiation with actinic rays is divided into two stages.
- actinic rays are irradiated in the above-described manner within 0.001 to 2 seconds after ink landing, and after all printing is completed, actinic rays are further irradiated.
- This method is also a preferred embodiment.
- an actinic ray having the highest illuminance in a wavelength region of 254 nm it is preferable to use an actinic ray having the highest illuminance in a wavelength region of 254 nm, and a high-definition image can be formed even with a light source having a total power consumption of 1 kW'hr or more, and a recording material The contraction of is also kept within a practically acceptable level.
- the total power consumption of the light source for irradiating actinic rays is less than lkW'hr.
- Examples of light sources with a total power consumption of less than lkW'hr include, but are not limited to, fluorescent tubes, cold cathode tubes, hot cathode tubes, and LEDs.
- FIG. 1 is a front view showing a configuration of a main part of a recording apparatus used in the image forming method of the present invention.
- the recording apparatus 1 includes a head carriage 2, a recording head 3, an irradiation unit 4, a platen unit 5, and the like.
- This recording apparatus 1 has a platen part 5 installed under a recording material P. Yes.
- the platen section 5 has a function of absorbing ultraviolet rays and absorbs excess ultraviolet rays that have passed through the recording material P. As a result, a high-definition image can be reproduced very stably.
- the recording material P is guided by the guide member 6 and moves from the near side to the far side in FIG. 1 by the operation of the conveying means (not shown).
- a head scanning means (not shown) scans the recording head 3 held by the head carriage 2 by reciprocating the head carriage 2 in the Y direction in FIG.
- the head carriage 2 is installed on the upper side of the recording material P, and a plurality of recording heads 3, which will be described later, are arranged on the lower side according to the number of colors used for image printing on the recording material P. Store.
- the head carriage 2 is installed on the main body of the recording apparatus 1 in such a manner that it can reciprocate in the Y direction in FIG. 1, and reciprocates in the Y direction in FIG. 1 by driving the head scanning means.
- the head carriage 2 is depicted as accommodating the recording head 3.
- the number of colors of the recording head 3 accommodated in the head carriage 2 is appropriately determined. It is.
- the recording head 3 operates an ejection means (not shown) provided with a plurality of actinic ray curable inks (for example, UV curable ink) supplied by an ink supply means (not shown).
- a plurality of actinic ray curable inks for example, UV curable ink
- the UV ink discharged from the recording head 3 is composed of pigments, polymerizable monomers, polymerization initiators, etc., and crosslinks the monomers as the polymerization initiators act as a catalyst when irradiated with ultraviolet rays. It has the property of being cured by a polymerization reaction.
- the recording head 3 moves from one end of the recording material P to the other end of the recording material P in the Y direction in FIG. UV ink is ejected as ink droplets onto the possible area), and ink droplets are landed on the landable area.
- the irradiation means 4 includes an ultraviolet lamp that emits ultraviolet light in a specific wavelength region with stable exposure energy and a filter that transmits ultraviolet light of a specific wavelength.
- ultraviolet lamp that emits ultraviolet light in a specific wavelength region with stable exposure energy
- a filter that transmits ultraviolet light of a specific wavelength.
- mercury lamps, metal nanoride lamps, excimer lasers, ultraviolet lasers, cold-indicator tubes, hot-indicator tubes, black lights, LEDs (Light emitting diodes), etc. are applicable as UV lamps.
- Metal lamps, cold cathode tubes, hot cathode tubes, mercury lamps or black lights are preferred.
- a low-pressure mercury lamp, a hot cathode tube, a cold cathode tube, and a germicidal lamp that emit ultraviolet light having a wavelength of 254 nm are preferable because they can prevent bleeding and control the dot diameter efficiently.
- black light as the radiation source of the irradiation means 4, the irradiation means 4 for curing the UV ink can be produced at low cost.
- the irradiating means 4 is the largest one that can be set by the recording apparatus (UV inkjet printer) 1 among the landable areas in which the recording head 3 ejects UV ink by one scan by driving the head scanning means.
- the shape is almost the same or larger than the landable area.
- the irradiation means 4 is installed on both sides of the head carriage 2 so as to be substantially parallel to the recording material P.
- the entire recording head 3 is shielded, but in addition, the recording head can be determined from the distance hi between the irradiation means 4 and the recording material P. It is effective to increase the distance h2 between the ink ejection part 31 and the recording material P in Fig. 3 (hl ⁇ h2), or to increase the distance d between the recording head 3 and the irradiation means 4 (d is increased). is there. Further, it is more preferable that the space between the recording head 3 and the irradiation means 4 is a bellows structure 7.
- the wavelength of the ultraviolet rays irradiated by the irradiation means 4 can be appropriately changed by replacing the ultraviolet lamp or filter provided in the irradiation means 4.
- the ink of the present invention has very excellent ejection stability and is particularly effective when an image is formed using a line head type recording apparatus.
- FIG. 2 is a top view showing another example of the configuration of the main part of the ink jet recording apparatus.
- the ink jet recording apparatus shown in FIG. 2 is called a line head system.
- a plurality of ink jet recording heads 3 of each color are covered with the head carriage 2 so as to cover the entire width of the recording material P. , Fixedly arranged.
- an irradiation means 4 arranged so as to cover the entire width of the recording material P and to cover the entire ink printing surface.
- the ultraviolet lamp used for the illumination means 4 can be the same as described in FIG.
- the head carriage 2 and the irradiation means 4 are fixed, and only the recording material P is transported, and ink ejection and curing are performed to form an image.
- a part represents a mass part.
- PB822 manufactured by Ajinomoto Fine Technone, polymer dispersant with basic functional group, acid value 1
- Pigment dispersion D-1 In preparation of pigment dispersion D-1, OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane compound) Pigment dispersion D-2 was prepared in the same manner except that OXT212 (manufactured by Toa Gosei Co., Ltd., oxetane compound) was used instead.
- Pigment dispersion D-3 was prepared in the same manner except that CI Pigment Yellow 139 was used instead of CI Pigment Yellow 185 in the preparation of Pigment Dispersion D-1.
- the following compounds were placed in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a 50 ° C hot plate.
- ED-251 manufactured by Enomoto Kasei Co., Ltd., polymer dispersant having basic functional group, acid value 14 mgKOH / g, amine value 20 mgKOHZg 5 parts
- the following compounds were placed in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a 50 ° C hot plate.
- Solspers 32000 manufactured by Abyssia, polymer dispersant having basic functional group, acid value 2
- the following compounds were placed in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a 50 ° C hot plate.
- Solspers 24000GR manufactured by Avicia, polymer dispersant having basic functional group, acid value 35 mgKOHZg, valency 36 mgKOHZg 5 parts
- the following compounds were placed in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a 50 ° C hot plate.
- Solspers 26000 manufactured by Abyssia, polymer dispersant having acidic functional group, acid value 12
- the following compounds were placed in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a 50 ° C hot plate.
- Solspers 18000 manufactured by Abyssia, polymer dispersant having basic functional group, acid value 1 lmgKOH / g, amine value OmgKOHZg 5 parts
- OXT221 Toa Gosei Co., Ltd., oxetane compound 85 parts
- the following pigment was added to the solution, sealed in a polypropylene container with 100 g of Zircoyu beads having a diameter of 0.5 mm, and dispersed in a paint shaker for 6 hours.
- the pigment dispersion D-8 was prepared by removing the zircoyour beads.
- Pigment dispersion D-9 was prepared in the same manner except that C.I. Pigment Yellow 120 (benzimidazolone series) was used instead of C.I. Pigment Yellow 185 in the preparation of pigment dispersion D-1.
- Pigment dispersion D-10 was prepared in the same manner except that CI Pigment Yellow 138 (quinophthalone type) was used in place of CI Pigment Yellow 185 in the preparation of Pigment Dispersion D-1.
- PY185 C. I. Pigment Yellow 185PY120: C. I. Pigment Yellow 120PY 138: C. I. Pigment Yellow 138S. 32000: Solsnoise 32000S.
- the polymer dispersant was dissolved in methyl isobutyl ketone, and potentiometric titration was performed with 0. OlmolZL of potassium methoxy domethyl isobutyl ketone Z methanol (4: 1), and the acid value was converted to mgKOH Zg.
- the potentiometric titration was measured using an automatic titrator COM-1500 manufactured by Hiranuma Sangyo Co., Ltd.
- the polymer dispersant was dissolved in methyl isobutyl ketone, potentiometric titration was performed with 0. OlmolZL of methyl perchlorate isoptyl ketone solution, and the value converted to mgKOHZg was defined as the ammine number.
- an automatic titrator COM-1500 manufactured by Hiranuma Sangyo Co., Ltd. was used for potentiometric titration.
- Ink 1 to 23 were prepared by sequentially mixing each additive with each of the pigment dispersions prepared above based on the ink formulation described in Table 3 and filtering the mixture with a 1.0 m membrane filter. .
- the addition amount described in Table 3 represents mass%.
- a compound with a xylan ring Polymer dispersing agent A compound with a xylan ring Polymer dispersing agent
- OXT-212 Toagosei Co., Ltd.
- ⁇ -7 Exemplary compounds ⁇ — 7
- EPD-9 Exemplified compound EPD-9
- SP-152 Triphenylsulfurium salt, Adekaoptomer SP-152, manufactured by Asahi Denka Co., Ltd. (surfactant)
- F475 Megafax F475, acrylic oligomer containing perfluoroalkyl group, manufactured by Dainippon Ink & Chemicals, Inc.
- Each of the inks 1 to 23 prepared above is loaded into a carriage-type ink jet recording apparatus having the piezo-type ink jet nozzle, which has the structural power shown in FIG. 1, and is a long 120m thick, 600mm long, 500m long
- a solid image was continuously printed on the polyethylene terephthalate film to obtain an inkjet image.
- the ink supply system was an ink tank, supply pipe, front chamber ink tank just before the head, pipe with filter, and piezo head force. Heating was performed from the front chamber tank to the head part at 50 ° C.
- the piezo head was driven so that 2 to 20p 1 multi-size dots could be ejected at a resolution of 720 x 720 dpi, and each ink was ejected continuously.
- the inkjet recording apparatus of the line head recording method shown in FIG. 2 was used as the inkjet recording apparatus, and the same procedure was performed except that each of the prepared inks 1 to 23 was loaded. I got an image.
- Irradiation light source used in recording device A High-pressure mercury lamp VZero085 (manufactured by INTEGRATION T ECHNOLOGY, peak wavelength: 254 nm, maximum illumination: 400 mWZcm 2 )
- Irradiation light source used in recording device B Low-pressure mercury lamp (Iwasaki Electric's custom-made product, 5 linear light sources, irradiation area 120 mm (longitudinal direction) X 620 mm (lateral direction), peak wavelength: 254 ⁇ m Maximum illumination: 50 mWZcm 2 )
- the illuminance of each irradiation light source was displayed by measuring the integrated illuminance at 254 nm using UVPF-A1 manufactured by Iwasaki Electric Co., Ltd.
- Rate of change in average particle size (average particle size of ink after storage at 60 ° C for 1 week 60 ° C average particle size of ink before storage for 1 week) ⁇ (average particle size of ink before storage at 60 ° C for 1 week) X 100 (%)
- the rate of change in the average particle size of the ink is less than 5%
- the rate of change in the average particle size of the ink is 25 to less than 50%
- the change rate of the average particle size of the ink is 50% or more
- each actinic ray curable ink listed in Table 3 was prepared by the method described in Image Forming Method A and Image Forming Method B, and a solid image was created to check for the occurrence of wrinkles. ? Observing and observing, the scissors were evaluated according to the following criteria.
- a yellow color image is formed from the prepared ink according to image formation method A, and the colorimeter (sag Using Tag Macbeth, spectrolino keywizard), the concentration was measured under the following conditions: o
- the yellow color image density (O.D value) was evaluated according to the following criteria.
- ⁇ Yellow color reflection density is 1.1 or higher
- Yellow color reflection density is 0.9 or more and less than 1.1
- Yellow color reflection density is 0.7 or more and less than 0.9
- a yellow color image was formed from the prepared ink according to image forming method A, and the brightness of each image was evaluated visually according to the following criteria.
- the actinic ray curable inkjet ink of the present invention can be used in comparison with the comparative example even if a carriage type inkjet recording apparatus or a line head type inkjet recording apparatus is used. It can be seen that the curability is excellent with no generation of wrinkles.
- the ink of the present invention showed excellent color reproducibility with high image density (OD value) and no gloss unevenness. Furthermore, the ink of the present invention was ejected normally from almost all nozzles, while the ink of the comparative example did not eject normally even in terms of light emission. Furthermore, it can be seen that the storage stability of the ink is very excellent with no pigment aggregation compared to the comparative example. Comparative inks 22 and 23 are the cases where the pigment P.Y185 used in ink 1 of the present invention was used instead of P.Y120 and P.Y138, but the image density and gloss unevenness were the inks of the present invention. The result was inferior to 1.
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- Life Sciences & Earth Sciences (AREA)
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- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
Description
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2004002668A (ja) * | 2002-04-24 | 2004-01-08 | Toshiba Corp | 液体インクおよび記録装置 |
JP2004181951A (ja) * | 2002-11-20 | 2004-07-02 | Konica Minolta Holdings Inc | 画像記録装置及び画像記録方法 |
JP2004244624A (ja) * | 2003-01-21 | 2004-09-02 | Konica Minolta Holdings Inc | インクジェット記録方法 |
JP2004244498A (ja) * | 2003-02-13 | 2004-09-02 | Konica Minolta Holdings Inc | 活性光線硬化型インク組成物、それを用いた画像形成方法及びインクジェット記録装置 |
JP2004315778A (ja) * | 2003-02-24 | 2004-11-11 | Konica Minolta Holdings Inc | 活性エネルギー線硬化組成物 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004002668A (ja) * | 2002-04-24 | 2004-01-08 | Toshiba Corp | 液体インクおよび記録装置 |
JP2004181951A (ja) * | 2002-11-20 | 2004-07-02 | Konica Minolta Holdings Inc | 画像記録装置及び画像記録方法 |
JP2004244624A (ja) * | 2003-01-21 | 2004-09-02 | Konica Minolta Holdings Inc | インクジェット記録方法 |
JP2004244498A (ja) * | 2003-02-13 | 2004-09-02 | Konica Minolta Holdings Inc | 活性光線硬化型インク組成物、それを用いた画像形成方法及びインクジェット記録装置 |
JP2004315778A (ja) * | 2003-02-24 | 2004-11-11 | Konica Minolta Holdings Inc | 活性エネルギー線硬化組成物 |
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