WO2011065095A1 - インクジェット画像形成方法及びインクジェットインクセット - Google Patents
インクジェット画像形成方法及びインクジェットインクセット Download PDFInfo
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- WO2011065095A1 WO2011065095A1 PCT/JP2010/065706 JP2010065706W WO2011065095A1 WO 2011065095 A1 WO2011065095 A1 WO 2011065095A1 JP 2010065706 W JP2010065706 W JP 2010065706W WO 2011065095 A1 WO2011065095 A1 WO 2011065095A1
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- gelling agent
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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
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
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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
- C09D11/12—Printing inks based on waxes or bitumen
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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
- C09D11/30—Inkjet printing inks
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet 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
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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
- B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
Definitions
- the present invention relates to a method for forming an image on a substrate using an active energy ray-curable inkjet ink set, and more specifically, printing durability, resistance to back-through of plain paper, and gloss uniformity of coated paper.
- the present invention relates to an ink jet image forming method and an ink jet ink set using an active energy ray-curable ink jet ink which is excellent in paper feed compatibility and does not show off when a printed portion after printing is stored in an overlapping manner.
- the inkjet image forming method is capable of recording high-definition images with a relatively simple device, and has been rapidly developed in various fields.
- various uses to which the inkjet image forming method is applied and a recording medium or ink suitable for each purpose is used.
- the recording speed has been greatly improved, and printers having performance capable of withstanding light printing applications have been developed.
- ink is ejected from an ink jet head and landed on a recording medium to form an image.
- the ink In order for the ink to be ejected from the inkjet head, the ink needs to have a low viscosity.
- high-viscosity ink is necessary to prevent color mixing called bleeding, which occurs when a plurality of ink droplets having different hues land on a recording medium.
- an ultraviolet curable ink jet recording method using an active energy ray curable ink has been put into practical use. This is because the active energy ray-curable monomer and the photoinitiator are contained in the ink, and after landing on the recording medium, the active energy ray is irradiated with, for example, ultraviolet rays to cure the ink, thereby ensuring the emission property. This is a technology that achieves both prevention of bleeding.
- the active energy ray-curable ink and the hot melt ink do not contain a solvent in the ink component, they have an advantage that an image can be formed even on a recording material having no ink absorbability.
- the active energy ray-curable ink component contains a material that causes a gelling action due to temperature changes, and after the ink ejected from the inkjet head has landed on the recording material
- a technique for forming an image by temperature change and active energy ray irradiation is disclosed (for example, see Patent Documents 2 and 3).
- the present invention has been made in view of the above-mentioned problems, and its purpose is excellent in printing durability, gloss uniformity of coated paper, paper feeding compatibility, and show-off when the printed portions after printing are stacked and stored.
- An object of the present invention is to provide an inkjet image forming method and an inkjet ink set using an active energy ray-curable inkjet ink having excellent resistance.
- It includes a gelling agent that forms an active energy ray-curable composition and a thermoreversible gel, and after applying a colorless ink that does not contain a coloring material to a substrate, it is heated and then irradiated with active energy rays.
- An ink jet image forming method An ink jet image forming method.
- An active energy ray-curable composition a colored ink containing a gelling agent and a coloring material that forms a thermoreversible gel
- An active energy ray-curable composition and a gelation that forms a thermoreversible gel An ink-jet ink set comprising a colorless ink containing an agent and no colorant.
- the inkjet ink set according to any one of 3 to 5 is used.
- 1) A colored ink containing an active energy ray-curable composition, a gelling agent that forms a thermoreversible gel, and a coloring material is used as an image forming region.
- 2) an active energy ray-curable composition, a gelling agent that forms a thermoreversible gel, and a colorless ink containing no coloring material is applied to the entire surface of the image forming area, heated, and then activated.
- An inkjet image forming method comprising irradiating energy rays.
- the active energy ray-curable composition and a gelling agent that forms a thermoreversible gel are included, and after applying a colorless ink not containing a coloring material to a substrate, heating is performed, and then An inkjet image forming method characterized by irradiating active energy rays, or 1) colored ink containing an active energy ray-curable composition, a gelling agent that forms a thermoreversible gel and a coloring material, and 2) active energy
- an inkjet ink set comprising a linear curable composition, a gelling agent that forms a thermoreversible gel, and no colorant, a non-printing part and a printing part
- an active energy ray-curable inkjet ink having excellent printing durability, gloss uniformity on coated paper, paper feeding compatibility, and excellent resistance to set-off when the printed portions after printing are stored in layers is used.
- Ink jet image forming method and ink jet ink set can be provided.
- FIG. 3 is a schematic flow diagram showing an example of a process flow of an ink jet recording apparatus used in the ink jet image forming method of the present invention.
- the inventors of the present invention include a gelling agent that forms a thermoreversible gel with an active energy ray-curable composition, and provides a base material with colorless ink that does not include a coloring material.
- an ink jet image forming method characterized by heating and then irradiating active energy rays, or 1) an active energy ray curable composition, a gelling agent and a colorant for forming a thermoreversible gel.
- An ink-jet ink set comprising: a colored ink containing 2) an active energy ray-curable composition; and a colorless ink containing a gelling agent that forms a thermoreversible gel and no colorant Therefore, it has excellent printing durability, anti-through-through resistance on plain paper, gloss uniformity on coated paper, and paper feed compatibility, but also has excellent anti-set-off resistance when storing the printed parts after printing.
- the viscosity of the ink is low when the colorless ink lands on the substrate, and the dots of the landed ink spread in two dimensions or absorb.
- the base material since the image surface cannot be efficiently coated by penetrating the base material, the landed colored ink dots are easily peeled off, and there is a problem in image durability.
- a gelling agent added to the colorless ink, the colorless ink after landing does not diffuse more than necessary, and the applied colorless ink is applied at a desired position.
- the gel referred to in the present invention means that the solute has independent mobility due to the interaction such as lamellar structure, polymer network formed by covalent bond or hydrogen bond, polymer network formed by physical aggregation, and aggregate structure of fine particles. It has a structure that has been lost and assembled, and is a solidified or semi-solidified state with a sudden increase in viscosity and a significant increase in elasticity.
- the gelling agent in the present invention refers to a compound that can form the gel when added to other compounds.
- a gelling agent is a compound that can form the gel when added to a compound other than water.
- a gel becomes a fluid solution (sometimes called a sol) by heating, a thermoreversible gel that returns to the original gel when cooled, and once gelled, it can be reheated even if heated. There is a heat irreversible gel that does not return.
- the phase transition temperature as used in the present invention refers to a temperature at which the viscosity suddenly changes from a fluid solution state to a gel state.
- Gel transition temperature, gel dissolution temperature, gel softening temperature, sol-gel phase It is synonymous with terms called transition temperature and gel point.
- the melting temperature in the present invention is a temperature at which a gelling gelling agent starts melting.
- the phase transition temperature of the ink is low. It is preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 45 ° C. or higher and 130 ° C. or lower. If the ink phase transition temperature is 40 ° C. or higher, stable ejection is not affected by the printing environment temperature when ejecting ink droplets from the recording head (hereinafter referred to as “ejection”). If the temperature is 150 ° C. or lower, it is not necessary to heat the ink jet recording apparatus to an excessively high temperature, and the load on the head of the ink jet recording apparatus and the members of the ink supply system can be reduced.
- the method for measuring the phase transition temperature of the ink is, for example, a method in which a small iron piece sealed in a glass tube is placed in an dilatometer and the phase transition point is a point at which the ink liquid does not naturally fall in response to a temperature change ( J. Polym. Sci., 21, 57 (1956)), a method in which an aluminum cylinder is placed on ink and the temperature at which the aluminum cylinder naturally falls when the gel temperature is changed is measured as a phase transition temperature ( Journal of the Japan Society of Rheology, Vol. 17, 86 (1989)).
- place a gel-like test piece on the heat plate heat the heat plate, measure the temperature at which the shape of the test piece collapses, and obtain this as the sol-gel phase transition temperature. Can do.
- a compound in which the gelling agent itself can form a fibrous aggregate is preferable. Formation of the fibrous aggregate can be easily confirmed by morphological observation with a transmission electron microscope.
- Compounds preferably used as the gelling agent according to the present invention include polyethylene wax, polypropylene wax, polystyrene wax, stearone, stearic acid, glycerin monostearate, glycerin monolacrate, glycerin mono-12-hydroxystearate, octadocoic acid, Monoglyceride, stearyl stearate, stearyl alcohol, behenic acid, new oil smectite, rosin oil gelling agent, behenyl alcohol, glyceryl behenate, inulin stearate, dextrin palmitate, N, N-tylenedioctadecanamide, N-stearyl stearin Acid amide, N-oleyl palmitate amide, dextrin palmitate, N-lauroyl-L-glutamic acid dibutylamide, N-2 Tylhexanoyl-L-glutamic acid dibutylamide, 1,3:
- the gelling agent can be used in an amount of 0.1 to 30% by mass, preferably 0.3 to 15% by mass, based on the total mass of the ink. It is particularly preferable that the content is% by mass. By setting the content of the gelling agent in this range, more stable emission characteristics can be obtained.
- the ink viscosity at a temperature of the ink phase transition temperature + 5 ° C. is preferably 1 to 15 mPa ⁇ s, more preferably 1 to 10 mPa ⁇ s. Within this range, more stable emission characteristics can be obtained, and the object and effects of the present invention can be further exhibited.
- active energy ray-curable composition examples include an active energy ray polymerizable compound and an active energy ray polymerization initiator. This will be specifically described below.
- the active energy ray polymerizable compound is preferably selected from a radical polymerizable compound and a cationic polymerizable compound.
- active energy ray polymerizable compositions described in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863 and the like are used.
- Active energy ray curable materials and cationic polymerization active energy ray curable resins used are known, and photocationic polymerization active energy ray curability recently sensitized to a longer wavelength range beyond visible light. Examples of the resin are disclosed in JP-A-6-43633 and JP-A-8-324137.
- the radical polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization, and may be any compound as long as it has at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. , Oligomers, polymers and the like having a chemical form. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties.
- Examples of compounds having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, urethanes, amides. And radically polymerizable compounds such as various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides and unsaturated urethanes.
- the amount of the radical polymerizable compound added is preferably 1 to 97% by mass, more preferably 30 to 95% by mass with respect to the ink.
- radical polymerization initiators examples include triazine derivatives described in JP-B-59-1281, JP-A-69-1621, JP-A-60-60104, JP-A-59-1504, and JP-A-61-61. No. 243807 and other publications, JP-B Nos. 43-23684, 44-6413, 47-1604, etc. and U.S. Pat. No. 3,567,453 Diazonium compounds, organic azide compounds described in U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853, JP-B 36-22062, 37- Ortho-quinonediazides described in JP-A Nos.
- Examples of the cationically polymerizable compound include vinyl ether compounds, epoxy compounds, oxetane compounds and other cyclic compounds. This will be specifically described below.
- epoxy compound any of monomers, oligomers, and polymers that are usually used as epoxy resins can be used. Specific examples include conventionally known aromatic epoxides, alicyclic epoxides and aliphatic epoxides. Hereinafter, the epoxide means a monomer or an oligomer thereof. You may use these compounds 1 type or 2 types or more as needed.
- a preferable aromatic epoxide is a di- or polyglycidyl ether produced by the reaction of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof and epichlorohydrin, such as bisphenol A or an alkylene thereof.
- examples thereof include di- or polyglycidyl ethers of oxide adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or alkylene oxide adducts thereof, and novolak-type epoxy resins.
- examples of the alkylene oxide include ethylene oxide and propylene oxide.
- cyclohexene oxide or cyclopentene obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide or peracid.
- Oxide-containing compounds are preferred, and specific examples include, for example, Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2080, Celoxide 2000, Epoxide GT301, Epolide GT302, Epolide GT401, Epolide GT403, EHPE-3150, manufactured by Daicel Chemical Industries, Ltd. EHPEL3150CE; Union Carbide UVR-6105, UVR-6110, UVR-6128, UVR-6100, UVR-6216, VR-6000, and the like can be given.
- Preferable aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether or 1, Diglycidyl ethers of alkylene glycols such as 6-hexanediol diglycidyl ether, polyglycidyl ethers of polyhydric alcohols such as di- or triglycidyl ethers of glycerin or its alkylene oxide adducts, diglycidyl of polyethylene glycol or its alkylene oxide adducts Diglycidies of polyalkylene glycols such as ether, polypropylene glycol or diglycidyl ether of alkylene oxide adducts thereof Ether and the like.
- examples of the alkylene oxide include ethylene oxide and propylene oxide.
- monoglycidyl ethers of higher aliphatic alcohols and monoglycidyl ethers of phenol and cresol can also be used.
- aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable in consideration of fast curability.
- epoxy compounds are blended in a liquid component composed of an oxetane compound and a vinyl ether compound in an amount of 0 to 20% by mass, preferably 0 to 10% by mass, so that the curability, the flexibility of the cured film, and the adhesion to the substrate are obtained. This is preferable.
- An oxetane compound is a compound having one or more oxetane (trimethylene oxide) rings in the molecule. Specifically, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd .: OXT101, etc.), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene (OXT121, etc.), 3- Ethyl-3- (phenoxymethyl) oxetane (same as OXT211), di (1-ethyl-3-oxetanyl) methyl ether (same as XT221), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (same as above) OXT212, etc.), di (1-methyl-3-oxetanyl) methyl ether, etc.
- oxetane compounds are blended in a liquid component composed of an epoxy compound, an oxetane ring-containing compound, and a vinyl ether compound in an amount of 0 to 20% by mass, preferably 0 to 10% by mass. From the viewpoint of adhesiveness.
- Vinyl ether compound A vinyl ether compound can also be used as the cationically polymerizable compound used in the present invention.
- vinyl ether initiates polymerization by changing the vinyl group in the molecule to a vinyl cation by an acid generated by active energy rays.
- the vinyl ether compound refers to an organic compound having a vinyl ether group, preferably a compound having a molecular weight of 100 to 2,000. More preferably, it is 200-1200.
- the viscosity can be adjusted by adding a vinyl ether oligomer.
- VECTOMER divinyl ether resin from Allied Signal (for example, VECTOMER 2010, VECTOMER 2020, VECTOMER 4010 and VECTOMER). 4020 and equivalents available from other manufacturers) and mixtures thereof.
- a blend any ratio of one or more vinyl ether resins and / or one or more epoxy resins can also be used.
- Polyhydroxy functional materials (such as those described in US Pat. No. 5,856,373 (Kaisaki et al.)) Are also used in combination with epoxy- and / or vinyl ether-functional materials. It can also be used.
- a known cyclic compound capable of cationic polymerization may be contained.
- ⁇ Active energy ray polymerization initiator As the active energy ray polymerization initiator that can be used in the ink according to the present invention, a known active energy ray acid generator can be used. Specifically, arylsulfonium salt derivatives (Syracure UVI-6990, Syracure UVI-6974, manufactured by Union Carbide, Inc .; Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, manufactured by ADEKA) Adekaoptomer SP-172, CPI-100, CPI-110P, CPI-110A manufactured by Sun Apro, TS-91 manufactured by Sanwa Chemical, Esacure 1187, Esacure 1188 manufactured by Lamberti, etc.), allyl iodonium salt derivatives (RP-2074 manufactured by Rhodia, Irgacure 250 manufactured by BASF Japan), allene-ion complex derivatives (Irgacure 250 manufactured by BASF Japan), diazonium salt
- the active energy ray polymerization initiator is preferably contained in a ratio of 0.2 to 10 parts by mass, and further 0.5 to 5 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound or radical polymerizable compound. By setting the content of the initiator in this range, the storage stability of the ink is improved.
- These active energy ray polymerization initiators can be used alone or in combination of two or more.
- sensitizers for active energy ray polymerization initiators include anthracene and anthracene derivatives (such as ADEKA OPTMER SP-100, diethoxyanthracene, and dibutoxyanthracene manufactured by ADEKA) when a sulfonium salt is used as the initiator. It is done. When an iodonium salt is used as an initiator, thioxanthones can be used. These sensitizers can be used alone or in combination.
- the addition amount is preferably 0.2 to 5 parts by mass, more preferably 0.5 to 4 parts by mass with respect to 100 parts by mass of the cationically polymerizable compound. The sensitizing effect is enhanced by making the addition amount within the range.
- the colored ink according to the present invention is prepared by coloring the ink according to the present invention, it is preferable to use a pigment or an oil-soluble dye as a coloring material.
- organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow and pyrazolone red, soluble azo pigments such as ritole red, heliobordeaux, pigment scarlet, and permanent red 2B; alizarin, indanthrone, thio Derivatives from vat dyes such as indigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; isoindolinone Isoindolinone organic pigments such as yellow and isoindolinone orange; Pyranthrone organic pigments such as pyranthrone red and pyranthro
- Organic pigment is color index (CI) No. This is illustrated below.
- quinacridone-based, phthalocyanine-based, benzimidazolone-based, isoindolinone-based, condensed azo-based, quinophthalone-based, and isoindoline-based organic pigments are preferable because of their excellent light resistance.
- the trace amount of metal ion components contained in organic pigments causes the light from the UV light source to strike the nozzle surface of the inkjet head, forming a salt with the initiator component in the UV ink, causing poor injection, and cationic light. Since unnecessary polymerization of the polymerizable monomer may be promoted, it is desirable to remove the trace metal ion component by washing in advance.
- the organic pigment is preferably fine particles having an average particle diameter in the ink of 10 to 150 nm as measured by laser scattering.
- the average particle diameter of the pigment is set to 150 to 300 nm, preferably 180 to 250 nm, in order to provide whiteness and concealment.
- coarse particles are removed by sufficient dispersion or filtration so that the maximum particle size of the pigment in the ink does not exceed 1 ⁇ m. This improves the discharge stability.
- the organic pigment can be refined by the following method. That is, a mixture composed of at least three components of an organic pigment, a water-soluble inorganic salt of 3 mass times or more of the organic pigment, and a water-soluble solvent is made into a clay, and is kneaded strongly with a kneader or the like to be refined, and then poured into water. Stir 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.
- water-soluble inorganic salts used in the refinement process include sodium chloride and potassium chloride. These inorganic salts are used in the range of 3 to 20 times by mass of the organic pigment. If the amount of the inorganic salt is less than 3 times the mass of the organic pigment, a treated pigment having a desired size cannot be obtained. If the amount of the inorganic salt is more than 20 times the mass, the washing process in the subsequent step is enormous. Substantial processing of pigment is reduced.
- the water-soluble solvent is not particularly limited as long as it is a solvent that can be used for making an appropriate clay state of an organic pigment and a water-soluble inorganic salt used as a crushing aid and performing sufficient crushing efficiently, and is soluble in water.
- a high boiling point solvent having a boiling point of 120 to 250 ° C. is preferable from the viewpoint of safety.
- the pigment is in the range of 1.5 to 8% by mass in the case of a color excluding white in the ink, and in the range of 10 to 30% by mass in the case of a white ink using titanium oxide. It is preferably included.
- Oil-soluble dyes include disperse dyes, vat dyes, sulfur dyes, azo dyes, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, Examples include benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes, perinone dyes, and phthalocyanine dyes, but the present invention is not limited thereto.
- I. Solvent Blue 2 4, 5, 7, 10, 11, 12, 14, 22, 25, 26, 35, 36, 37, 38, 43, 44, 45, 48, 49, 50, 51, 59, 63, 64, 66, 67, 68, 70, 72, 79, 81, 83, 91, 94, 95, 97, 98, 99, 100, 102, 104, 105, 108, 111, 112, 116, 117, 118, 122, 127, 128, 129, 130, 131, 132, 133, 134, etc .; C. I. Solvent Black 3, 5, 6, 7, 8, 13, 22, 22: 1, 23, 26, 27, 28, 29, 33, 34, 35, 39, 40, 41, 42, 43, 45, 46, 47, 48, 49, 50 etc. can be mentioned.
- oil-soluble dyes C.I. I. Solvent Yellow 3, 14, 16, 33, 56, C.I. I. Solvent Red 18, 24, 27, 122, 135, C.I. I. Solvent Blue 14, 25, 35, 48, 108, C.I. I. Solvent Black 3, 7, 22, 34, and 50 can be suitably used since the fastness of the dye is high.
- a preferable addition amount of the oil-soluble dye is 0.5 to 90%, more preferably 1 to 70% with respect to the ink.
- the pigment dispersant examples include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester, Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl Examples thereof include phenyl ether, stearylamine acetate, and pigment derivatives.
- Anti-Terra-U polyaminoamide phosphate
- Anti-Terra-203 / 204 high molecular weight polycarboxylate
- Disbyk-101 polyaminoamide phosphate manufactured by BYK Chemie.
- Salt (acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 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) ”,“ Lactimon (long chain amine and unsaturated acid polycarboxylic acid and Reconfiguration) "and the like.
- Demol RN N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18” manufactured by Kao Corporation.
- pigment dispersants are preferably contained in an amount of 5 to 70% by mass, preferably 10 to 50% by mass, based on the pigment 100. By setting the content of the pigment dispersant in the above range, dispersion stability and ejection stability are improved.
- these pigment dispersants preferably have a solubility of 5% by mass or more in the whole cationic polymerizable compound or radical polymerizable compound at 0 ° C.
- solubility range By setting the solubility range to this range, the storage stability and ejection stability of the ink are improved.
- a cationic polymerization inhibitor it is preferable to add a cationic polymerization inhibitor to the ink containing the cationic polysynthetic compound. Since vinyl ether is highly reactive and a dark reaction is likely to proceed due to residual acid or acid generated slightly from the polymerization initiator during storage, it is preferable to intentionally add a polymerization inhibitor.
- the polymerization inhibitor include alkali metal compounds and / or alkaline earth metal compounds or amines. Since it is preferable not to add alkali metal ions as much as possible, amines are suitable.
- Preferred amines are alkanolamines, N, N-dimethylalkylamines, N, N-dimethylalkenylamines, N, N-dimethylalkynylamines, and more specifically, triethanolamine, triethanolamine, Isopropanolamine, tributanolamine, N-ethyldiethanolamine, propanolamine, n-butylamine, sec-butylamine, 2-aminoethanol, 2-methylaminoethanol, 3-methylamino-1-propanol, 3-methylamino-1, 2-propanediol, 2-ethylaminoethanol, 4-ethylamino-1-butanol, 4- (n-butylamino) -1-butanol, 2- (t-butylamino) ethanol, N, N-dimethylundeca Nord, N, N-dimethyldodecanol N, N-dimethyltridecanolamine, N, N-
- the addition amount of the cationic polymerization inhibitor is preferably 10 to 5000 ppm. By setting the addition amount of the cationic polymerization inhibitor within the range, storage stability, ejection stability and curing sensitivity are improved.
- the ink according to the present invention it is preferable to add a radical polymerization inhibitor after adding a cationic polymerization inhibitor to the ink containing a cationic polysynthetic compound.
- a radical polymerization inhibitor in combination, the storage stability of the ink can be improved even if impurities and residual acid are present in the ink.
- radical polymerization inhibitors methoquinone (hydroquinone monomethyl ether), hydroquinone, 4-methoxy-1-naphthol, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants Agents, ascorbic acids, zinc sulfate, thiocyanates, thiourea derivatives, various sugars, phosphate antioxidants, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, polycondensates of dicyandiamide and polyalkylene polyamines, etc. Is mentioned.
- the addition amount of the radical polymerization inhibitor is preferably 10 to 5000 ppm. By setting the addition amount of the radical polymerization inhibitor within the range, storage stability, ejection stability and curing sensitivity are improved.
- Metal ions In the ink according to the present invention, the total amount of Na ions, Ca ions and Mg ions in the ink containing the cationic polysynthetic compound is preferably 100 ppm or less. These ions can be quantified by ion chromatography by mixing ink and pure water, separating the aqueous phase, and then extracting the ions extracted into the aqueous phase.
- alkali metal ions do not cause any problems during normal ink storage, but form slightly soluble salts when the ink receives active energy rays and various decomposition products and active species are generated from the polymerization initiator. There are things to do. Therefore, when ink is ejected for a long period of time, a hardly soluble precipitate is generated in the vicinity of the opening of the ink jet nozzle, and the ejection accuracy is lowered.
- the method of reducing the amount of alkali metal ions in the ink is achieved by purifying various materials used.
- various materials used In particular, generally used pigments, polymerization initiators such as sulfonium salts, dispersants, and cationic polymerization initiators such as vinyl ether / oxetane / epoxy may contain alkali metal ions as impurities in the production process. It is preferable to use after appropriately purifying the material. By refining these alkali metals, the content of the counter anion is also reduced, and there is an effect that a decrease in cationic polymerizability due to impurities can be suppressed.
- halogen ion species such as chlorine as much as possible.
- the total amount of halogen ions is less than 50 ppm, preferably less than 10 ppm.
- the reduction of the halogen ion species can be achieved by refining the raw material in the same manner as the reduction of the alkali metal ion species described above.
- the following organic solvents can be used.
- solids examples include beeswax, carnauba wax, rice wax, wood wax, jojoba oil, whale wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and petrolatum.
- Natural wax polyethylene wax, chlorinated hydrocarbon, palmitic acid, stearic acid, behenic acid, tiglic acid, 2-acetonaphthobehenic acid, 12-hydroxystearic acid, dihydroxystearic acid and other organic acids; dodecanol, tetradecanol, Hexadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetracenol, hexadecenol, eicosenol, docosenol, Nene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, mesythelin, hexanediol, decanediol, tetradecandiol, hexa
- liquid oily medium examples include one organic solvent or a mixed solvent of two or more organic solvents.
- organic solvent examples include ethanol, pentanol, heptanol, octanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anis alcohol, and the like; ethylene glycol monoethyl ether, ethylene glycol monophenyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, ethylene glycol Monoethyl ether ace And glycol derivatives such as propylene glycol diacetate; ketones such as benzyl ether
- esters of hydrocarbons include hydrocarbon solvents such as petroleum ether, petroleum benzyl, tetralin, delican, 1-amylbenzene, dimethylnaphthalene; acetonitrile, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane
- polar solvents such as propylene carbonate, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and N, N-diethyldodecanamide. These solvents may be used alone or in combination of two or more.
- the ink according to the present invention may contain various additives such as a surfactant, a lubricant, a filler, a rust inhibitor, an antifoaming agent, a thickener, a gelling agent, and polymers as necessary. .
- solvent such as an ester solvent, an ether solvent, an ether ester solvent, a ketone solvent, an aromatic hydrocarbon solvent, or a nitrogen-containing organic solvent can be added.
- a preferred form of the physical properties of the ink according to the present invention is that the calorific value per unit mass is 10 mJ / mg or more when the ink is subjected to DSC measurement in the range of 25 ° C. to ⁇ 25 ° C. at a rate of 5 ° C. per minute. It does not show an exothermic peak.
- the calorific value per unit mass is 10 mJ / mg or more when the ink is subjected to DSC measurement in the range of 25 ° C. to ⁇ 25 ° C. at a rate of 5 ° C. per minute. It does not show an exothermic peak.
- the ink according to the present invention is produced by well dispersing a pigment together with a vinyl ether and a pigment dispersant using an ordinary dispersing machine such as a sand mill. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and dilute with an active energy ray-curable compound. Sufficient dispersion is possible even with dispersion by ordinary dispersers. Therefore, excessive dispersion energy is not applied and a large amount of dispersion time is not required, so it is difficult to cause deterioration during dispersion of ink components, and stability. Can be prepared.
- the prepared ink is preferably filtered through a filter having a pore diameter of 3 ⁇ m or less, and more preferably 1 ⁇ m or less.
- the pigment is preferably dispersed with an average particle size of 0.08 to 0.5 ⁇ m, and the maximum particle size of 0.3 to 10 ⁇ m, preferably 0.3 to 3 ⁇ m.
- the average particle diameter is an average value of diameters (sphere-converted particle diameters) when primary particles or aggregates thereof are converted into spheres having the same volume, and this value can be evaluated from an electron micrograph. Specifically, using an image processing program provided in a JEOL transmission electron microscope (JEM2010F), it is possible to calculate an average value of spherical equivalent particle diameters.
- the value obtained by calculating the average value is there.
- the particle size By controlling the particle size, clogging of the head nozzle can be suppressed, and ink storage stability, ink transparency, and curing sensitivity can be maintained.
- the amount of pigment or oil-soluble dye added is preferably 0.1 to 20% by mass, more preferably 0.4 to 10% by mass. If it is 0.1% by mass or more, good image quality can be obtained, and if it is 20% by mass or less, an appropriate ink viscosity in ink ejection can be obtained. In addition, two or more kinds of colorants can be mixed as appropriate for color adjustment.
- Base material As a base material used for inkjet recording, all of a wide range of conventional synthetic resins used in various applications have been targeted. Specifically, for example, polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene, acrylic resin, polycarbonate , Polystyrene, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate, etc., and the thickness and shape of these synthetic resin substrates are not limited at all. In addition, metals, glass, printing paper, etc. can be used.
- Non-coated paper includes printing paper A using 100% chemical pulp, printing paper B using 70% or more chemical pulp, printing paper C using 40% or more and less than 70% chemical pulp, and printing using less than 40% chemical pulp. Examples thereof include paper D, gravure paper containing mechanical pulp and subjected to calendar treatment. More details are described in detail in “Latest Paper Processing Handbook” edited by the Paper Processing Handbook Editorial Committee, published by Tech Times, “Printing Engineering Handbook” edited by the Japan Printing Society.
- Plain paper is 80 to 200 ⁇ m uncoated paper belonging to a part of uncoated paper, special printing paper and information paper.
- the plain paper used in the present invention includes, for example, high-grade printing paper, intermediate-grade printing paper, low-grade printing paper, thin-like printing paper, fine-coating printing paper, special printing paper such as fine-quality printing paper, foam paper, PPC paper, and others There are information sheets and the like, and the present invention is not particularly limited thereto.
- polyester film As the various films, all commonly used films can be used.
- a polyolefin film As the various films, all commonly used films can be used.
- Resin-coated paper that is photographic printing paper or YUPO paper that is synthetic paper can also be used.
- An inkjet ink set of the present invention (hereinafter also referred to as an ink set) includes a colored ink containing a gelling agent and a colorant that form a thermoreversible gel with an active energy ray-curable composition, and an active energy ray-curable composition. And a colorless ink that contains a gelling agent and no colorant, and the melting temperature of the gelling agent contained in the colored ink is higher than the melting temperature of the gelling agent contained in the colorless ink And
- the ink according to the present invention is ejected onto a recording medium using an inkjet recording head to form an image.
- the inkjet recording head used in the inkjet image forming method of the present invention includes: An on-demand system or a continuous system may be used.
- an electro-mechanical conversion method for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.
- an electro-thermal conversion method for example, thermal ink jet
- Specific examples include a mold, a bubble jet (registered trademark) type, an electrostatic attraction method (for example, an electric field control type, a slit jet type, etc.), and a discharge method (for example, a spark jet type).
- any discharge method may be used.
- the ink jet image forming method of the present invention is characterized in that an ink jet recording head having a line head method that is severely demanded for clogging is used as a printing method.
- a line-type ink jet recording head is an ink jet recording head that is longer than the width of the recording medium, and even if it is a long head having a large number of nozzles, a plurality of ink jet recording heads are unitized to make it longer Even such a head can be preferably used.
- a carriage equipped with the recording head scans in a direction perpendicular to the direction in which the recording medium is transported, so that more recording can be performed in a shorter time than a serial head that forms an image. It becomes possible to do it, and productivity improves dramatically.
- the ink ejection conditions it is preferable from the viewpoint of ejection stability that the recording head and ink are heated to 35 to 130 ° C. and ejected.
- the ink of the present invention has a large viscosity fluctuation range due to temperature fluctuation, and the viscosity fluctuation directly affects the droplet size and droplet ejection speed, causing image quality degradation. It is preferable to keep in and emit in that state.
- the predetermined temperature range is preferably set temperature ⁇ 5 ° C., more preferably set temperature ⁇ 2 ° C., and further preferably set temperature ⁇ 1 ° C.
- the set temperature here refers to a reference temperature set as the temperature of ink when ink is ejected.
- the droplet size of the colored ink ejected from each nozzle of the recording head is preferably 1 to 15 pl.
- the droplet size is preferably 1 to 15 pl.
- the aforementioned discharge stability becomes particularly severe. According to the present invention, even when ejection is performed with a small droplet amount such as an ink droplet size of 1 to 15 pl, the ejection stability is improved, and a high-definition image can be stably formed.
- forming an image using colored and colorless inks specifically, after applying colored ink to a substrate, uniformly applying colorless ink to the entire image forming area, or in a reverse image manner
- uniformly means to apply a constant amount of colorless ink, and to apply in a reverse image-like manner, to give the colored ink and the amount of colorless ink so that the sum of the applied amounts of colored ink and colorless ink is constant.
- the portion where the amount of application is small increases the amount of colorless ink applied, and when the amount is large, the reverse is applied.
- applying to the entire surface of the image forming area means applying colorless ink to the entire surface of the base material to which colored ink is applied, which will be a final product.
- the total amount of colored ink and colorless ink is preferably 5 ml / m 2 or more, more preferably 5 to 30 ml / m 2 , and particularly preferably 5 to 20 ml / m 2 .
- this applied amount it is possible to obtain a printed matter having a high density and excellent paper transportability and printing durability.
- the colorless ink application amount in a reverse image manner to the colored ink application amount. That is, when the amount of colored ink applied is small, the amount of colorless ink applied is increased. As a result, the total applied amount of the colored ink and the colorless ink is made constant over the entire image recording area, so that the transportability and printing durability during continuous printing can be further improved.
- the sum of the applied amounts of the colored ink and the colorless ink means that the total applied amount of the colored ink and the colorless ink falls within a range of ⁇ 5% with respect to a preset reference amount.
- the colorless ink when colorless ink is ejected from an ink jet head, it can be made larger than the droplet size of colored ink.
- the colorless ink is preferably 1 to 65 pl larger than the colored ink. More preferably, it is 4 to 35 pl larger.
- the role of colorless ink is to apply it uniformly or inversely to the entire image area. For this reason, the colorless ink does not need to be printed with high definition, and printing with a reduced resolution is advantageous for uniform application.
- the droplet size of the colored ink is 1 to 15 pl, but the colorless ink preferably has a droplet size of 2 to 80 pl. More preferably, it is 5 to 50 pl.
- the melting temperature of the gelling agent contained in the colored ink can be increased as compared with the melting temperature of the gelling agent contained in the colorless ink.
- the melting temperature of the gelling agent contained in the colored ink is preferably 5 to 80 ° C. higher than the melting temperature of the gelling agent contained in the colorless ink. More preferably, it is 10 to 50 ° C.
- a radical monomer or a cationic monomer can be applied as a colorless ink.
- the transparency of an image or an image formed by a colored ink of a colorless ink can be used.
- the monomers used for the colored ink and the colorless ink are preferably of the same class.
- the effect of the invention can be achieved by imparting further smoothness of the printed matter by imparting physical energy to the ink imparted on the substrate after the colored ink and colorless ink are imparted on the substrate. Is further enhanced.
- a heating or pressurizing method in an image forming apparatus using an electrophotographic process such as an electrophotographic copying machine or an electrophotographic printer, a toner image transferred from a photoreceptor surface to a transfer object such as a copy paper is covered.
- a method similar to passing a copy paper between a heating roll and a pressure roll that are pressed against each other for fixing to a transfer product is preferable.
- a method using a fixing belt a method using a fixing belt in which a surface layer containing a curable modified silicone resin is provided on the outermost surface (corresponding to a releasable layer) farthest from a base (base material) of a fixing member It is preferable to carry out a post-treatment using.
- the heating temperature is preferably in the range of 50 to 200 ° C., more preferably 60 to 160 ° C. Range.
- the heating may be performed with a heater built in the printer or with a heater provided separately.
- a heating roller for both the fixing roller and the fixing belt in terms of suppressing occurrence of fixing unevenness and enabling continuous processing in a small space.
- these apparatuses can be used as an electrophotographic heat fixing machine, and using them is advantageous in terms of cost.
- the heating roller has a hollow roller as a constituent component and is rotated by a driving means.
- a heating element such as a halogen lamp heater, a ceramic heater, or a nichrome wire is incorporated in the hollow portion as a heat source. It is preferable.
- the roller is preferably made of a material having high thermal conductivity, and in particular, a metal roller is preferable, and nickel is preferably used.
- the pressure applied is preferably in the range of 9.8 ⁇ 10 4 Pa to 4.9 ⁇ 10 6 Pa.
- examples of the active energy rays applied to the ink landed on the recording medium include electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, ⁇ rays, and X-rays. Dangerous, easy to handle, and electron beams and ultraviolet rays that are widely used industrially are preferable. In the present invention, ultraviolet rays are particularly preferable.
- the amount of electron beam to be irradiated is preferably in the range of 0.1 to 30 Mrad. This is because the irradiation effect is enhanced by setting the amount of the electron beam in the range.
- the light source is, for example, a low pressure, medium pressure, high pressure mercury lamp, metal halide lamp, xenon lamp having a light emission wavelength in the ultraviolet region, cold cathode tube, hot cathode tube having an operating pressure of several hundred Pa to 1 MPa.
- a conventionally well-known thing, such as LED, is used.
- Preparation of ink for ink set> [Preparation of colored ink] (Preparation of colored ink 101: hot melt colored ink) Color material: C.I. I. Pigment Blue 15: 3 (average particle size: 100 nm) 5 parts by mass Paraffin wax (Nippon Seiwa Co., Ltd., 155) 45 parts by mass Behenic acid (Wako Pure Chemical Industries, Ltd.) 30 parts by mass Oleic acid amide (Kao Co., Ltd., fatty acid amide ON) 20 parts by mass After mixing and heating to 150 ° C. and stirring, the obtained liquid was filtered with a filter under heating and cooled to prepare colored ink 101.
- Color material C.I. I. Pigment Blue 15: 3 (average particle size: 100 nm) 5 parts by mass Paraffin wax (Nippon Seiwa Co., Ltd., 155) 45 parts by mass Behenic acid (Wako Pure Chemical Industries, Ltd.) 30 parts by mass Oleic acid amide (Kao Co.,
- Cyan pigment dispersion 1 20 parts by weight
- Photopolymerizable compound 1 Lauryl acrylate (monofunctional) 5 parts by weight
- Photopolymerizable compound 2 Ethylene oxide-modified trimethylolpropane triacrylate (trifunctional) 5 parts by weight
- Photopolymerizable compound 3 Caprolactam-modified dipentaerythritol hexaacrylate (hexafunctional) 35 parts by weight
- Photopolymerizable compound 4 tetraethylene glycol diacrylate (bifunctional) 30 parts by mass
- Polymerization initiator 1 Irgacure 184 (manufactured by BASF Japan) 2.5 parts by mass
- Polymerization initiator 2 Irgacure 907 (manufactured by BASF Japan) 2.5 parts by mass
- the above additives were sequentially added and mixed, and then filtered using a filter having an absolute filtration accuracy of 2 ⁇ m to prepare colored ink 102.
- a colored ink 104 was prepared in the same manner as in the preparation of the colored ink 103 except that the gelling agent was changed from 12-hydroxystearic acid to stearone (manufactured by Alfa Aesar).
- Cyan pigment dispersion 2 20 parts by weight
- Polymerizable compound 1 Alicyclic epoxy compound (CEL2021P, manufactured by Daicel Chemical Industries) 15 parts by weight
- Polymerizable compound 2 Oxetane compound (OXT221, manufactured by Toagosei Co., Ltd.) 62 parts by mass
- CPI-100P 50% propylene carbonate solution of triallylsulfonium salt (manufactured by San Apro) 2 parts by mass Thioxanthone (DETX, manufactured by Nippon Kayaku) 1.0 part by mass
- Colored ink 105 was prepared by filtration using a filter having an absolute filtration accuracy of 2 ⁇ m.
- Cyan pigment dispersion 2 20 parts by mass Polymerizable compound 1: Alicyclic epoxy compound (CEL2021P, manufactured by Daicel Chemical Industries) 15 parts by mass Polymerizable compound 2: Oxetane compound (OXT221, manufactured by Toagosei Co., Ltd.) 51.5 parts by mass Gelling agent: Stearon (manufactured by Alfa Aesar) 10 parts by mass Photopolymerization initiator 1: iodonium salt (IBPF, manufactured by Sanwa Chemical) 2.5 parts by mass Thioxanthone (DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by mass The above additives were sequentially added and mixed, and then filtered using a filter having an absolute filtration accuracy of 2 ⁇ m to prepare colored ink 106. .
- a colored ink 107 was prepared in the same manner as in the preparation of the ink 106 except that the gelling agent was changed from stearone to EB-21 (manufactured by Ajinomoto Co., Inc.).
- Cyan pigment dispersion 3 20 parts by mass Cyclohexane divinyl ether (CHDVE manufactured by Nippon Carbide Industries Co., Ltd.) 58 parts by mass Vinyl ether oligomer (produced by Vectormer 2020 Aldrich) 20 parts by mass TEMPO (2,2,6,6-tetramethylpiperidine 1- Oxyl) 0.03 parts by mass CPI-100P: 50% propylene carbonate solution of triallylsulfonium salt (manufactured by San Apro) 2 parts by mass After sequentially adding and mixing the above additives, the mixture was filtered using a filter with an absolute filtration accuracy of 2 ⁇ m. Thus, colored ink 108 was prepared.
- CHDVE Cyclohexane divinyl ether
- TEMPO 2,2,6,6-tetramethylpiperidine 1- Oxyl
- CPI-100P 50% propylene carbonate solution of triallylsulfonium salt (manufactured by San Apro) 2 parts by mass
- a colored ink 110 was prepared in the same manner as in the preparation of the colored ink 109 except that the gelling agent was changed from CROTHIX OG-CS to inulin stearate (Leopard ISK2 manufactured by Chiba Flour Milling Co., Ltd.).
- Photopolymerizable compound 1 Lauryl acrylate (monofunctional) 25 parts by mass
- Photopolymerizable compound 2 Ethylene oxide modified trimethylolpropane triacrylate (trifunctional) 5 parts by mass
- Photopolymerizable compound 3 Caprolactam modified dipentaerythritol hexa Acrylate (hexafunctional) 35 parts by weight
- Photopolymerizable compound 4 Tetraethylene glycol diacrylate (bifunctional) 30 parts by mass Polymerization initiator 1: Irgacure 184 (manufactured by BASF Japan) 2.5 parts by mass
- Polymerization initiator 2 Irgacure 907 (manufactured by BASF Japan) 2.5 parts by mass
- the above additives were sequentially added and mixed, and then filtered using a filter with an absolute filtration accuracy of 2 ⁇ m to prepare colorless ink 201.
- Photopolymerizable compound 1 Lauryl acrylate (monofunctional) 25 parts by mass
- Photopolymerizable compound 2 Ethylene oxide modified trimethylolpropane triacrylate (trifunctional) 5 parts by mass
- Photopolymerizable compound 3 Caprolactam modified dipentaerythritol hexa Acrylate (hexafunctional) 25 parts by weight
- Photopolymerizable compound 4 Tetraethylene glycol diacrylate (bifunctional) 30 parts by mass
- Gelling agent 12-hydroxystearic acid (Alfa Aesar) 10 parts by mass
- Polymerization initiator 1 Irgacure 184 (manufactured by BASF Japan) 2.5 parts by mass
- Polymerization initiator 2 Irgacure 907 (manufactured by BASF Japan) 2.5 parts by mass
- the above additives were sequentially added and mixed, and then filtered using a filter having an absolute filtration accuracy
- colorless ink 203 radical UV colorless ink, with gelling agent
- a colorless ink 203 was prepared in the same manner as in the preparation of the colorless ink 202 except that the gelling agent was changed from 12-hydroxystearic acid to stearone (manufactured by Alfa Aesar).
- colorless ink 206 cationic UV colorless ink with gelling agent
- a colorless ink 206 was prepared in the same manner as in the preparation of the colorless ink 205 except that the gelling agent was changed from stearone to EB-21 (dibutylethylhexanoylglutamide Ajinomoto Co., Inc.).
- colorless ink 207 cationic UV colorless ink, no gelling agent
- Cyclohexane divinyl ether (CHDVE manufactured by Nippon Carbide Industries Co., Ltd.) 78 parts by mass Vinyl ether oligomer (produced by Vectormer 2020 Aldrich) 20 parts by mass TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) 0.03 parts by mass
- CPI-100P 50% propylene carbonate solution of triallylsulfonium salt (manufactured by San Apro) 2 parts by mass
- the mixture was filtered using a filter with an absolute filtration accuracy of 2 ⁇ m.
- a colorless ink 207 was prepared.
- colorless ink 209 cationic UV colorless ink, with gelling agent
- a colorless ink 209 was prepared in the same manner as in the preparation of the colorless ink 208 except that the gelling agent was changed from CROTHIX OG-CS to inulin stearate (Leopard ISK2 manufactured by Chiba Flour Milling Co., Ltd.).
- Table 1 summarizes the ink types and melting temperatures of the added gelling agents (temperatures at which the gelling gelling agent starts melting) for the colored inks 101 to 110 prepared above.
- the melting temperature of the gelling agent was measured by placing a test piece of each gelling agent on a melting point measuring machine (ATM 01 ATM-01) and heating at a heating rate of 5 ° C./min or less. The melted temperature was measured, and this operation was repeated three times to obtain an average value. The first decimal place was rounded off to obtain the melting temperature of the gelling agent.
- the ink type and the melting temperature of the added gelling agent are listed in Table 2.
- the gelling agent is the same as the gelling agent described in Table 1, and the melting temperature measured above is described.
- ink sets 1 to 31 were prepared according to the combinations shown in Table 3. For convenience, an ink set number is assigned even for a colored ink alone.
- Inkjet image formation A line head type ink jet recording apparatus equipped with a piezo-type head is loaded with each of the colored inks and colorless inks prepared as described above.
- the substrate is resistant to set-off as a base material (XEROX 4024 manufactured by XEROX).
- a black solid and wedge-like image was printed using paper (special diamond art double-sided N manufactured by Mitsubishi Paper Industries).
- the colorless ink is arranged on the downstream side of the colored ink head group, and as shown in Table 4, a colorless ink application method for uniformly applying the colorless ink regardless of the applied amount of the colored ink (in Table 4, The printing was performed separately for the application method of colorless ink to be applied in a reverse image-like manner to the applied amount of colored ink to be applied (described as “reverse image-like” in Table 4).
- the ink supply system consists of an ink tank, a supply pipe, a front chamber ink tank immediately before the head, a pipe with a filter, and a recording head.
- the temperature from the front chamber tank to the recording head is insulated from the others and heated at 120 ° C. It was.
- the recording head was driven so as to eject 4 pl multi-size dots at a resolution of 1440 ⁇ 1440 dpi and continuously ejected with ink.
- the droplet size of the inkjet head used was 4 pl for colored ink and 14 pl for colorless ink.
- the dpi referred to in the present invention represents the number of dots per 2.54 cm (1 inch).
- the ink was cured by irradiating with ultraviolet rays from a high pressure mercury lamp VZero085 (manufactured by INTEGRATION TECHNOLOGY) at an energy density of 140 W / cm and an illuminance of 20 mJ / cm 2 (integrated light amount).
- VZero085 manufactured by INTEGRATION TECHNOLOGY
- the heating / pressurizing treatment after printing was performed using the apparatus having the heating / pressurizing belt pair shown in FIG.
- the heating belt surface temperature at this time was processed at a temperature 10 ° C. higher than the temperature at which the gelling agent used solidifies.
- the conveyance speed was set to 20 mm / second.
- heat-pressing processing was performed at the timing before irradiating an active energy ray.
- Sample 1 prepared using hot melt ink is inferior in performance other than set-off resistance. This is because the hot melt ink is solidified due to the rapid temperature drop of the ink droplets after landing, so that no ink permeates into the paper.
- Samples 2 to 4 prepared using the active energy ray-curable ink are inferior to Sample 1 in the set-off resistance. This is presumably because the ink itself has a smaller thickening effect due to lowering the temperature than the hot melt ink and penetrates into the paper fiber after landing.
- the performance other than this is somewhat improved compared to the sample 1, but it is generally insufficient.
- Samples 5 to 7 prepared using an ink obtained by adding a gelling agent to an active energy ray-curable ink are improved in terms of strike-through resistance, paper feed compatibility, and set-off resistance compared to Samples 2 to 4. Be looked at. This is because the application of a gelling agent causes the viscosity to increase rapidly after ink droplet landing, and the film strength is improved by curing the photopolymerizable monomer by light irradiation. It can be presumed that the adhesion of the material has improved. However, it can be seen that the effect is not sufficient even in these samples.
- samples 8 to 10 prepared by uniformly applying colorless ink to the image area are also suitable for paper feeding, resistance to set-off, gloss uniformity, It can be seen that the abrasion resistance is improved.
- the anti-set-off resistance, abrasion resistance, and the like are considered to have been improved by protecting the image surface by uniformly applying colorless ink and reducing the difference in gloss between the printed portion and the non-printed portion.
- Samples 11 to 13 prepared by applying this colorless ink in a reverse image form have further improved paper feeding compatibility and gloss uniformity. This is because by applying colorless ink in a reverse image-like manner, the height due to the difference in the amount of ink applied in the area of the created image is eliminated, so that the paper transportability after printing becomes smooth, and it looks It can be estimated that the uniformity of gloss is improved. These effects can be confirmed in any of the inks having different types of photocurable monomers.
- the samples 14 and 16 in which the colored ink is higher than the colorless ink as the melting temperature of the gelling agent contained in the ink have characteristics such as showthrough resistance, paper feed compatibility, and abrasion resistance.
- the samples 25 to 31 have the same or slightly inferior performance. This is because, even when colorless ink is applied on the image surface by not applying heat, the impacted dots are not sufficiently smoothed. The result is a slightly inferior balance between performance and abrasion resistance.
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Abstract
Description
本発明でいうゲルとは、ラメラ構造、共有結合や水素結合した高分子網目、物理的な凝集によって形成される高分子網目、微粒子の凝集構造などの相互作用により、溶質が独立した運動性を失って集合した構造を持ち、急激な粘度上昇や著しい弾性増加を伴って固化または半固化した状態のことを言う。
活性エネルギー線硬化性組成物の構成成分の例としては、活性エネルギー線重合性化合物及び活性エネルギー線重合開始剤等が挙げられる。以下具体的に説明していく。
活性エネルギー線重合性化合物としては、ラジカル重合性化合物、カチオン重合性化合物から選択することが好ましい。
エポキシ化合物としては、通常、エポキシ樹脂として用いられるモノマー、オリゴマー又はポリマーの何れも使用可能である。具体的には、従来公知の芳香族エポキシド、脂環族エポキシド及び脂肪族エポキシドが挙げられる。尚、以下、エポキシドとは、モノマー又はそのオリゴマーを意味する。これらの化合物は1種又は必要に応じて2種以上用いてもよい。
オキセタン化合物は、分子内に1以上のオキセタン(トリメチレンオキシド)環を有する化合物である。具体的には3-エチル-3-ヒドロキシメチルオキセタン(東亞合成社製:OXT101等)、1,4-ビス[(3-エチル-3-オキセタニル)メトキシメチル]ベンゼン(同OXT121等)、3-エチル-3-(フェノキシメチル)オキセタン(同OXT211等)、ジ(1-エチル-3-オキセタニル)メチルエーテル(同OXT221等)、3-エチル-3-(2-エチルヘキシロキシメチル)オキセタン(同OXT212等)、ジ(1-メチル-3-オキセタニル)メチルエーテル等を好ましく用いることができ、特に3-エチル-3-ヒドロキシメチルオキセタン、3-エチル-3-(フェノキシメチル)オキセタン、ジ(1-エチル-3-オキセタニル)メチルエーテルが好ましい。これらは単独で、あるいは2種以上を組み合わせて用いることができる。これらオキセタン化合物は、エポキシ化合物、オキセタン環含有化合物、ビニルエーテル化合物から成る液状成分中、0~20質量%、好ましくは0~10質量%配合されることが硬化性、硬化膜の柔軟性、基材との密着性の点で好ましい。
本発明に用いるカチオン重合性化合物として、ビニルエーテル化合物も用いることができる。一般にビニルエーテルは、活性エネルギー線により発生した酸により、分子内のビニル基がビニルカチオンに変化して重合を開始する。
ブチルビニルエーテル、ヘキシルビニルエーテル、エチルヘキシルビニルエーテル、フェニルビニルエーテル、ベンジルビニルエーテル、エチルエトキシビニルエーテル、アセチルエトキシエトキシビニルエーテル、シクロヘキシルビニルエーテル、アダマンチルビニルエーテル、
(2価のジビニルエーテル)
エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールビニルエーテル、ブチレンジビニルエーテル、ジブチレングリコールジビニルエーテル、ネオペンチルグリコールジビニルエーテル、シクロヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ノルボルニルジメタノールジビニルエーテル、イソバイニルジビニルエーテル、ジビニルレゾルシン、ジビニルハイドロキノン
(3価のトリビニルエーテル)
グリセリントリビニルエーテル、グリセリンエチレンオキシド付加物トリビニルエーテル(エチレンオキシドの付加モル数6)、トリメチロールプロパントリビニルエーテル、トリビニルエーテルエチレンオキシド付加物トリビニルエーテル(エチレンオキシドの付加モル数3)
(4価のテトラビニルエーテル)
ペンタエリスリトールトリビニルエーテル、ペンタエリスリトールエチレンオキシド付加物トリビニルエーテル(エチレンオキシドの付加モル数9)
(6価のヘキサビニルエーテル)
ジトリメチロールプロパンヘキサビニルエーテル、ジトリメチロールプロパンエチレンオキシド付加物ヘキサビニルエーテル(エチレンオキシドの付加モル数6)
上記ビニルエーテルのうち、特に好ましくは、2価以上のビニルエーテルである。2価以上のビニルエーテルを用いると、酸による重合反応が速やかに起こり、活性エネルギー線硬化感度が高くより好ましい。
本発明に係るインクで用いることのできる活性エネルギー線重合開始剤としては、公知の活性エネルギー線酸発生剤を用いることができる。具体的には、アリールスルホニウム塩誘導体(ユニオン・カーバイド社製のサイラキュアUVI-6990、サイラキュアUVI-6974;ADEKA社製のアデカオプトマーSP-150、アデカオプトマーSP-152、アデカオプトマーSP-170、アデカオプトマーSP-172、サン・アプロ社製のCPI-100、CPI-110P、CPI-110A、三和ケミカル社製のTS-91、Lamberti社製のEsacure1187、Esacure1188等)、アリルヨードニウム塩誘導体(ローディア社製のRP-2074、BASFジャパン社製のイルガキュア250等)、アレン-イオン錯体誘導体(BASFジャパン社製のイルガキュア250等)、ジアゾニウム塩誘導体、トリアジン系開始剤及びその他のハロゲン化物等の酸発生剤が挙げられる。
本発明に係るインクを着色して本発明に係る有色インクを調製する場合は、顔料または油溶性染料を色材として用いることが好ましい。
C.I.ピグメントオレンジ16、36、43、51、55、59、61、
C.I.ピグメントレッド9、48、49、52、53、57、97、122、123、149、168、177、180、192、202、206、215、216、217、220、223、224、226、227、228、238、240、
C.I.ピグメントバイオレット19、23、29、30、37、40、50、
C.I.ピグメントブルー15、15:1、15:3、15:4、15:6、22、60、64、
C.I.ピグメントグリーン7、36、
C.I.ピグメントブラウン23、25、26、
上記顔料の中でも、キナクリドン系、フタロシアニン系、ベンズイミダゾロン系、イソインドリノン系、縮合アゾ系、キノフタロン系、イソインドリン系有機顔料等は耐光性が優れているため好ましい。
C.I.Solvent Yellow 1,2,3,4,6,7,8,10,12,13,14,16,18,19,21,25,25:1,28,29,30,32,33,34,36,37,38,40,42,43,44,47,48,55,56,58,60,62,64,65,72,73,77,79,81,82,83,83:1,85,88,89,93,94,96,98,103,104,105,107,109,112,114,116,117,122,123,124,128,129,130,131,133,134,135,138,139,140,141,143,146,147,148,149,150,151,152,153,157,158,159,160:1,161,162,163,164,165,167,168,169,170,171,172等;
C.I.Solvent Red 1,2,3,4,7,8,13,14,17,18,19,23,24,25,26,27,29,30,33,35,37,39,41,42,43,45,46,47,48,49,49:1,52,68,69,72,73,74,80,81,82,83,83:1,84,84:1,89,90,90:1,91,92,106,109,111,117,118,119,122,124,125,127,130,132,135,138,140,143,145,146,149,150,151,152,155,160,164,165,166,168,169,172,175,176,177,179,180,181,182,185,188,189,195,198,202,203,204,205,206,207,208,209,210,212,213,214,215,216,217,218,219,220,221,222,223,224,225,226,227,228,229等;
C.I.Solvent Blue 2,4,5,7,10,11,12,14,22,25,26,35,36,37,38,43,44,45,48,49,50,51,59,63,64,66,67,68,70,72,79,81,83,91,94,95,97,98,99,100,102,104,105,108,111,112,116,117,118,122,127,128,129,130,131,132,133,134等;
C.I.Solvent Black 3,5,6,7,8,13,22,22:1,23,26,27,28,29,33,34,35,39,40,41,42,43,45,46,47,48,49,50等を挙げることが出来る。
顔料分散剤としては、水酸基含有カルボン酸エステル、長鎖ポリアミノアマイドと高分子量酸エステルの塩、高分子量ポリカルボン酸の塩、長鎖ポリアミノアマイドと極性酸エステルの塩、高分子量不飽和酸エステル、高分子共重合物、変性ポリウレタン、変性ポリアクリレート、ポリエーテルエステル型アニオン系活性剤、ナフタレンスルホン酸ホルマリン縮合物塩、芳香族スルホン酸ホルマリン縮合物塩、ポリオキシエチレンアルキル燐酸エステル、ポリオキシエチレンノニルフェニルエーテル、ステアリルアミンアセテート、顔料誘導体等を挙げることができる。
本発明においては、カチオン重合成化合物を含有したインクに対してカチオン重合禁止剤を添加することが好ましい。ビニルエーテルは反応性が高く、残留酸や、保存時に僅かに重合開始剤から発生する酸によって、暗反応が進行しやすいので、重合禁止剤は意図的に添加することが好ましい。重合禁止剤としては、アルカリ金属化合物および/またはアルカリ土類金属化合物もしくは、アミン類を挙げることができる。アルカリ金属イオン類は後述するようにできるだけ添加しない方が好ましいので、アミン類が適している。
本発明に係るインクにおいては、カチオン重合成化合物を含有したインク中のNaイオン、Caイオン及びMgイオンの総量が100ppm以下であることが好ましい。これらのイオンは、インクと純水とを混合し、水相を分離した後に水相に抽出されたイオンをイオンクロマト法によって定量することができる。
本発明に係るインクには、必要に応じて界面活性剤、滑剤、充填剤、防錆剤、消泡剤、増粘剤、ゲル化剤、ポリマー類など各種の添加剤を含有させることが出来る。
本発明に係るインクの物性として好ましい形態は、毎分5℃の降下速度で25℃から-25℃の範囲でインクのDSC測定を行ったとき、単位質量あたりの発熱量が10mJ/mg以上の発熱ピークを示さないことである。本発明の構成に従って素材の選定を行うことにより、DSC測定において一定量以上の発熱を抑えることが出来る。このような構成とすることにより、インクを低温で保存した場合においてもゲルの発生や、析出物の発生を抑えることが出来る。
本発明に係るインクは、ビニルエーテル、顔料分散剤と共に、顔料をサンドミル等の通常の分散機を用いてよく分散することにより製造される。予め顔料高濃度の濃縮液を作製しておき、活性エネルギー線硬化性化合物で希釈することが好ましい。通常の分散機による分散においても充分な分散が可能であり、このため、過剰な分散エネルギーが掛からず、多大な分散時間を必要としないので、インク成分の分散時の変質を招き難く、安定性に優れたインクが調製できる。調製されたインクは、孔径3μm以下、更には1μm以下のフィルターで濾過することが好ましい。
インクジェット記録に用いる基材としては、従来、各種の用途で使用されている広汎な合成樹脂が全て対象となり、具体的には、例えばポリエステル、ポリ塩化ビニル、ポリエチレン、ポリウレタン、ポリプロピレン、アクリル樹脂、ポリカーボネート、ポリスチレン、アクリロニトリル-ブタジエン-スチレン共重合体、ポリエチレンテレフタレート、ポリブタジエンテレフタレート等が挙げられ、これらの合成樹脂基材の厚みや形状は何ら限定されない。この他にも金属類、ガラス、印刷用紙なども使用できる。
本発明のインクジェットインクセット(以下、インクセットともいう)は、活性エネルギー線硬化性組成物と熱可逆性ゲルを形成するゲル化剤及び色材を含む有色インクと、活性エネルギー線硬化性組成物とゲル化剤を含み、色材を含まない無色インクとから構成され、有色インクに含まれるゲル化剤の溶融温度が、無色インクに含まれるゲル化剤の溶融温度に比べて高いことを特徴とする。
本発明のインクジェット画像形成方法においては、本発明に係るインクをインクジェット記録ヘッドを用いて、記録媒体に吐出して画像形成するが、本発明のインクジェット画像形成方法で使用するインクジェット記録ヘッドとしては、オンデマンド方式でもコンティニュアス方式でも構わない。また吐出方式としては、電気-機械変換方式(例えば、シングルキャビティー型、ダブルキャビティー型、ベンダー型、ピストン型、シェアーモード型、シェアードウォール型等)、電気-熱変換方式(例えば、サーマルインクジェット型、バブルジェット(登録商標)型等)、静電吸引方式(例えば、電界制御型、スリットジェット型等)及び放電方式(例えば、スパークジェット型等)などを具体的な例として挙げることができるが、いずれの吐出方式を用いても構わない。
また、本発明のインクジェット画像形成方法においては、印字方式としては、目詰まりに対する要求が厳しいラインヘッド方式を有するインクジェット記録ヘッドを用いることを特徴とする。ライン型インクジェット記録ヘッドとは、記録媒体の幅以上の長尺のインクジェット記録ヘッドであり、多数のノズル数を有する長尺のヘッドであっても、複数のインクジェット記録ヘッドをユニット化して長尺化したヘッドであっても好ましく用いることができる。ライン型インクジェット記録ヘッドを用いることで、記録ヘッドを搭載したキャリッジが記録媒体を搬送する方向に対して垂直方向に走査することで画像を形成するシリアルヘッドに比べて、短時間で多くの記録を行うことができるようになり、生産性が飛躍的に向上する。
インクの吐出条件としては、記録ヘッド及びインクを35~130℃に加熱し、吐出することが吐出安定性の点で好ましい。本発明のインクは、温度変動による粘度変動幅が大きく、粘度変動はそのまま液滴サイズ、液滴出射速度に大きく影響を与え、画質劣化を起こすため、インク温度を上げながらその温度を所定の範囲内に保ち、その状態で出射することが好ましい。この所定の温度範囲としては、好ましくは設定温度±5℃、より好ましくは設定温度±2℃、更に好ましくは設定温度±1℃である。ここでいう設定温度とは、インクを出射する際のインクの温度として設定された基準の温度をいう。
本発明の効果を得るための画像形成方法として、色材を含有する有色インクと無色インクを併用することが必要となる。これは有色インク中に含有されるゲル化剤の効果により、インクジェットヘッドから吐出された液滴は、印刷基材に着弾後、急速に液滴温度が低下し、基材上で固化する。このため着弾後のドットの拡散はほとんどみられず、インク液滴は基材上に盛り上がった状態で存在する。このために、印字部と非印字部の高低差が大きく、光沢性が低く、画像耐刷性、連続印字時の用紙搬送性が低下することが本発明者の検討により明らかとなった。これに対して有色及び無色インクを用いて画像形成すること、具体的には、有色インクを基材に付与した後に、無色インクを画像形成領域全面に均一に付与する、あるいは、逆像様に付与することで上記性能を改良できる。ここで均一に付与するとは、無色インクの付与量を一定にして付与することであり、逆像様に付与するとは、有色インクと無色インクの付与量の合計が一定となるように、有色インクの付与量が少ない部分は無色インク付与量を増やし、多い場合はその逆にして付与することをいう。
本発明の効果を更に高めるために、有色インク、無色インクを付与した後、活性エネルギー線を照射するまえに、基材上に付与したインクを加熱及び/または加圧することが好ましい。
〔有色インクの調製〕
(有色インク101の調製:ホットメルト有色インク)
色材:C.I.ピグメントブルー15:3(平均粒径:100nm)
5質量部
パラフィンワックス(日本精蝋社製、155) 45質量部
ベヘン酸(和光純薬社製) 30質量部
オレイン酸アミド(花王社製、脂肪酸アマイドON) 20質量部
上記各添加物を順次混合し、150℃に加熱して攪拌した後、得られた液体を加熱下、フィルターでろ過し、冷却して有色インク101を調製した。
〈シアン顔料分散物1の調製〉
C.I.ピグメントブルー15:3 20質量部
高分子分散剤(Zeneca社製 Solsperseシリーズ)
5質量部
ステアリルアクリレート 75質量部
上記各添加剤を混合した後、顔料粒子の平均粒径が0.2~0.3μmの範囲となるように、公知の分散装置を用い、分散条件を適宜調整して分散を行い、次いで、加熱下でフィルター濾過を行って、シアン顔料分散物1を調製した。
シアン顔料分散物1 20質量部
光重合性化合物1:ラウリルアクリレート(単官能) 5質量部
光重合性化合物2:エチレンオキサイド変性トリメチロールプロパントリアクリレート(三官能) 5質量部
光重合性化合物3:カプローラクタム変性ジペンタエリスリトールヘキサアクリレート(六官能) 35質量部
光重合性化合物4:テトラエチレングリコールジアクリレート(二官能)
30質量部
重合開始剤1:イルガキュア184(BASFジャパン社製)
2.5質量部
重合開始剤2:イルガキュア907(BASFジャパン社製)
2.5質量部
上記各添加剤を順次添加、混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、有色インク102を調製した。
〈有色インクの調製〉
シアン顔料分散物1(前出) 20質量部
光重合性化合物1:ラウリルアクリレート(単官能) 10質量部
光重合性化合物2:エチレンオキサイド変性トリメチロールプロパントリアクリレート(三官能) 10質量部
光重合性化合物3:カプローラクタム変性ジペンタエリスリトールヘキサアクリレート(六官能) 20質量部
光重合性化合物4:テトラエチレングリコールジアクリレート(二官能)
25質量部
ゲル化剤:12-ヒドロキシステアリン酸(Alfa Aesar社製)
10質量部
重合開始剤1:イルガキュア184(BASFジャパン社製)
2.5質量部
重合開始剤2:イルガキュア907(BASFジャパン社製)
2.5質量部
上記各添加剤を順次添加し、100℃で混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、有色インク103を調製した。
上記有色インク103の調製において、ゲル化剤を12-ヒドロキシステアリン酸から、ステアロン(Alfa Aesar社製)に変更した以外は同様にして、有色インク104を調製した。
〈シアン顔料分散物2の調製〉
C.I.ピグメントブルー15:3 20質量部
PB822(味の素ファインテクノ社製、高分子分散剤) 8質量部
オキセタン化合物(OXT221、東亞合成社製) 72質量部
上記各添加剤を混合した後、顔料粒子の平均粒径が0.2~0.3μmの範囲となるように、公知の分散装置を用い、分散条件を適宜調整して分散を行い、次いで加熱下でフィルター濾過を行って、シアン顔料分散物2を調製した。
シアン顔料分散物2 20質量部
重合性化合物1:脂環式エポキシ化合物(CEL2021P、ダイセル化学社製) 15質量部
重合性化合物2:オキセタン化合物(OXT221、東亞合成社製)
62質量部
CPI-100P:トリアリルスルホニウム塩のプロピレンカーボネート50%溶液(サンアプロ社製) 2質量部
チオキサントン(DETX、日本化薬製) 1.0質量部
上記各添加剤を順次添加、混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、有色インク105を調製した。
シアン顔料分散物2(前出) 20質量部
重合性化合物1:脂環式エポキシ化合物(CEL2021P、ダイセル化学社製) 15質量部
重合性化合物2:オキセタン化合物(OXT221、東亞合成社製)
51.5質量部
ゲル化剤:ステアロン(Alfa Aesar社製) 10質量部
光重合開始剤1:ヨードニウム塩(IBPF、三和ケミカル製)
2.5質量部
チオキサントン(DETX、日本化薬製) 1.0質量部
上記各添加剤を順次添加、混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、有色インク106を調製した。
上記インク106の調製において、ゲル化剤をステアロンから、EB-21(ジブチルエチルヘキサノイルグルタミド 味の素株式会社製)に変更した以外は同様にして、有色インク107を調製した。
〈シアン顔料分散液3の調製〉
C.I.ピグメントブルー15:3 20質量部
PB822(味の素ファインテクノ社製、高分子分散剤) 8質量部
シクロヘキサンジビニルエーテル(CHDVE 日本カーバイド工業株式会社製) 72質量部
PB822及びCHDVEを順次添加し、100℃で混合した後、室温まで冷却し、これに上記顔料の20質量部を加えて、直径0.5mmのジルコニアビーズ200質量部と共にガラス瓶に入れ密栓し、ペイントシェーカーにて10時間で分散処理した後、ジルコニアビーズを除去し、シアン顔料分散液3を調製した。
シアン顔料分散液3 20質量部
シクロヘキサンジビニルエーテル(CHDVE 日本カーバイド工業株式会社製) 58質量部
ビニルエーテルオリゴマー(Vectomer 2020 Aldrich社製) 20質量部
TEMPO(2,2,6,6-テトラメチルピペリジン 1-オキシル)
0.03質量部
CPI-100P:トリアリルスルホニウム塩のプロピレンカーボネート50%溶液(サンアプロ社製) 2質量部
上記各添加剤を順次添加、混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、有色インク108を調製した。
〈有色インクの調製〉
シアン顔料分散液3(前出) 20質量部
シクロヘキサンジビニルエーテル(CHDVE 日本カーバイド工業株式会社製) 53質量部
ビニルエーテルオリゴマー(Vectomer 2020 Aldrich社製) 20質量部
ゲル化剤:CROTHIX OG-CS(Croda社製) 5質量部
TEMPO(2,2,6,6-テトラメチルピペリジン 1-オキシル)
0.03質量部
CPI-100P:トリアリルスルホニウム塩のプロピレンカーボネート50%溶液(サンアプロ社製) 2質量部
上記各添加剤を順次添加し、120℃で混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、有色インク109を調製した。
上記有色インク109の調製において、ゲル化剤を、CROTHIX OG-CSからステアリン酸イヌリン(レオパールISK2 千葉製粉株式会社製)に変更した以外は同様にして、有色インク110を調製した。
(無色インク201の調製:ラジカルUV無色インク、ゲル化剤無)
光重合性化合物1:ラウリルアクリレート(単官能) 25質量部
光重合性化合物2:エチレンオキサイド変性トリメチロールプロパントリアクリレート(三官能) 5質量部
光重合性化合物3:カプローラクタム変性ジペンタエリスリトールヘキサアクリレート(六官能) 35質量部
光重合性化合物4:テトラエチレングリコールジアクリレート(二官能)
30質量部
重合開始剤1:イルガキュア184(BASFジャパン社製)
2.5質量部
重合開始剤2:イルガキュア907(BASFジャパン社製)
2.5質量部
上記各添加剤を順次添加、混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、無色インク201を調製した。
光重合性化合物1:ラウリルアクリレート(単官能) 25質量部
光重合性化合物2:エチレンオキサイド変性トリメチロールプロパントリアクリレート(三官能) 5質量部
光重合性化合物3:カプローラクタム変性ジペンタエリスリトールヘキサアクリレート(六官能) 25質量部
光重合性化合物4:テトラエチレングリコールジアクリレート(二官能)
30質量部
ゲル化剤:12-ヒドロキシステアリン酸(Alfa Aesar社製)
10質量部
重合開始剤1:イルガキュア184(BASFジャパン社製)
2.5質量部
重合開始剤2:イルガキュア907(BASFジャパン社製)
2.5質量部
上記各添加剤を順次添加、混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、無色インク202を調製した。
上記無色インク202の調製において、ゲル化剤を、12-ヒドロキシステアリン酸からステアロン(Alfa Aesar社製)に変更した以外は同様にして、無色インク203を調製した。
重合性化合物1:脂環式エポキシ化合物(CEL2021P、ダイセル化学社製) 25質量部
重合性化合物2:オキセタン(OXT221、東亞合成社製)72質量部
CPI-100P:トリアリルスルホニウム塩のプロピレンカーボネート50%溶液(サンアプロ社製) 2質量部
チオキサントン(DETX、日本化薬製) 1.0質量部
上記各添加剤を順次添加、混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、無色インク204を調製した。
重合性化合物1:脂環式エポキシ化合物(CEL2021P、ダイセル化学社製) 25質量部
重合性化合物2:オキセタン化合物(OXT221、東亞合成社製)
61.5質量部
ゲル化剤:ステアロン(Alfa Aesar社製) 10質量部
光重合開始剤1:ヨードニウム塩(IBPF、三和ケミカル製)
2.5質量部
チオキサントン(DETX、日本化薬製) 1.0質量部
上記各添加剤を順次添加、混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、無色インク205を調製した。
上記無色インク205の調製において、ゲル化剤を、ステアロンからEB-21(ジブチルエチルヘキサノイルグルタミド 味の素株式会社製)に変更した以外は同様にして、無色インク206を調製した。
シクロヘキサンジビニルエーテル(CHDVE 日本カーバイド工業株式会社製) 78質量部
ビニルエーテルオリゴマー(Vectomer 2020 Aldrich社製) 20質量部
TEMPO(2,2,6,6-テトラメチルピペリジン 1-オキシル)
0.03質量部
CPI-100P:トリアリルスルホニウム塩のプロピレンカーボネート50%溶液(サンアプロ社製) 2質量部
上記各添加剤を順次添加、混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、無色インク207を調製した。
シクロヘキサンジビニルエーテル(CHDVE 日本カーバイド工業株式会社製) 73質量部
ビニルエーテルオリゴマー(Vectomer 2020 Aldrich社製) 20質量部
ゲル化剤:CROTHIX OG-CS(Croda社製) 5質量部
TEMPO(2,2,6,6-テトラメチルピペリジン 1-オキシル)
0.03質量部
CPI-100P:トリアリルスルホニウム塩のプロピレンカーボネート50%溶液(サンアプロ社製) 2質量部
上記各添加剤を順次添加し、120℃で混合した後、絶対ろ過精度2μmのフィルターを用いてろ過して、無色インク208を調製した。
上記無色インク208の調製において、ゲル化剤を、CROTHIX OG-CSからステアリン酸イヌリン(レオパールISK2 千葉製粉株式会社製)に変更した以外は同様にして、無色インク209を調製した。
上記調製した各有色インク及び無色インクについて、表3に記載の組み合わせでインクセット1~31を調製した。なお、便宜上、有色インク単独であっても、インクセット番号を付与した。
ピエゾ型ヘッドを備え、ラインヘッド方式のインクジェット記録装置に上記調製した各有色インク、無色インクを装填し、基材として裏移り耐性は普通紙(XEROX社製 XEROX4024)、それ以外の評価項目ではアート紙(三菱製紙社製 特菱アート両面N)を用いて黒ベタ、楔様画像を印刷した。尚、無色インクは有色インク用ヘッド群に比べ下流側に配置し、表4に記載した様に、有色インクの付与量にかかわらず無色インクを均一に付与する無色インクの付与方法(表4では「均一」と記載)と、付与する有色インクの付与量に対し逆像様に付与する無色インクの付与方法(表4には、「逆像様」と記載)に分けて印刷を行った。
上記調製した各インクセットについて、上記方法に従って作成した印画サンプルについて評価を行った。
基材として普通紙を用いて画像印字した各基材の裏面を目視観察し、下記の評価基準に従って裏抜け耐性を評価した。
○:わずかににじみ及び裏抜けの発生が認められるが、実用上許容される品質である
△:裏面にインクのにじみ及び裏抜けが認められ、裏面印刷に対しては不適の品質
×:明らかな裏面へのインクのにじみ及び裏抜けの発生が認められる
〔給紙適合性〕
各基材(普通紙、アート紙)上に連続50枚の画像出力を行った後、ジャミングの発生による停止の有無、搬送ローラへの異物付着および形成画像の剥がれについて観察を行い、下記基準に従い給紙適合性を評価した。
○:連続出力を行っても、ジャミングの発生がなく、また搬送ローラへの異物付着や形成画像の膜剥がれが認められなかったが、ごく一部の形成画像で軽微な膜剥がれが発生が認められるが、実用上許容される品質である
△:連続出力を行った場合、ジャミングあるいは搬送ローラへの異物付着が1回発生するか、一部の形成画像で軽微な膜剥がれの発生が認められ、実用上問題となる品質である
×:連続出力時に数回のジャミングが発生し、さらに搬送ローラへの異物付着や形成画像の膜剥がれが認めら、実用に耐えない品質である
〔裏移り耐性の評価〕
上記方法により印刷物を100部作成し、印刷面が隣り合う紙の裏面(非印字面)と接するように100枚重ね合わせて、40℃、80%RHの環境下で3日間放置した。その後、重ね合わせた印刷物を上記環境から取り出し、1枚ずつ印刷紙をめくり、その際に表裏くっつきが起きる枚数をカウントし、下記基準に従って裏移り耐性を評価した。
○:表裏くっつきの発生数が1枚であるが、その程度も軽微
△:表裏くっつきの発生数が1~4枚であり、実用上許容できない品質
×:表裏くっつきの発生数が5枚以上であり、実用に耐えない品質である
〔光沢均一性の評価〕
楔状に印刷濃度を連続的に変化させた画像を形成し、その光沢の均一性を目視評価し、下記の基準に従って、光沢均一性を評価した。
○:一部の濃度領域において軽微な光沢不均一性がみられるが、実用上許容される品質
△:濃度による光沢の不均一性の発生が認められ、実用上問題となる品質である
×:全濃度領域にわたり、強い光沢の不均一が発生し、実用に耐えない品質である
〔耐擦性の評価〕
アート紙上にベタ画像を印字した後に、スクラッチ強度試験機HEIDON-18(HEIDON社製)を用い、測定針は0.8mmRのサファイヤ針を用いてスクラッチ強度の測定を行った。測定は、一定荷重で10cm引っかき試験を3回行い、基材に傷が入り始める直前の荷重をスクラッチ強度と定義し、その測定値より下記基準に従って耐擦性を評価した。
○:スクラッチ強度が、150g以上、200g未満である
△:スクラッチ強度が、100g以上、150g未満である
×:スクラッチ強度が、100g未満である
以上により得られた各評価結果を、表4に示す。
2 記録媒体の搬送手段
21 搬送ローラ対
3 記録ヘッド
34 記録媒体保持部
4 加熱加圧手段
41 加熱ローラ
42 圧着ローラ
43 発熱体
44 加熱ベルト
45 下部圧着ベルト
46 従動ローラ
5 温度センサ
6 記録媒体の切断手段
61、62 カッタ
7 たるみ形成手段
71 第1のローラ対
72 第2のローラ対
Claims (6)
- 活性エネルギー線硬化性組成物と熱可逆性ゲルを形成するゲル化剤を含み、色材を含まない無色インクを基材に付与した後に、加熱を行い、その後に活性エネルギー線を照射することを特徴とするインクジェット画像形成方法。
- 前記無色インクを基材に付与した後、前記ゲル化剤の溶融温度に対し、10℃以上高い温度で基材を加熱した後、前記活性エネルギー線を照射することを特徴とする請求項1に記載のインクジェット画像形成方法。
- 1)活性エネルギー線硬化性組成物、熱可逆性ゲルを形成するゲル化剤及び色材を含む有色インクと、2)活性エネルギー線硬化性組成物、熱可逆性ゲルを形成するゲル化剤を含み、色材を含まない無色インクとから構成されることを特徴とするインクジェットインクセット。
- 前記有色インク及び前記無色インクが含有する活性エネルギー線硬化性組成物が、いずれもラジカル重合性化合物であることを特徴とする請求項3に記載のインクジェットインクセット。
- 前記有色インク及び前記無色インクが含有する活性エネルギー線硬化性組成物が、いずれもカチオン重合性化合物であることを特徴とする請求項3に記載のインクジェットインクセット。
- 請求項3から5のいずれか1項に記載のインクジェットインクセットを用い、1)活性エネルギー線硬化性組成物、熱可逆性ゲルを形成するゲル化剤及び色材を含む有色インクを画像形成領域に付与した後、2)活性エネルギー線硬化性組成物、熱可逆性ゲルを形成するゲル化剤を含み、色材を含まない無色インクを画像形成領域全面に付与し、加熱を行い、その後に活性エネルギー線を照射することを特徴とするインクジェット画像形成方法。
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JP5250854B2 (ja) | 2013-07-31 |
US9499703B2 (en) | 2016-11-22 |
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