WO2015156267A1 - 活性光線硬化型インクジェット白色インクおよび画像形成方法 - Google Patents
活性光線硬化型インクジェット白色インクおよび画像形成方法 Download PDFInfo
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- WO2015156267A1 WO2015156267A1 PCT/JP2015/060793 JP2015060793W WO2015156267A1 WO 2015156267 A1 WO2015156267 A1 WO 2015156267A1 JP 2015060793 W JP2015060793 W JP 2015060793W WO 2015156267 A1 WO2015156267 A1 WO 2015156267A1
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Images
Classifications
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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
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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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
-
- 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
-
- 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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- 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
-
- 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
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- 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
- C09D11/34—Hot-melt inks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/21—Ink jet for multi-colour printing
- B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
- B41J2/2114—Ejecting specialized liquids, e.g. transparent or processing liquids
- B41J2/2117—Ejecting white liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/21—Ink jet for multi-colour printing
- B41J2/2132—Print quality control characterised by dot disposition, e.g. for reducing white stripes or banding
- B41J2/2146—Print quality control characterised by dot disposition, e.g. for reducing white stripes or banding for line print heads
Definitions
- the present invention relates to an actinic ray curable inkjet white ink and an image forming method.
- the ink jet recording method is used in various printing fields because it can form an image easily and inexpensively.
- an actinic ray curable ink jet method in which droplets of ultraviolet curable ink are landed on a recording medium and then cured by irradiation with actinic rays to form an image.
- the actinic ray curable ink jet method has been attracting attention in recent years because it has high adhesion even when applied to a recording medium having no ink absorption or when it is overcoated with other ink.
- the actinic ray curable inkjet ink contains a wax or a gelling agent for the purpose of preventing unnecessary mixing between the inks and enhancing the scratching of the resulting image.
- the technology to make it known is known.
- the sol-gel phase transition is possible due to the temperature change by the wax or the gelling agent, the ink is gelled when adhering to the recording medium, so that mixing of the inks and spreading of the dots can be prevented.
- the viscosity of the ink can be increased even at a low temperature, it is possible to obtain a printed matter having excellent scratch resistance at room temperature.
- Patent Document 1 and Patent Document 2 describe image forming methods that produce a desired aesthetic appearance by using color ink and white ink together. At this time, by forming the white ink into an actinic ray curable ink-jet ink capable of sol-gel phase transition by temperature change, image formation can be performed by a simpler method. In addition, the white ink can be used for overcoating or undercoating for image formation with other inks to form a background color.
- a pigment such as titanium dioxide is used. Since titanium dioxide has a problem in light resistance as it is, it is used after surface coating with alumina or the like. However, since alumina is easily polarized, it is difficult to stably disperse in non-polar solvents such as those used in actinic ray curable inkjet inks, and particles are likely to associate with each other. Therefore, in an ink containing titanium dioxide as a pigment, the dispersibility of the pigment is increased by containing a dispersant in the ink, and the ink is stably stored.
- Patent Document 3 in an ink containing a white pigment such as titanium dioxide, the pigment is dispersed in a dispersant containing a copolymer having a pigment affinity group or a block copolymer.
- a dispersant containing a copolymer having a pigment affinity group or a block copolymer.
- these dispersants those having a secondary amine as a pigment affinity group are disclosed.
- the gelling agent a free radical curable gelling agent polymerized by an amide bond is used.
- Titanium dioxide can also be used to suppress ink blooming.
- an actinic ray curable inkjet ink that can be gelled with wax contains less than 5% of titanium dioxide as inorganic fine particles with weak coloring power.
- JP 2007-63553 A Japanese Patent No. 4765256 JP 2009-41015 A JP 2013-121992 A
- Inkjet ink is heated to a temperature close to 85 ° C. during ejection. At this time, if the adsorption of the dispersant to the pigment is weak, the dispersant is detached from the pigment, causing re-aggregation of the pigments and increasing the viscosity of the ink. When the viscosity of the ink increases, ejection failure and clogging of the ink ejection recording head are likely to occur.
- sodium ions used for the surface coating remain on the surface of the titanium dioxide surface-coated with alumina, and the interaction between the sodium ions and the gelling agent or wax contained in the ink causes the ink to Gelation may be suppressed. If the gelation of the ink is suppressed, the ink spreads without being sufficiently pinned, and the surface of the ink that has landed on the recording medium is excessively smoothed, resulting in excessive glossiness of the ink. There may be a difference in gloss from the color. In particular, when white ink is used for overcoating or undercoating (background), the appearance of an image may be impaired if there is a difference in gloss from other color inks used for image formation. In addition, when sodium ions derived from titanium dioxide form a metal salt with a gelling agent or a fatty acid residue contained in the wax, the deposited metal salt may clog the ink discharge recording head.
- the present invention relates to the actinic ray curable inkjet white ink described below.
- An actinic ray curable inkjet white ink containing a pigment, a dispersant, a wax, a photopolymerizable compound, and a photopolymerization initiator and capable of undergoing a sol-gel phase transition by temperature change, wherein the pigment is surface-coated with alumina Titanium dioxide is included, and the content of the titanium dioxide is 10% by mass or more and 15% by mass or less in the total mass of the ink, the ink contains 200 ppm or less sodium ion in a mass ratio with respect to the pigment, An ink comprising a comb block copolymer having a tertiary amine group.
- the present invention also relates to an image forming method described below.
- [6] The step of ejecting the actinic radiation curable inkjet white ink according to any one of [1] to [5] from a recording head for ejecting ink and adhering the recording medium to the recording medium; Irradiating an inkjet white ink with actinic rays.
- the image forming method according to [6] further comprising a step of attaching one or a plurality of color inks on the recording medium and a step of fixing the attached color inks.
- the color ink is an actinic ray curable ink containing a photopolymerizable compound and a photopolymerization initiator, and the step of fixing the attached color ink is a step of irradiating the attached color ink with an actinic ray.
- the step of irradiating the color ink with an actinic ray and the step of irradiating the attached actinic ray curable inkjet white ink with an actinic ray are performed by a single actinic ray irradiation, any of [7] to [9] The method of crab.
- an actinic ray curable inkjet white ink capable of sol-gel phase transition by temperature change even when titanium dioxide is used as a pigment, an increase in the viscosity of the ink is suppressed, and gloss equivalent to other colors is achieved. And an actinic ray curable inkjet white ink and an image forming method using the ink are provided.
- FIG. 1A is a side view of an example of a configuration of a main part of a line recording type inkjet recording apparatus that can be used for image formation according to an aspect of the present invention.
- FIG. 1B is a top view of an example of a configuration of a main part of a line recording type inkjet recording apparatus that can be used for image formation according to an embodiment of the present invention.
- FIG. 2A is a side view of another example of the configuration of the main part of a line recording type inkjet recording apparatus that can be used for image formation according to another aspect of the present invention.
- FIG. 2B is a top view of another example of the configuration of the main part of the line recording type inkjet recording apparatus that can be used for image formation according to another aspect of the present invention.
- FIG. 3 is a top view illustrating an example of a configuration of a main part of a serial recording type inkjet recording apparatus that can be used for image formation according to still another aspect of the present invention.
- Actinic ray curable inkjet white ink The ink according to the present invention is an actinic ray curable inkjet white ink (hereinafter also simply referred to as white ink) containing a pigment, a dispersant, a wax, a photopolymerizable compound, and a photopolymerization initiator.
- the pigment is titanium dioxide surface-coated with alumina
- the ink contains 10% by mass to 15% by mass of the titanium dioxide in the total mass of the ink
- the ink contains 200 ppm or less of sodium ions.
- the dispersant is an ink containing a comb-type block copolymer having a tertiary amine group.
- the actinic ray curable inkjet white ink of the present invention contains a pigment.
- Pigments include titanium dioxide surface coated with alumina.
- the actinic ray curable inkjet white ink of the present invention contains titanium dioxide surface-coated with alumina in a content of 10% by mass to 15% by mass.
- the crystal form of titanium dioxide includes rutile type, anatase type and blue kite type.
- the anatase type is preferable from the viewpoint of low specific gravity and easy particle size reduction, and the rutile type is preferable from the viewpoint of high refractive index and high concealability.
- a combination of titanium oxides having different crystal forms may be used.
- the weight average particle diameter of titanium dioxide is preferably 50 nm or more and 500 nm or less, and more preferably 100 nm or more and 300 nm or less. By setting the weight average particle diameter of titanium dioxide to 50 nm or more, an ink having a sufficient hiding property can be obtained. On the other hand, when the weight average particle diameter of titanium dioxide is 500 nm or less, titanium dioxide can be stably dispersed, and ink storage stability and ejection stability can be improved.
- surface coating of titanium dioxide with alumina a known method described in Japanese Patent No. 3546064 and Japanese Patent No. 2833820 can be used.
- surface coating of titanium dioxide with alumina can be performed by the following procedure. 1) Disperse titanium oxide in water to form a slurry. 2) The slurry obtained in 1) is adjusted to a predetermined temperature, and a soluble aluminum compound (sodium aluminate) as a surface treatment agent is added and dissolved. 3) While maintaining the pH of the slurry obtained in 2) within a predetermined range, an acid precipitating agent is added to neutralize the aluminum hydrate.
- a soluble aluminum compound sodium aluminate
- commercially available titanium dioxide may be used.
- Preferred examples of commercially available titanium dioxide that can be used in the present invention include CR-EL (Ishihara Sangyo Co., Ltd.), CR-50 (Ishihara Sangyo Co., Ltd.), CR-80 (Ishihara Sangyo Co., Ltd.), and CR-90.
- sodium ions (Na + ) that are residual ions of sodium aluminate may remain. If the amount of sodium ions present in the surface of titanium dioxide or desorbed from the surface of titanium dioxide is high in the ink, the interaction between the sodium ions and the wax in the inkjet ink will cause the wax to gel sufficiently. In other words, the droplet diameter may increase due to insufficient pinning and excessive gloss may occur. Further, when sodium ions form a metal salt with a fatty acid contained in the wax and deposit it, the ink ejection recording head may be clogged. Therefore, in the present invention, it is preferable to remove sodium ions remaining in titanium dioxide before preparing the ink. Sodium ions remaining in the titanium dioxide can be removed by a method such as treatment with a fatty acid, water washing, or a combination of water washing and ultrasonic washing.
- the amount of sodium ions in the ink is set to 200 ppm or less in terms of the mass ratio to the pigment.
- the amount of sodium ions in the ink means the amount of sodium ions present on the surface of titanium dioxide or the amount of sodium ions present free in the ink.
- the amount of sodium ions in the ink derived from other than titanium dioxide is often negligible, if the amount of sodium ions remaining in the titanium dioxide used in the ink of the present invention can be measured, the amount is It may be the amount of sodium ions in the ink.
- commercially available titanium dioxide having a sodium ion amount of 200 ppm or less may be used, or the above-mentioned removal treatment may be applied to commercially available titanium dioxide so that the residual sodium ion amount is 200 ppm.
- the amount of sodium ions By setting the amount of sodium ions to 200 ppm or less, it is possible to prevent insufficient gelation of the wax due to the interaction between the sodium ions and the wax, and to suppress the precipitation of the metal salt caused by the binding between the sodium ions and the fatty acid residues, Clogging of the ink ejection recording head can be suppressed.
- the amount of sodium ions in the ink can be measured, for example, by the following procedure. 1) Methanol is added to the ink, and the resulting solution is put into a centrifuge tube, and centrifuged at 20000 rpm for 1 hour to separate it into a solid and a solution. 2) The dried solid is decomposed with a mixed acid of concentrated nitric acid / concentrated hydrochloric acid (molar ratio 1/10) by a sealed microwave decomposition apparatus to form a solution. 3) The amount of sodium ion in the concentrated nitric acid / concentrated hydrochloric acid solution obtained in 2) is measured by ICP-AES (manufactured by Seiko Instruments Inc.
- the amount of residual sodium ions contained in titanium dioxide can be measured, for example, by the following procedure. 1) The surface-treated titanium dioxide powder is decomposed with a mixed acid of concentrated nitric acid / concentrated hydrochloric acid (molar ratio 1/10) by a sealed microwave decomposition apparatus to form a solution. 2) The amount of sodium ion in the concentrated nitric acid / concentrated hydrochloric acid solution obtained in 1) is measured by ICP-AES (SEPS Instruments Co., Ltd. SPS3520UV).
- the surface treatment amount (surface coating amount) by alumina is preferably 0.3% by mass or more and 0.8% by mass or less, and 0.5% by mass or more and 0.7% by mass or less with respect to untreated titanium oxide. It is more preferable that By setting the surface treatment amount to 0.3% by mass or more, the weather resistance of the cured film of the ink can be obtained. On the other hand, when the surface treatment amount is 0.8% by mass or less, the amount of residual sodium ions can be easily reduced to a preferable range.
- the surface treatment amount of the surface-treated titanium oxide can be measured by the following procedure. That is, 1) The surface-treated titanium oxide powder is decomposed with an aqueous hydrofluoric acid solution into a solution by a sealed microwave decomposition apparatus. 2) The amount of Al in the obtained aqueous solution is measured by ICP-AES.
- the titanium dioxide surface-coated with the alumina of the present invention may be surface-coated by combining other metal oxides in addition to alumina.
- the actinic ray curable inkjet white ink of the present invention contains 10% by mass to 15% by mass of titanium dioxide whose surface is coated with alumina in the total mass of the ink.
- the content of titanium dioxide surface-coated with alumina is 10% by mass or more, white color development is sufficient.
- the actinic ray curable inkjet white ink of the present invention may contain a known white pigment other than titanium dioxide whose surface is coated with alumina.
- These known white pigments include inorganic white pigments, organic white pigments, white hollow polymer fine particles and the like.
- the actinic ray curable inkjet white ink of the present invention may contain a dye or a pigment other than white in order to adjust the color tone.
- the pigment can be dispersed by, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like.
- the actinic ray curable inkjet ink of the present invention may further contain at least one of an ultraviolet absorber and an antioxidant in order to improve the weather resistance of the cured product.
- the ultraviolet absorber preferably has a long wavelength end of 410 nm or less from the viewpoint of light resistance and ozone resistance.
- the absorption wavelength of the ultraviolet absorber can be determined by measuring an ultraviolet-visible absorption spectrum.
- the content of the ultraviolet absorber is preferably 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less with respect to the entire ink.
- the content of the ultraviolet absorber is preferably 0.1% by mass or more.
- the content of the antioxidant is preferably 0.8% by mass or less, and more preferably 0.5% by mass or less, based on the entire ink. When there is too much content of antioxidant, sclerosis
- the total amount of the ultraviolet absorber and the antioxidant is preferably 2.0% by mass or less, and more preferably 1.0% by mass or less with respect to the entire ink.
- the total amount of the ultraviolet absorber and the antioxidant is more than 2.0% by mass, the viscosity of the ink becomes high, and the injection stability may be lowered or the curability may be lowered.
- the actinic ray curable inkjet white ink of the present invention contains a dispersant.
- a dispersant in the ink, the dispersibility of the pigment can be enhanced.
- the present invention includes a comb-type block copolymer having a tertiary amine group (hereinafter, also simply referred to as “copolymer according to the present invention”) in the dispersant.
- the comb block copolymer is a copolymer in which another type of polymer is graft-polymerized as a side chain for each unit of monomers constituting the main chain with respect to a linear polymer forming the main chain.
- the content of the copolymer according to the present invention is not limited, but is preferably 2.0% by mass or more and 8.0% by mass or less in the total mass of the ink.
- the content of the copolymer according to the present invention is 2.0% by mass or more, the dispersibility of the pigment can be further improved due to the steric hindrance effect of the dispersant.
- the content of the copolymer according to the present invention is 8.0% by mass or less, an increase in viscosity due to the entanglement of the copolymers can be prevented, and clogging of the ink ejection recording head can be suppressed.
- the content of the copolymer according to the present invention is more preferably 2.0% by mass or more and 5.0% by mass or less in the total mass of the ink.
- the copolymer according to the present invention has a tertiary amine group, the electron density of the amine, which is a functional group having adsorptivity to the pigment, is increased, and strong basicity is exhibited. It can be adsorbed firmly. Therefore, the copolymer according to the present invention hardly dissociates from the pigment even at around 85 ° C. where the inkjet ink is ejected. Further, when a copolymer having a tertiary amine group in the main chain is used as the copolymer according to the present invention, the side chain is compatible with the photopolymerizable compound described later, and the dispersant itself is easily dispersed, so that the dispersant is adsorbed. The dispersibility of the obtained pigment can also be improved.
- the substituent of the amine is not particularly limited, but an alkyl group having 1 or 2 carbon atoms is preferable.
- the type of the copolymer according to the present invention is not particularly limited as long as it is a dispersant satisfying the above conditions.
- Preferred examples of such a dispersant include BYK-2164, BYK-168, BYK-N-22024, manufactured by BYK Chemie, BYK JET-9150, BYK JET-9151, manufactured by Altana, EFKA 4310, manufactured by BASF, and EFKA. 4320, EFKA 4401, Avecia's SOLPERSE 39000, Ajinomoto Fine Techno Co., Ltd. Ajisper PB-821 and the like.
- the amine group of the comb block copolymer having a secondary or primary amine group may be tertiary by substituting hydrogen having an amine group with another substituent by a known method.
- the secondary amine group or primary amine group of the comb block copolymer can be reacted with an alcohol such as decyl alcohol in the presence of a reduction catalyst to form a tertiary amine group substituted with an alkyl group. .
- the white ink of the present invention includes, for example, 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 polarity.
- Dispersants such as polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl phenyl ether, and stearylamine acetate. Examples of commercially available dispersants include Avecia's Solsperse series and Ajinomoto Fine-Techno's PB series.
- the actinic ray curable inkjet white ink of the present invention may further contain a dispersion aid as necessary.
- the dispersion aid may be selected according to the pigment.
- the actinic ray curable inkjet white ink of the present invention may further include a dispersion medium for dispersing the pigment as necessary.
- a solvent may be included in the ink as the dispersion medium, it is preferable that a photopolymerizable compound described later is the dispersion medium in order to suppress residual solvent in the formed image.
- the actinic ray curable inkjet white ink of the present invention contains a wax.
- the wax is defined as “an organic substance that is solid at room temperature and becomes liquid when heated”.
- the actinic ray curable inkjet white ink of the present invention preferably contains 1.2% by mass or more and less than 5.5% by mass of wax in the total mass of the ink.
- the wax content By setting the wax content to 1.2% by mass or more, the slipperiness of the image surface is increased, and the scratch resistance of the image can be improved.
- By setting the wax content to 5.5% by mass or less generation of excessive gloss due to the wax deposited on the image surface can be prevented, and ink ejection properties from the inkjet head can be improved.
- the type of wax is not particularly limited, but examples include higher fatty acids, higher alcohols, fatty acid esters, triglycerides, fatty acid amines, aliphatic ketones, fatty acid amides, and the like.
- the wax of the present invention has a function of reversibly sol-gel phase transition of ink according to temperature.
- the wax should be soluble in the photopolymerizable compound at a temperature higher than the gelation temperature, and should be crystallized in the ink at a temperature lower than the gelation temperature.
- the wax is crystallized in the ink
- a plate crystal which is a crystallized product of the wax forms a three-dimensional space
- the actinic ray curable compound is included in the space.
- the structure in which the actinic ray curable compound is encapsulated in the space three-dimensionally surrounded by the plate crystal is sometimes referred to as “card house structure”.
- the liquid actinic radiation curable compound can be retained and the ink droplets can be pinned. Thereby, coalescence of the droplets can be suppressed, and generation of excessive gloss due to the smoothing of the ink can be suppressed.
- the actinic ray curable compound dissolved in the ink and the wax are compatible.
- the actinic ray curable compound dissolved in the ink and the wax are phase-separated, it may be difficult to form a card house structure.
- Preferred examples of the wax include aliphatic ketone compounds such as 18-pentatriacontanone and 16-hentriacontanone (for example, Kao Wax T1 manufactured by Kao Corporation); cetyl palmitate, stearyl stearate, behenyl behenate, etc.
- Aliphatic monoester compounds for example, UNISTA-M-2222SL (manufactured by NOF Corporation), EXCEPARL SS (manufactured by Kao Corporation, melting point 60 ° C.), EMALEX CC-18 (manufactured by Nippon Emulsion Co., Ltd.), Amreps PC (high grade) Alcohol Kogyo Co., Ltd.), Exepar MY-M (Kao Co., Ltd.), Spalm Aceti (Nippon Oil Co., Ltd.), EMALEX CC-10 (Nihon Emulsion Co., Ltd.), etc.); N-lauroyl-L-glutamic acid dibutylamide N- (2-ethylhexanoyl) -L-glutamic acid dibuty Amide compounds such as amides (available from Ajinomoto Fine Techno); 1,3: 2,4-bis-O-benzylidene-D-glucitol (available from Gelol D Shin Nippo
- behenic acid arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid and higher fatty acids such as erucic acid; higher alcohols such as stearyl alcohol and behenyl alcohol; hydroxystearic acid such as 12-hydroxystearic acid A fatty acid amide such as lauric acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, 12-hydroxystearic acid amide (for example, Nikka Amide manufactured by Nippon Kasei Co., Ltd.); Series, ITOWAX series manufactured by Ito Oil Co., Ltd., FATTYAMID series manufactured by Kao Corporation, etc.); N-substituted fatty acid amides such as N-stearyl stearamide, N-oleyl palmitate amide; N, N′-ethylenebis Special fatty acid amides such as thet
- Sucrose fatty acid esters such as sucrose stearic acid and sucrose palmitic acid (eg Ryoto Sugar Ester series Mitsubishi Chemical Foods); synthetic waxes such as polyethylene wax and ⁇ -olefin maleic anhydride copolymer wax; polymerizable waxes (UNILIN series etc. manufactured by Baker-Petrolite); dimer acids; dimer diols (PRIDOR series manufactured by CRODA etc.) ) Etc. are included. These waxes may be used alone or in combination of two or more.
- an aliphatic ketone and a fatty acid ester can be used in combination as the wax.
- the wax is attracted to the polarized alumina, and the wax may not be sufficiently gelled. If the wax is not sufficiently gelled, ink droplets are likely to spread due to insufficient pinning of the ink, and the surface of the ink is excessively smoothed, resulting in excessive gloss.
- aliphatic ketones are difficult to be attracted to alumina, if aliphatic ketones are used as waxes, the ink can be gelled well and the droplets are difficult to spread.
- the total of the aliphatic ketone content and the fatty acid ester content in the total mass of the actinic ray curable inkjet white ink of the present invention is preferably 2.0% by mass or more and 5.0% by mass or less.
- the total content of these waxes is 2.0% by mass or more, the ink sufficiently undergoes sol-gel phase transition, so that the dot diameter can be prevented from spreading, and the gloss is adjusted to the same level as other inks. be able to.
- the total content of these waxes is 5.0% by mass or less, an increase in viscosity due to excessive wax can be prevented.
- the actinic ray curable inkjet white ink of the present invention is the same amount as the fatty acid ester content or more than the fatty acid ester content. It is preferable that the said aliphatic ketone is included.
- the aliphatic ketone as the wax is represented by, for example, the following formula (1).
- R1 and R2 are each independently an aliphatic hydrocarbon group containing a straight chain portion having 9 to 25 carbon atoms.
- the number of carbon atoms of the aliphatic hydrocarbon groups represented by R1 and R2 in the formula (1) may be approximately the same.
- the aliphatic hydrocarbon group may be a saturated or unsaturated aliphatic hydrocarbon group, but is preferably a saturated aliphatic hydrocarbon group (alkylene group) from the viewpoint of increasing the gelation temperature of the ink.
- the melting point of the compound in which R1 and R2 in the formula (1) are saturated aliphatic hydrocarbon groups is higher than the melting point of the compound in which R1 and R2 in the formula (1) are unsaturated aliphatic hydrocarbon groups.
- the saturated aliphatic hydrocarbon group may be an aliphatic hydrocarbon group which may have a branched portion, but in order to obtain high crystallinity, a saturated aliphatic hydrocarbon group preferably having no branched portion is preferable. (Linear alkylene group).
- the number of carbon atoms in the linear portion contained in R1 and R2 in the formula (1) is preferably 9 or more and 25 or less.
- the straight chain portion contained in the aliphatic hydrocarbon group has 9 or more carbon atoms, the crystallinity of the wax is sufficient, and in the card house structure described above, the actinic ray curable compound is included. Sufficient space is easily formed.
- the straight-chain portion contained in the aliphatic hydrocarbon group has 25 or less carbon atoms, the melting point does not become too high. Therefore, the wax is used even at the ink ejection temperature from the ink discharge recording head that is normally used. Is easily dissolved in the ink.
- R1 and R2 are particularly preferably a linear saturated aliphatic hydrocarbon group (straight chain alkylene group) having 11 to 23 carbon atoms.
- Examples of the aliphatic hydrocarbon group containing a straight chain portion having 9 to 25 carbon atoms include docosanyl group (C22), icosanyl group (C20), octadecanyl group (C18), heptadecanyl group (C17), hexadecanyl group ( C16), pentadecanyl group (C15), tetradecanyl group (C14), tridecanyl group (C13), dodecanyl group (C12), undecanyl group (C11), decanyl group (C10) and the like.
- the fatty acid ester as the wax is represented by the following formula (2), for example.
- R3 and R4 are each independently an aliphatic hydrocarbon group containing a straight chain portion having 9 to 26 carbon atoms.
- the number of carbon atoms of the aliphatic hydrocarbon groups represented by R3 and R4 in the formula (2) may be approximately the same.
- the aliphatic hydrocarbon group may be a saturated or unsaturated aliphatic hydrocarbon group, but is preferably a saturated aliphatic hydrocarbon group (alkylene group) from the viewpoint of increasing the gelation temperature of the ink.
- the melting point of the compound in which R3 and R4 in the formula (2) are saturated aliphatic hydrocarbon groups is higher than the melting point of the compound in which R3 and R4 in the formula (2) are unsaturated aliphatic hydrocarbon groups.
- the saturated aliphatic hydrocarbon group may be an aliphatic hydrocarbon group which may have a branched portion, but in order to obtain high crystallinity, a saturated aliphatic hydrocarbon group preferably having no branched portion is preferable. (Linear alkylene group).
- the number of carbon atoms of the straight chain portion contained in R3 and R4 of the formula (2) is 9 or more and 26 or less.
- the straight chain portion contained in the aliphatic hydrocarbon group has 9 or more carbon atoms, the crystallinity of the wax is sufficient, and in the card house structure described above, the actinic ray curable compound is included. Sufficient space is easily formed.
- the straight-chain portion contained in the aliphatic hydrocarbon group has 26 or less carbon atoms, the melting point does not become too high. Therefore, the wax is used even at the ink ejection temperature from the normally used ink discharge recording head. Is easily dissolved in the ink.
- the number of carbon atoms in the straight chain portion contained in the aliphatic hydrocarbon group of R3 is 11 or more and less than 23, and the fatty acid of R4 It is preferable that the straight chain portion contained in the group hydrocarbon group has 12 or more and less than 24 carbon atoms. Therefore, it is particularly preferable that R3 is a linear alkylene group having 11 to 23 carbon atoms, and R4 is a linear alkylene group having 12 to 24 carbon atoms.
- Examples of the aliphatic hydrocarbon group containing a straight chain part having 9 to 26 carbon atoms are the same as the aliphatic hydrocarbon group containing a straight chain part having 9 to 25 carbon atoms in the above formula (1). Is included.
- the ink according to the present invention contains a predetermined amount of wax, the ink is ejected from the ink ejection recording head, adheres to the recording medium as ink droplets, and quickly decreases to a temperature lower than the gelling temperature. It becomes a gel state. For this reason, mixing of dots and dot coalescence are suppressed, and high image quality can be formed during high-speed printing. Thereafter, the gelled ink droplets are irradiated with light and cured, whereby the ink droplets are fixed on the recording medium to form a strong image film.
- the ink droplets that have landed on the recording medium are quickly gelled, so that the ink droplets do not diffuse on the recording medium, so that oxygen in the environment does not easily enter the ink droplets. Therefore, it becomes difficult to be affected by oxygen inhibition during curing.
- the actinic ray curable inkjet white ink of the present invention contains a photopolymerizable compound.
- the photopolymerizable compound is a compound that crosslinks or polymerizes with actinic rays.
- the actinic rays are, for example, electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, and X-rays, preferably ultraviolet rays and electron beams, and more preferably ultraviolet rays.
- the photopolymerizable compound is a radically polymerizable compound or a cationically polymerizable compound, preferably a radically polymerizable compound.
- the radical polymerizable compound is a compound (monomer, oligomer, polymer or mixture thereof) having an ethylenically unsaturated bond capable of radical polymerization. Only one kind of radically polymerizable compound may be contained in the actinic ray curable inkjet white ink, or two or more kinds thereof may be contained.
- Examples of the compound having an ethylenically unsaturated bond capable of radical polymerization include an unsaturated carboxylic acid and a salt thereof, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid urethane compound, an unsaturated carboxylic acid amide compound and an anhydride thereof, Examples include acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane.
- Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like.
- the radical polymerizable compound is preferably an unsaturated carboxylic acid ester compound, and more preferably a (meth) acrylate compound.
- the (meth) acrylate compound may be not only a monomer described later, but also an oligomer, a mixture of a monomer and an oligomer, a modified product, an oligomer having a polymerizable functional group, and the like.
- (meth) acrylate includes acrylate monomer and / or acrylate oligomer, methacrylate monomer and / or methacrylate oligomer.
- Examples of (meth) acrylate compounds include isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) ) Acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate , Methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth)
- (meth) acrylate compounds are stearyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isobornyl (meth) acrylate, tetraethylene glycol di (Meth) acrylate, glycerin propoxytri (meth) acrylate and the like are preferable.
- the (meth) acrylate compound may be a modified product.
- modified products include ethylene oxide-modified (meth) acrylate compounds such as ethylene oxide-modified trimethylolpropane tri (meth) acrylate and ethylene oxide-modified pentaerythritol tetraacrylate; caprolactone such as caprolactone-modified trimethylolpropane tri (meth) acrylate Modified (meth) acrylate compounds; and caprolactam-modified (meth) acrylate compounds such as caprolactam-modified dipentaerythritol hexa (meth) acrylate.
- the (meth) acrylate compound is an ethylene oxide-modified (meth) acrylate compound.
- the ethylene oxide-modified (meth) acrylate compound has high photosensitivity and easily forms a card house structure when the ink gels at a low temperature.
- the ethylene oxide-modified (meth) acrylate compound is easily dissolved in other ink components at high temperatures and has little curing shrinkage, so that curling of the printed matter hardly occurs.
- Examples of ethylene oxide-modified (meth) acrylate compounds include 4EO-modified hexanediol diacrylate CD561 (molecular weight 358), 3EO-modified trimethylolpropane triacrylate SR454 (molecular weight 429), 6EO-modified trimethylolpropane triacrylate SR499 manufactured by Sartomer. (Molecular weight 560), 4EO-modified pentaerythritol tetraacrylate SR494 (molecular weight 528); Shin-Nakamura Chemical Co., Ltd.
- polyethylene glycol diacrylate NK ester A-400 (molecular weight 508), polyethylene glycol diacrylate NK ester A-600 (molecular weight 742) , Polyethylene glycol dimethacrylate NK ester 9G (molecular weight 536), polyethylene glycol dimethacrylate NK Este 14G (molecular weight 770); Tetraethylene glycol diacrylate V # 335HP (molecular weight 302) manufactured by Osaka Organic Chemical Co .; 3PO-modified trimethylolpropane triacrylate Photomer 4072 (molecular weight 471) manufactured by Cognis; 1 manufactured by Shin-Nakamura Chemical Co., Ltd.
- 10-decanediol dimethacrylate NK ester DOD-N (molecular weight 310)
- tricyclodecane dimethanol diacrylate NK ester A-DCP molecular weight 304
- tricyclodecane dimethanol dimethacrylate NK ester DCP molecular weight 302.
- the (meth) acrylate compound may be a polymerizable oligomer.
- polymerizable oligomers include epoxy (meth) acrylate oligomers, aliphatic urethane (meth) acrylate oligomers, aromatic urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and linear (meth) acrylic oligomers. included.
- the cationically polymerizable compound can be an epoxy compound, a vinyl ether compound, an oxetane compound, or the like. Only one kind of the cationic polymerizable compound may be contained in the actinic ray curable inkjet white ink, or two or more kinds thereof may be contained.
- the epoxy compound is an aromatic epoxide, an alicyclic epoxide, an aliphatic epoxide, or the like, and an aromatic epoxide or an alicyclic epoxide is preferable in order to increase curability.
- the aromatic epoxide may be a di- or polyglycidyl ether obtained by reacting a polyhydric phenol or an alkylene oxide adduct thereof with epichlorohydrin.
- examples of the polyhydric phenol to be reacted or its alkylene oxide adduct include bisphenol A or its alkylene oxide adduct.
- the alkylene oxide in the alkylene oxide adduct can be ethylene oxide, propylene oxide, and the like.
- the alicyclic epoxide can be a cycloalkane oxide-containing compound obtained by epoxidizing a cycloalkane-containing compound with an oxidizing agent such as hydrogen peroxide or peracid.
- the cycloalkane in the cycloalkane oxide-containing compound can be cyclohexene or cyclopentene.
- the aliphatic epoxide can be a di- or polyglycidyl ether obtained by reacting an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof with epichlorohydrin.
- the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, alkylene glycol such as 1,6-hexanediol, and the like.
- the alkylene oxide in the alkylene oxide adduct can be ethylene oxide, propylene oxide, and the like.
- vinyl ether compounds include ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether.
- monovinyl ether compounds such as -o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether; Diethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane trivinyl ether, etc. Or a trivinyl ether compound etc. are contained. Of these vinyl ether compounds, di- or trivinyl ether compounds are preferred in view of curability and adhesion.
- An oxetane compound is a compound having an oxetane ring, and examples thereof include oxetane compounds described in JP-A Nos. 2001-220526, 2001-310937, and JP-A-2005-255821.
- the compound represented by the general formula (1) described in paragraph No. 0089 of JP-A No. 2005-255821 the compound represented by the general formula (2) described in paragraph No. 0092 of the same publication
- the paragraph Examples include a compound represented by general formula (7) of number 0107, a compound represented by general formula (8) of paragraph number 0109, a compound represented by general formula (9) of paragraph number 0116, and the like.
- the general formulas (1), (2), (7), (8), and (9) described in JP-A-2005-255821 are shown below.
- the content of the photopolymerizable compound in the actinic ray curable inkjet white ink is preferably 1 to 97% by mass, and more preferably 30 to 95% by mass.
- the actinic ray curable inkjet white ink of the present invention contains a photopolymerization initiator.
- the photopolymerizable compound is a radical polymerizable compound, it can be used as a radical polymerization initiator, and when the photopolymerizable compound is a cationic polymerizable compound, it can be used as a photoacid generator.
- Radical polymerization initiators include an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type.
- intramolecular bond cleavage type photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2.
- intramolecular hydrogen abstraction type photopolymerization initiators examples include benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl.
- Benzophenones such as sulfide, acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 -Thioxanthone series such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone series such as Michler ketone, 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethyl Anthraquinone, 9,10-phenanthrene Quinone, include camphor quinone and the like.
- the content of the photopolymerization initiator in the actinic ray curable inkjet white ink is preferably 0.01% by mass to 10% by mass, although it depends on the type of actinic ray or photopolymerizable compound.
- the actinic ray curable inkjet white ink may contain a photoacid generator as a photopolymerization initiator.
- photoacid generators include chemically amplified photoresists and compounds used for photocationic polymerization (Organic Electronics Materials Study Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), 187. See page 192).
- the actinic ray curable inkjet white ink may further contain a photopolymerization initiator auxiliary agent or a polymerization inhibitor, if necessary.
- the photopolymerization initiator assistant may be a tertiary amine compound, preferably an aromatic tertiary amine compound.
- aromatic tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine and the like are included.
- N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. Only one kind of these compounds may be contained in the actinic ray curable inkjet white ink, or two or more kinds thereof may be contained.
- polymerization inhibitors include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone , Nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino- 1,3-dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxime
- the actinic ray curable inkjet white ink may further contain other components as necessary.
- Other components may be various additives, other resins, and the like.
- the additive include a surfactant, a leveling additive, a matting agent, an infrared absorber, an antibacterial agent, and a basic compound for enhancing the storage stability of the ink.
- basic compounds include basic alkali metal compounds, basic alkaline earth metal compounds, basic organic compounds such as amines, and the like.
- other resins include resins for adjusting the physical properties of the cured film, such as polyester resins, polyurethane resins, vinyl resins, acrylic resins, and rubber resins.
- the actinic ray curable inkjet white ink can be obtained by mixing the above-mentioned pigment, dispersant, wax, photopolymerizable compound and photopolymerization initiator with any of the components under heating. It is preferable to filter the obtained liquid mixture with a predetermined filter. At this time, a dispersion containing a pigment and a dispersant may be prepared in advance, and the remaining components may be added thereto and mixed while heating.
- the actinic ray curable inkjet white ink of the present invention contains a wax, it can reversibly undergo a sol-gel phase transition depending on the temperature.
- the sol-gel phase transition type actinic ray curable ink is a sol at a high temperature (for example, about 80 ° C.) and can be ejected from an ink ejection recording head. However, after landing on a recording medium, the gel is naturally cooled. Turn into. Thereby, coalescence of adjacent dots can be suppressed and image quality can be improved.
- the viscosity of the ink at a high temperature is not more than a certain value.
- the viscosity of the ink at 80 ° C. is preferably 3 to 20 mPa ⁇ s, more preferably 6.0 to 15.0 mPas, and even more preferably 7.0 to 12.0 mPas.
- the viscosity of the ink at normal temperature after landing is a certain level or more.
- the viscosity at 25 ° C. of the actinic ray curable inkjet white ink is preferably 1000 mPa ⁇ s or more.
- the gelling temperature of the actinic ray curable inkjet white ink of the present invention is preferably 40 ° C. or higher and 70 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower. If the gelation temperature of the ink exceeds 70 ° C. when the ejection temperature is in the vicinity of 80 ° C., gelation tends to occur at the time of ejection, resulting in poor ejection properties. On the other hand, if the gelation temperature is less than 40 ° C., the gelation does not occur immediately after landing on the recording medium.
- the gelation temperature is a temperature at which the fluidity decreases due to gelation in the process of cooling the ink in the sol state.
- the viscosity at 80 ° C., the viscosity at 25 ° C. and the gelation temperature of the actinic ray curable inkjet white ink of the present invention can be determined by measuring the temperature change of the dynamic viscoelasticity of the ink with a rheometer. Specifically, a temperature change curve of viscosity is obtained when the ink is heated to 100 ° C. and cooled to 25 ° C. under conditions of a shear rate of 11.7 (1 / s) and a temperature decrease rate of 0.1 ° C./s. .
- the viscosity in 80 degreeC and the viscosity in 25 degreeC can be calculated
- the gelation temperature can be determined as the temperature at which the viscosity becomes 200 mPa ⁇ s in the temperature change curve of the viscosity.
- the rheometer can be a stress control type rheometer Physica MCR series manufactured by Anton Paar.
- the cone plate can have a diameter of 75 mm and a cone angle of 1.0 °.
- the actinic ray curable inkjet white ink of the present invention and a color ink may be combined to form an ink set.
- the color ink used in the ink set is not particularly limited, and an appropriate ink can be selected according to the target image.
- the color ink is preferably an ink that can be ejected by ink jet as in the actinic ray curable inkjet white ink of the present invention, and is preferably an actinic ray curable ink.
- the color ink is preferably an ink that can undergo a sol-gel phase transition by containing a wax or a gelling agent.
- the actinic ray curable inkjet white ink of the present invention is applied, and the topcoat portion or the undercoat portion of the image is applied. Can be formed.
- the color ink can be, for example, black, cyan, magenta, yellow, and other color inks.
- the color ink refers to an ink other than the actinic ray curable inkjet white ink of the present invention.
- An image forming method includes (a) a step of ejecting the actinic radiation curable inkjet white ink from a recording head for ejecting ink and adhering it onto a recording medium, and (b) an actinic ray curable inkjet adhering thereto. Irradiating the white ink with an actinic ray.
- the ink when the white ink or the color ink described later is attached to the recording medium, the ink may be attached directly to the recording medium, or further on the ink that has already adhered or cured to the recording medium. Ink may be attached.
- white ink may be adhered and cured on the color ink that is adhered or cured on the recording medium, or the white ink that is adhered or cured directly after the white ink is adhered and cured on the recording medium.
- a color ink may be further deposited and cured on the ink.
- an image having an overcoating portion or an undercoating portion with the actinic ray curable inkjet white ink of the present invention can be formed.
- only the actinic ray curable inkjet white ink of the present invention can be deposited and cured on a recording medium without using a color ink, whereby an image consisting of only white can be formed.
- the inkjet ink in the ink ejection recording head In the step of ejecting the actinic ray curable inkjet white ink from the ink ejection recording head and depositing it on the recording medium, in order to improve the ejection property of the white ink, the inkjet ink in the ink ejection recording head
- the temperature is preferably set to a temperature 10 to 30 ° C. higher than the gel transition temperature of the white ink.
- the white ink can be heated by an ink discharge recording head of an ink jet recording apparatus, an ink flow path connected to the ink discharge recording head, an ink tank connected to the ink flow path, or the like.
- the droplet volume per droplet of white ink ejected from each nozzle of the ink ejection recording head is preferably 0.5 to 10 pl, depending on the viscosity of the white ink, etc., and is ejected only to a desired region. In order to achieve this, it is more preferably 0.5 to 4.0 pl, and even more preferably 1.5 to 4.0 pl. Even when such an amount of ink is applied, since the sol-gel phase transition is performed in the white ink of the present invention, the ink does not excessively wet and spread, and can be discharged only to a desired location.
- the white ink droplets adhering to the recording medium are cooled and rapidly gelled by the sol-gel phase transition. Thereby, it is possible to perform pinning without excessively spreading white ink droplets. Furthermore, since the droplets gel quickly, it is difficult for oxygen to enter the droplets, and the curing of the photopolymerizable compound is not easily inhibited by oxygen.
- the white ink droplets adhere to the recording medium.
- the temperature of the recording medium when the white ink droplets adhere is preferably set to a temperature that is 10 to 20 ° C. lower than the gelation temperature of the ink. If the temperature of the recording medium is too low, the white ink droplets gel too quickly and pin. On the other hand, if the temperature of the recording medium is too high, the ink droplets are difficult to gel, and adjacent dots of the ink droplets may be mixed together. By appropriately adjusting the temperature of the recording medium, it is possible to achieve appropriate leveling and appropriate pinning so that adjacent dots of ink droplets do not mix with each other.
- the recording medium may be paper or a resin film.
- paper include coated paper for printing, coated paper B for printing, and the like.
- the resin film include a polyethylene terephthalate film, a polypropylene film, and a vinyl chloride film.
- the conveyance speed of the recording medium is preferably 30 to 120 m / s.
- the higher the conveyance speed the higher the image forming speed, which is preferable.
- the conveyance speed is too high, the image quality deteriorates and the photocuring (described later) of the white ink becomes insufficient.
- the photopolymerizable compound contained in the ink is irradiated by irradiating the actinic ray to the droplet of the white ink adhering to the recording medium.
- Each ink droplet is cured by crosslinking or polymerization.
- the actinic ray applied to the white ink droplet attached to the recording medium can be ultraviolet light from a metal halide lamp or LED light source.
- LED light source by using the LED, it is possible to suppress the white ink droplets from being melted by the radiant heat of the light source and causing the curing failure on the cured film surface of the ink droplets.
- Examples of LEDs include 395 nm, water-cooled LED, etc., manufactured by Phoseon Technology.
- the light source is installed such that ultraviolet light of 360 to 410 nm is provided so that the peak illuminance on the image surface is 0.5 to 10 W / cm 2 and 1 to 5 W / cm 2 .
- the amount of light applied to the image is preferably less than 500 mJ / cm 2 .
- the image forming method of the present invention is such that (a) the actinic ray curable inkjet white ink described above is ejected from an ink ejection recording head and adhered onto the recording medium. And (b) a step of irradiating the attached actinic ray curable inkjet white ink with actinic rays, (c) a step of attaching one or a plurality of color inks onto the recording medium, and (d) You may have the process of fixing the adhering color ink.
- fixing the color ink means curing the color ink attached to the recording medium.
- the actinic ray curable inkjet white ink of the present invention is gelled at the time of adhesion, it is difficult to mix with the color ink.
- the step of irradiating the attached white ink with actinic rays may be performed before (c) the step of depositing the color ink on the recording medium, or after that.
- the step (b) is performed before the step (c)
- the color ink adheres to the cured white ink, so that the mixing of the color ink with the white ink can be further reduced.
- step (b) is performed after step (c)
- the color ink curing step and (b) the white ink curing step can be performed continuously or simultaneously, thereby reducing the image formation time. Can do.
- the color ink is an actinic ray curable ink containing a photopolymerizable compound and a photopolymerization initiator
- the color ink is preferably an ink containing a wax or a gelling agent, and is sol-like by heating before adhering to the recording medium, but becomes gel-like due to sol-gel phase transition when it adheres to the recording medium and the temperature decreases. Ink is preferred. When such a color ink is used, both the color ink and the white ink are gelated by the sol-gel phase transition when adhering to the recording medium. Even when the coating is performed, mixing of the coating film of the white ink before curing and the coating film of the color ink before curing is less likely to occur.
- the actinic radiation curable inkjet white ink of the present invention When the actinic radiation curable inkjet white ink of the present invention is used for overcoating, (a) the actinic radiation curable inkjet white ink is deposited on the recording medium after the step (c) depositing the color ink on the recording medium. Perform the process. As a result, the color ink can be coated with the actinic ray curable inkjet white ink, and the durability of the formed image is increased.
- the color ink is attached or cured to the recording medium having light transmittance and then the white ink is attached and cured, the recording medium is viewed from the side opposite to the surface on which the image is formed. The refractive index of the background portion of can be increased. At this time, since the white ink of the present invention becomes the background color, the appearance of the formed image can be enhanced.
- the step of fixing the attached color ink may be performed before (a) the step of depositing the white ink on the recording medium, or may be performed thereafter.
- the white ink adheres to the cured color ink, so that the mixing of the white ink into the color ink can be reduced.
- the step (d) is performed after the step (a)
- the color ink curing step and (b) the white ink curing step can be performed continuously or simultaneously, thereby reducing the image formation time. Can do.
- the color ink is an actinic ray curable ink containing a photopolymerizable compound and a photopolymerization initiator
- the color ink is preferably an ink containing a wax or a gelling agent, and is sol-like by heating before adhering to the recording medium, but becomes gel-like due to sol-gel phase transition when it adheres to the recording medium and the temperature decreases. Ink is preferred. When such a color ink is used, both the color ink and the white ink are gelated by the sol-gel phase transition when adhering to the recording medium. Even when the coating is performed, mixing of the color ink coating before curing and the white ink coating before curing is less likely to occur.
- the method of attaching is not limited, and an appropriate method may be selected according to the type of color ink to be used.
- a method of attaching for example, a method of applying with a wire bar or a roll coater, a method of spraying with a spray, an offset printing method, an ink jet printing method, or the like can be used.
- a device configuration similar to the device configuration for attaching the white ink can be used.
- the apparatus can be simplified and is economical in terms of space and cost. When a plurality of color inks are used, each color ink is ejected and adhered to a recording medium.
- the temperature of the ink-jet ink in the ink discharge recording head is preferably within 10 ° C. above and below the temperature of the white ink in order to improve the discharge property of the color ink droplets.
- the amount of droplets per color ink ejected from each nozzle of the ink ejection recording head is preferably 0.5 to 10 pl, depending on the resolution of the image, so as to form a high-definition image. Is more preferably 0.5 to 4.0 pl.
- the color ink contains a wax or a gelling agent, a high-definition image can be stably formed even with such a droplet amount.
- the fixing method is not limited, and an appropriate method may be selected according to the type of color ink to be used. For example, a method of heating ink, a method of evaporating water contained in the ink, a method of pressurizing with a roller fixing device or a belt fixing device, or the like can be used.
- the color ink is an actinic ray curable ink containing a photopolymerizable compound and a photopolymerization initiator, the ink can be cured and fixed by irradiation with actinic rays.
- the total ink droplet thickness after curing is preferably 1 to 20 ⁇ m.
- the “total ink droplet thickness” is the maximum value of the thickness of the cured film of color ink and white ink drawn on the recording medium.
- FIGS. 1A to 3 Can be used.
- the actinic ray curable ink jet recording apparatus includes a line recording method (single pass recording method) and a serial recording method. Any method may be selected according to the required image resolution and recording speed, but the line recording method (single-pass recording method) is preferable from the viewpoint of high-speed recording.
- FIG. 1A is a side view of an example of a configuration of a main part of a line recording type ink jet recording apparatus, and FIG. 1B is a top view thereof.
- 2A is a side view of another example of the configuration of the main part of the line recording type ink jet recording apparatus, and FIG. 2B is a top view thereof.
- the ink jet recording apparatus 10 is connected to a head carriage 16 (16a, 16b) that houses a plurality of ink ejection recording heads 14 and the head carriage 16.
- a unit 18 (18a, 18b), and a temperature control unit 19 disposed on the lower surface of the recording medium 12.
- the color ink head carriage 16a, the color ink droplet curing light irradiation unit 18a, the white ink head carriage 16b, and the white ink droplet curing light irradiation unit. 18b are arranged in this order.
- the color ink and the white ink can be individually cured.
- the light irradiation unit 18a is omitted, Only the light irradiation unit 18b may be provided.
- the white ink head carriage 16b, the color ink head carriage 16a, and the light irradiation unit 18 are arranged in this order.
- the white ink and the color ink can be individually cured.
- the light irradiation unit 18a is omitted, Only the light irradiation unit 18b may be provided.
- the head carriage 16 of the inkjet recording apparatus 10 includes a head carriage 16a for color ink and a head carriage 16b for white ink.
- the color ink head carriage 16a includes a head carriage for each color.
- the head carriages 16a and 16b are fixedly arranged so as to cover the entire width of the recording medium 12, and accommodate a plurality of recording heads 14 for ejecting ink.
- Color ink or white ink is supplied from the ink tank 31 to the ink ejection recording head 14.
- a plurality of ink ejection recording heads 14 are arranged in the transport direction of the recording medium 12 for each color.
- the number of ink ejection recording heads 14 arranged in the conveyance direction of the recording medium 12 is set according to the nozzle density of the ink ejection recording head 14 and the resolution of the print image. For example, when an image having a resolution of 1440 dpi is formed using the ink ejection recording head 14 having a droplet amount of 2 pl and a nozzle density of 360 dpi, four ink ejection recording heads 14 are provided in the transport direction of the recording medium 12. What is necessary is just to shift and arrange.
- the two ink discharge recording heads 14 may be arranged in a shifted manner.
- dpi represents the number of ink droplets (dots) per 2.54 cm.
- the ink tank 31 is connected to the head carriage 16 via the ink flow path 30.
- the ink flow path 30 is a path for supplying the ink in the ink tank 31 to the head carriage 16.
- the ink in the ink tank 31, the ink flow path 30, the head carriage 16, and the ink ejection recording head 14 is heated to a predetermined temperature to maintain the gel state.
- the light irradiators 18a and 18b cover the entire width of the recording medium 12, and are arranged on the downstream side of the head carriage 16 in the recording medium conveyance direction.
- the light irradiators 18a and 18b irradiate the ink droplets ejected by the ink ejection recording head 14 and adhered onto the recording medium 12 to cure the droplets.
- the temperature control unit 19 is disposed on the lower surface of the recording medium 12 and maintains the recording medium 12 at a predetermined temperature.
- the temperature control unit 19 may be divided into a color ink head carriage 16a side and a white ink head carriage 16b side.
- the temperature control unit 19 can be, for example, various heaters.
- the recording medium 12 is conveyed between the color ink head carriage 16a and the temperature control unit 19 of the inkjet recording apparatus 10.
- the recording medium 12 is adjusted to a predetermined temperature by the temperature control unit 19.
- high-temperature ink droplets are ejected from the ink ejection recording head 14 of the color ink head carriage 16 a and adhered (landed) on the recording medium 12.
- the light irradiating unit 18a irradiates the ink droplets of the color ink adhering on the recording medium 12 with light, and cures.
- high-temperature ink droplets are ejected from the ink ejection recording head 14 of the white ink head carriage 16 b onto the recording medium 12 and adhered to the recording medium 12.
- the light irradiating unit 18b irradiates the ink droplets of the white ink attached on the recording medium 12 with light, and cures.
- the recording medium 12 is transported between the white ink head carriage 16b of the inkjet recording apparatus 10 and the temperature control unit 19.
- the recording medium 12 is adjusted to a predetermined temperature by the temperature control unit 19.
- high temperature ink droplets are ejected from the ink ejection recording head 14 of the head carriage 16 b for white ink, and are deposited on the recording medium 12.
- the light irradiating unit 18a irradiates the ink droplets of the white ink attached on the recording medium 12 with light to be cured.
- high-temperature ink droplets are ejected from the ink ejection recording head 14 of the color ink head carriage 16 a onto the recording medium 12 and adhered to the recording medium 12. Thereafter, the light irradiating unit 18b irradiates the ink droplets of the color ink adhered on the recording medium 12 with light, and cures.
- FIG. 3 is a diagram illustrating an example of a configuration of a main part of the serial recording type inkjet recording apparatus 20.
- the inkjet recording apparatus 20 has a width narrower than the entire width of the recording medium, instead of the head carriages 16a and 16b fixedly arranged so as to cover the entire width of the recording medium, and a plurality of inks.
- FIG. 1A and FIG. 1B except for having head carriages 26a and 26b for accommodating the discharge recording heads 24a and 24b, respectively, and guide portions 27a and 27b for moving the head carriage 26 in the width direction of the recording medium 12. It can be configured similarly.
- an ink droplet is ejected from an ink ejection recording head 24 accommodated in the head carriage 26 while the head carriage 26 moves in the width direction of the recording medium 12 along the guide portion 27. To do. After the head carriage 26 has completely moved in the width direction of the recording medium 12 (for each pass), the recording medium 12 is fed in the transport direction. Except for these operations, an image is recorded in substantially the same manner as the line recording type inkjet recording apparatus 10 described above.
- the color ink and white ink droplets are collectively exposed by the light irradiation unit 28, and if necessary, the color ink head carriage 26 a and the white ink ink are used.
- a light irradiation unit for curing the color ink droplets may be disposed between the head carriage 26b and the head carriage 26b.
- the head carriage 26a for attaching the color ink is arranged upstream, but the head carriage 26b for attaching the white ink may be arranged upstream of the head carriage 26a.
- Example 1 [Preparation of comb-type block copolymer having tertiary amine group]
- 500 g of active catalyst (zeolite) and lauryl alcohol (Calcoal 2098 manufactured by Kao Corporation) charged in the flask reactor were charged into a buffer tank, and the liquid was circulated between the buffer tank and the reactor while supplying hydrogen gas. I let you. Thereafter, the temperature inside the reactor was raised to 65 ° C., and then a DPGMA solution (Aronix M-120, manufactured by Toagosei Co., Ltd.) of PB-824 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was supplied to the reactor, followed by further reaction. The temperature inside the vessel was raised to 90 ° C.
- active catalyst zeolite
- lauryl alcohol Calcoal 2098 manufactured by Kao Corporation
- Dispersant J was prepared by the same procedure except that the type of dispersant was changed to BYK-2091 (manufactured by Big Chemie).
- a white pigment dispersion 1 was prepared with the following components.
- White pigment 1 CR-EL (Ishihara Sangyo) 25.0wt%
- Dispersant A BYK JET-9151 (Bic Chemie) 10.0 wt%
- Photopolymerizable compound dipropylene glycol monoacrylate 64.5 wt%
- Polymerization inhibitor Irgastab UV-10 (manufactured by BASF) 0.5 wt%
- Each component is placed in a 200 cc plastic bottle according to the above blending ratio, 120 g of zirconia beads having a media diameter of 0.5 mm ⁇ is further placed therein, the lid is closed, and a vibration mill (Red Devil 4500L manufactured by Nishimura Seisakusho Co., Ltd.) ) For 4 hours. After dispersion, the beads were separated and the dispersion was taken out.
- a vibration mill Red Devil 4500L manufactured by Nishimura Seisakusho Co., Ltd.
- Each actinic ray curable ink was filtered with a WAC filter (0.3 ⁇ m accuracy) manufactured by Pall Corporation. Thereafter, each ink was introduced into a Konica Minolta inkjet head (KM1048), and a solid image was printed under the conditions of a printing width of 100 mm ⁇ 100 mm and a resolution of 720 ⁇ 720 dpi.
- An OK top coat (printing paper) was used as a printing substrate.
- a Kyocera LED lamp was used as a UV irradiation light source, and the ink was cured by irradiating the ink printed with ultraviolet rays with an energy of 250 mJ.
- Viscosity change amount Each actinic ray curable ink was collected in a heat-resistant tube and stored in a high-temperature tank at 85 ° C. for 1 month. The ink viscosity before storage and the ink viscosity after storage are constant for 5 minutes at a temperature of 80 ° C. at a shear rate of 1000 (1 / sec) with a cone plate of 75 mm ⁇ using an Anton Paar stress rheometer model MCR-102. The torque at the time of rotation was measured in terms of viscosity.
- the dispersant was a comb block copolymer having a tertiary amine group
- the viscosity change amount and the gloss difference from other colors were small, and the head was not clogged.
- the dispersant has an amine other than the tertiary amine, there was a lot of clogging of the head, and the ink stored at high temperature tended to thicken more. This is presumably because the pigment was re-agglomerated because the dispersant had a weak adsorption power to the titanium dioxide surface-coated with alumina, and the dispersant was detached from the titanium dioxide pigment at a high temperature.
- the dispersing agent has a linear block copolymer
- a lot of clogging of the head occurred. This is presumably because the pigment was not sufficiently dispersed because the dispersibility of the dispersant was weak.
- Example 2 [Preparation of actinic ray curable ink] Using the white pigment dispersion A-2 of Example 1 (using BYK JET-9151 as a dispersant and TCR-52 as a white pigment), an actinic ray curable ink was prepared in the same procedure as in Example 1. At that time, the amount of BYK JET-9151 as a dispersant and the amount of Kao wax T-1 (aliphatic ketone) and Unistar M222 (fatty acid ester) as waxes were changed according to Tables 5 and 6, Light curable inks K-1 to R-6 were prepared.
- Kao wax T-1 aliphatic ketone
- Unistar M222 fatty acid ester
- Viscosity change amount In the same manner as in Example 1, the ink viscosity before and after storage in a high-temperature tank at 85 ° C. for 1 month was measured, and the viscosity change was determined.
- Droplet diameter The temperature of the substrate at the time of printing was set to 50 ° C., a solid 100% image was formed and cured, and the image after printing was observed with a microscope ( ⁇ 200) and randomly selected 10 locations The droplet diameter was measured. When the average value of the measured values is 60 ⁇ m or more and 65 ⁇ m or less, the pinning property is judged to be good (indicated by + in Tables 5 to 6), and when the average value is 60 ⁇ m or more and 62 ⁇ m or less, the pinning property is further increased. It was judged to be good (indicated in ++ in Tables 5 to 6).
- the content of the copolymer according to the present invention was 2.0% by mass or more and 8.0% by mass or less in the total mass of the ink, the amount of change in viscosity was smaller.
- the amount of the copolymer according to the present invention within this range, it is considered that the pigment is sufficiently dispersed, and no increase in viscosity due to entanglement between the dispersants is observed.
- the actinic ray curable inkjet white ink of the present invention can be used, for example, as an ink for overcoating or undercoating during image formation with other color inks.
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Abstract
Description
[1]顔料、分散剤、ワックス、光重合性化合物および光重合開始剤を含み、温度変化によってゾルゲル相転移可能な活性光線硬化型インクジェット白色インクであって、前記顔料はアルミナで表面被覆された二酸化チタンを含み、前記二酸化チタンの含有量は、インクの全質量中10質量%以上15質量%以下であり、前記インクは顔料に対する質量比率で200ppm以下のナトリウムイオンを含み、前記分散剤は、3級アミン基を有するくし型ブロックコポリマーを含む、インク。
[2]前記ブロックコポリマーの含有量は、インクの全質量中、2.0質量%以上8.0質量%以下である、[1]に記載のインク。
[3]前記ワックスは脂肪族ケトンおよび脂肪酸エステルを含む、[1]または[2]に記載のインク。
[4]前記脂肪族ケトン含有量と脂肪酸エステル含有量との合計は、インクの全質量中、2.0質量%以上5.0質量%以下である、[3]に記載のインク。
[5]前記脂肪酸エステルの含有量と同量または前記脂肪酸エステルの含有量より多い量の前記脂肪族ケトンを含む、[3]または[4]に記載のインク。
[6][1]~[5]のいずれかに記載の活性光線硬化型インクジェット白色インクをインク吐出用記録ヘッドから吐出させて記録媒体上に付着させる工程と、前記付着した前記活性光線硬化型インクジェット白色インクに活性光線を照射する工程と、を有する、画像形成方法。
[7]さらに、1または複数のカラーインクを前記記録媒体上に付着させる工程、および前記付着したカラーインクを定着させる工程を有する、[6]に記載の画像形成方法。
[8]前記カラーインクを記録媒体上に付着させる工程の後に、前記活性光線硬化型インクジェット白色インクを記録媒体上に付着させる工程を有する、[7]に記載の方法。
[9]前記活性光線硬化型インクジェット白色インクを記録媒体上に付着させる工程の後に、前記カラーインクを記録媒体上に付着させる工程を有する、[7]に記載の方法。
[10]前記カラーインクは光重合性化合物および光重合開始剤を含む活性光線硬化型インクであり、前記付着したカラーインクを定着させる工程は、付着したカラーインクに活性光線を照射する工程であり、前記カラーインクに活性光線を照射する工程および前記付着した活性光線硬化型インクジェット白色インクに活性光線を照射する工程は、1回の活性光線照射によって行われる、[7]~[9]のいずれかに記載の方法。
本発明に係るインクは、顔料、分散剤、ワックス、光重合性化合物および光重合開始剤を含む活性光線硬化型インクジェット白色インク(以下、単に白色インクともいう。)であって、前記顔料はアルミナで表面被覆された二酸化チタンであり、前記インクはインクの全質量中10質量%以上15質量%以下の前記二酸化チタンを含み、前記インクは200ppm以下のナトリウムイオンを含み、前記分散剤は、3級アミン基を有するくし型ブロックコポリマーを含む、インクである。
以下、各成分の詳細な説明を通じて本発明に係るインクについて説明を行う。
本発明の活性光線硬化型インクジェット白色インクには、顔料が含まれる。顔料には、アルミナで表面被覆された二酸化チタンが含まれる。本発明の活性光線硬化型インクジェット白色インクは、アルミナで表面被覆された二酸化チタンを、10質量%以上15質量%以下の含有量で含む。
1)酸化チタンを水に分散させてスラリーとする。
2)1)で得られたスラリーを所定の温度に調整し、表面処理剤である可溶性アルミニウム化合物(アルミン酸ナトリウム)を添加し、溶解させる。
3)2)で得られたスラリーのpHを所定範囲に維持した状態で、酸の沈殿剤を添加して中和し、アルミニウム水和物を沈着させる。
1)インクにメタノールを加え、得られた溶液を遠沈管に入れ、遠心分離装置で20000rpmで1時間かけ、固体と溶液とに分ける。
2)乾燥させた固体を、密閉式マイクロ波分解装置により、濃硝酸/濃塩酸(モル比1/10)の混酸で分解し、溶液化する。
3)2)で得られた濃硝酸/濃塩酸溶液中のナトリウムイオン量を、ICP-AES(セイコーインスツルメンツ(株)製 SPS3520UV)により測定し、固体成分のナトリウムイオン量を求める。
4)同様に、1)で得られた溶液のナトリウムイオン量を上記ICP-AESにより測定し、溶液成分のナトリウムイオン量を求める。
5)前記3)で求めた固体成分のナトリウムイオン量と、前記4)で求めた溶液成分のナトリウムイオン量とを合算して「インク中のナトリウムイオン量」とする。
1)表面処理された二酸化チタン粉末を、密閉式マイクロ波分解装置により、濃硝酸/濃塩酸(モル比1/10)の混酸で分解し、溶液化する。
2)1)で得られた濃硝酸/濃塩酸溶液中のナトリウムイオン量を、ICP-AES(セイコーインスツルメンツ(株)製 SPS3520UV)により測定する。
1)表面処理された酸化チタン粉末を、密閉式マイクロ波分解装置により、ふっ酸水溶液で分解し、溶液化する。
2)得られた水溶液中のAl量を、ICP-AESにより測定する。
本発明の活性光線硬化型インクジェット白色インクには、分散剤が含まれる。インクに分散剤を含ませることで、顔料の分散性を高めることができる。本発明は、分散剤に、3級アミン基を有するくし型ブロックコポリマー(以下、単に「本発明に係るコポリマー」ともいう。)を含む。なお、本発明において、くし型ブロックコポリマーとは、主鎖を形成する直鎖状のポリマーに対し、主鎖を構成するモノマーの1単位ごとに側鎖として別の種類のポリマーがグラフト重合したコポリマーをいう。
本発明の活性光線硬化型インクジェット白色インクには、ワックスが含まれる。本発明おいてワックスとは、「常温で固体、加熱すると液体となる有機物」と定義される。本発明の活性光線硬化型インクジェット白色インクには、インクの全質量中1.2質量%以上5.5質量%未満のワックスが含まれることが好ましい。ワックス含有量を1.2質量%以上とすることで、画像表面の滑り性が高まり、画像の耐擦過性を良好にすることができる。ワックス含有量を5.5質量%以下とすることで、画像表面に析出したワックスによる過剰な光沢の発生を防ぐことができるほか、インクジェットヘッドからのインク射出性が良好にすることができる。
これらのワックスは、単独で用いてもよいし、二種以上を組み合わせて用いてもよい。
本発明の活性光線硬化型インクジェット白色インクには、光重合性化合物が含まれる。
トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ジメチロール-トリシクロデカンジ(メタ)アクリレート、ビスフェノールAのPO付加物ジ(メタ)アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレート、ポリテトラメチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジアクリレート、トリプロピレングリコールジアクリレート等の二官能モノマー;
トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、グリセリンプロポキシトリ(メタ)アクリレート、ペンタエリスリトールエトキシテトラ(メタ)アクリレート等の三官能以上の多官能モノマー等が含まれる。
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ジビニルエーテル、ブタンジオールジビニルエーテル、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、トリメチロールプロパントリビニルエーテル等のジまたはトリビニルエーテル化合物等が含まれる。これらのビニルエーテル化合物のうち、硬化性や密着性などを考慮すると、ジまたはトリビニルエーテル化合物が好ましい。
本発明の活性光線硬化型インクジェット白色インクには、光重合開始剤が含まれる。光重合性化合物がラジカル重合性化合物であるときはラジカル重合開始剤とすることができ、光重合性化合物がカチオン重合性化合物であるときは光酸発生剤とすることができる。
活性光線硬化型インクジェット白色インクには、必要に応じて他の成分がさらに含まれていてもよい。他の成分は、各種添加剤や他の樹脂等であってよい。添加剤の例には、界面活性剤、レベリング添加剤、マット剤、赤外線吸収剤、抗菌剤、インクの保存安定性を高めるための塩基性化合物等も含まれる。塩基性化合物の例には、塩基性アルカリ金属化合物、塩基性アルカリ土類金属化合物、アミンなどの塩基性有機化合物などが含まれる。他の樹脂の例には、硬化膜の物性を調整するための樹脂などが含まれ、例えばポリエステル系樹脂、ポリウレタン系樹脂、ビニル系樹脂、アクリル系樹脂、およびゴム系樹脂等が含まれる。
活性光線硬化型インクジェット白色インクは、前述の顔料、分散剤、ワックス、光重合性化合物および光重合開始剤と、任意の各成分とを、加熱下において混合することにより得ることができる。得られた混合液を所定のフィルターで濾過することが好ましい。このとき、顔料および分散剤を含む分散体をあらかじめ調製しておき、これに残りの成分を添加して加熱しながら混合してもよい。
本発明の活性光線硬化型インクジェット白色インクは、ワックスを含むため、温度により可逆的にゾルゲル相転移することができる。ゾルゲル相転移型の活性光線硬化型インクは、高温(例えば80℃程度)ではゾルであるため、インク吐出用記録ヘッドから吐出することができるが、記録媒体に着弾した後、自然冷却されてゲル化する。これにより、隣り合うドット同士の合一を抑制し、画質を高めることができる。
本発明の活性光線硬化型インクジェット白色インクとカラーインクとを組み合わせて、インクセットとしてもよい。インクセットに用いられるカラーインクは特に限定されることはなく、目的とする画像にあわせて適当なインクを選択することができる。画像形成の容易さから、カラーインクは、本発明の活性光線硬化型インクジェット白色インクと同様にインクジェットによって吐出可能なインクであることが好ましく、また、活性光線硬化型のインクであることが好ましい。また、画像形成の容易さから、カラーインクは、ワックスまたはゲル化剤を含むことによりゾルゲル相転移が可能なインクであることが好ましい。
[画像形成方法]
本発明に係る画像形成方法は、(a)上記の活性光線硬化型インクジェット白色インクをインク吐出用記録ヘッドから吐出させて記録媒体上に付着させる工程、および(b)付着した活性光線硬化型インクジェット白色インクに活性光線を照射する工程、を有する。
前記インクセットを用いて画像を形成する場合、本発明の画像形成方法は、上述の(a)上記の活性光線硬化型インクジェット白色インクをインク吐出用記録ヘッドから吐出させて前記記録媒体上に付着させる工程、および(b)付着した前記活性光線硬化型インクジェット白色インクに活性光線を照射する工程のほかに、(c)1または複数のカラーインクを記録媒体上に付着させる工程、および(d)付着したカラーインクを定着させる工程を有してもよい。本発明において、カラーインクを定着させるとは、記録媒体に付着したカラーインクを硬化させることをいう。なお、本発明の活性光線硬化型インクジェット白色インクは付着時にゲル化するため、カラーインクとの混じりが生じにくい。
前記インクセットを用いて、本発明の活性光線硬化型インクジェット白色インクの付着および定着、ならびに活性光線硬化型のカラーインクの付着および定着を単一のインクジェット記録装置で行う場合、図1A~図3に記載のような構成の装置を用いることができる。なお、活性光線硬化型インクジェット方式のインクジェット記録装置には、ライン記録方式(シングルパス記録方式)のものと、シリアル記録方式のものとがある。求められる画像の解像度や記録速度に応じていずれの方式を選択してもよいが、高速記録の観点では、ライン記録方式(シングルパス記録方式)が好ましい。
[3級アミン基を有するくし型ブロックコポリマーの調製]
フラスコ反応器内部に装填された活性触媒(ゼオライト)およびラウリルアルコール(花王株式会社製 カルコール2098)500gを緩衝槽に仕込み、水素ガスを供給しながら、緩衝槽と反応器との間で液を循環させた。その後反応器内部の温度を65℃まで昇温してからPB-824(味の素ファインテクノ株式会社製)のDPGMA溶液(東亜合成株式会社製アローニックスM-120)を反応器に供給し、さらに反応器内部の温度を90℃まで昇温して反応を開始した。反応開始から3時間後にPB-824溶液の供給を停止し、全系を冷却して緩衝槽および反応器内部の液全量を抜き出して、分散剤D(DPGMA溶液中に50wt%固形分存在する)を調製した。
以下の成分により、白色顔料分散体1を調製した。
白色顔料1:CR-EL(石原産業社) 25.0wt%
分散剤A:BYK JET-9151(ビックケミー社) 10.0wt%
光重合性化合物:ジプロピレングリコールモノアクリレート 64.5wt%
重合禁止剤:Irgastab UV-10(BASF製) 0.5wt%
その後、それぞれの分散体を60℃に加熱しながら以下の比率に従って光重合性化合物、ワックスおよび光重合開始剤を加えて、活性光線硬化型インクA-1~J-6を調製した。
白色顔料分散体A-1~J-6:50.0wt%
光重合性化合物:ポリエチレングリコールジアクリレート(PEGDA)(ダイセル化学製) 25.0wt%
光重合性化合物:4EO変性ペンタエリスリトールテトラアクリレート(東亜合成製) 18.0wt%
ワックス:カオーワックスT-1(脂肪族ケトン)(花王株式会社製) 2.5wt%
ワックス:ユニスターM222(脂肪酸エステル)(ユニオンカーバイト製) 2.5wt%
光重合開始剤:ITX(BASF製) 0.3wt%
光重合開始剤:Irgacure 819(BASF製) 0.3wt%
それぞれの活性光線硬化型インクをポール(株)製 WACフィルター(0.3μm精度)でろ過した。その後、それぞれのインクをコニカミノルタインクジェットヘッド(KM1048)に導入し、印字幅100mm×100mm、解像度720×720dpiの条件でベタ画像を印字した。印字基材はOKトップコート(印刷用紙)を使用した。UV照射光源として京セラ製LEDランプを使用し、250mJのエネルギーで紫外線を印字したインクに照射してインクを硬化させた。
(1)粘度変化量
それぞれの活性光線硬化型インクを耐熱管に採取して、85℃で1ヶ月間高温槽に保存した。
保存前のインク粘度と保存後のインク粘度とを、アントンパール社製ストレスレオメーターMCR-102型を用いてコーンプレート75mmφにてせん断速度1000(1/sec)にて温度80℃で5分間一定回転させたときのトルクを粘度換算してそれぞれ測定した。保存前と保存後の粘度の差が10.0mPas以内である場合に粘度の変化は少ない(表3~6中、+で表記。)と判定し、粘度の差が1.0mPas以内である場合に粘度の変化はさらに少ない(表3~6中、++で表記。)と判定した。
それぞれの活性光線硬化型インクによるベタ画像の60℃反射光沢値をデジタルハンディ光沢計(堀場製作所製グロスチェッカーIG-331)で測定した。Yellow、Cyan、Blackのベタ画像の平均光沢値(40)からそれぞれの活性光線硬化型インクによる白色のベタ画像の反射光沢値がどれだけ減少しているかを調べ、反射光沢値の差の絶対値が10未満の場合に光沢差は少ない(表3~6中、+で表記。)と判定し、反射光沢値の差の絶対値が4未満の場合に光沢差はさらに少ない(表3~6中、++で表記。)と判定した。
上述の条件で連続100枚の印字を行い、ヘッドノズルの欠数を計測した。欠数が10未満の場合に、ヘッド詰まりは少ない(表3~4中、+で表記。)と判定し、欠数が5未満の場合に、ヘッド詰まりは少ない(表3~4中、++で表記。)と判定した。
[活性光線硬化型インクの調製]
実施例1の白色顔料分散体A-2(分散剤としてBYK JET-9151、白色顔料としてTCR-52を使用)を用い、実施例1と同様の手順で活性光線硬化型インクを調製した。その際、分散剤としてのBYK JET-9151の配合量、ならびにワックスとしてのカオーワックスT-1(脂肪族ケトン)およびユニスターM222(脂肪酸エステル)の配合量を表5および表6に従って変更し、活性光線硬化型インクK-1~R-6を調製した。
実施例1と同様の方法で、OKトップコート(印刷用紙)にそれぞれのインクでベタ画像を印字し、紫外線を印字したインクに照射してインクを硬化させた。
(1)粘度変化量
実施例1と同様の方法で、85℃で1ヶ月間高温槽に保存した前後のインク粘度を測定し、粘度変化を判定した。
実施例1と同様の方法で、Yellow、Cyan、Blackのベタ画像の平均光沢値(40)からそれぞれの活性光線硬化型インクによる白色のベタ画像の反射光沢値がどれだけ減少しているかを調べ、光沢差を判定した。
印字する際の基材の温度を50℃にしてベタ100%画像を形成し硬化させ、印字後の画像を顕微鏡(×200)で観察し、ランダムに選択した10か所の液滴径を測定した。測定した値の平均値が60μm以上65μm以下の場合にピニング性は良好である(表5~6中、+で表記。)と判定し、平均値が60μm以上62μm以下の場合にピニング性はさらに良好である(表5~6中、++で表記。)と判定した。
12 記録媒体
14、24 インク吐出用記録ヘッド
16、26 ヘッドキャリッジ
18、28 光照射部
19 温度制御部
27 ガイド部
Claims (10)
- 顔料、分散剤、ワックス、光重合性化合物および光重合開始剤を含み、温度変化によってゾルゲル相転移可能な活性光線硬化型インクジェット白色インクであって、
該顔料はアルミナで表面被覆された二酸化チタンを含み、
該二酸化チタンの含有量は、インクの全質量中10質量%以上15質量%以下であり、
該インクは顔料に対する質量比率で200ppm以下のナトリウムイオンを含み、
該分散剤は、3級アミン基を有するくし型ブロックコポリマーを含む、インク。 - 前記ブロックコポリマーの含有量は、インクの全質量中、2.0質量%以上8.0質量%以下である、請求項1に記載のインク。
- 前記ワックスは脂肪族ケトンおよび脂肪酸エステルを含む、請求項1または2に記載のインク。
- 前記脂肪族ケトン含有量と脂肪酸エステル含有量との合計は、インクの全質量中、2.0質量%以上5.0質量%以下である、請求項3に記載のインク。
- 前記脂肪酸エステルの含有量と同量または前記脂肪酸エステルの含有量より多い量の前記脂肪族ケトンを含む、請求項3または4に記載のインク。
- 請求項1~5のいずれか1項に記載の活性光線硬化型インクジェット白色インクをインク吐出用記録ヘッドから吐出させて記録媒体上に付着させる工程と、該付着した活性光線硬化型インクジェット白色インクに活性光線を照射する工程と、を有する、画像形成方法。
- さらに、1または複数のカラーインクを前記記録媒体上に付着させる工程、および該付着したカラーインクを定着させる工程を有する、請求項6に記載の画像形成方法。
- 前記カラーインクを記録媒体上に付着させる工程の後に、前記活性光線硬化型インクジェット白色インクを記録媒体上に付着させる工程を有する、請求項7に記載の方法。
- 前記活性光線硬化型インクジェット白色インクを記録媒体上に付着させる工程の後に、前記カラーインクを記録媒体上に付着させる工程を有する、請求項7に記載の方法。
- 前記カラーインクは光重合性化合物および光重合開始剤を含む活性光線硬化型インクであり、前記付着したカラーインクを定着させる工程は、付着したカラーインクに活性光線を照射する工程であり、該カラーインクに活性光線を照射する工程および前記付着した活性光線硬化型インクジェット白色インクに活性光線を照射する工程とは、1回の活性光線照射によって行われる、請求項7~9のいずれか1項に記載の方法。
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