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WO2017122447A1 - Encre pour jet d'encre et procédé de formation d'image - Google Patents

Encre pour jet d'encre et procédé de formation d'image Download PDF

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Publication number
WO2017122447A1
WO2017122447A1 PCT/JP2016/085469 JP2016085469W WO2017122447A1 WO 2017122447 A1 WO2017122447 A1 WO 2017122447A1 JP 2016085469 W JP2016085469 W JP 2016085469W WO 2017122447 A1 WO2017122447 A1 WO 2017122447A1
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WO
WIPO (PCT)
Prior art keywords
ink
organic material
inkjet ink
image
gelling agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/085469
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English (en)
Japanese (ja)
Inventor
石川　貴之
英也 三輪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of WO2017122447A1 publication Critical patent/WO2017122447A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • 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
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the present invention relates to an inkjet ink and an image forming method.
  • the inkjet method is an image forming method in which minute droplets of inkjet ink are ejected from nozzles of an inkjet head and landed on a substrate in the form of dots.
  • the ink jet method can easily and inexpensively form an image, and thus is applied to various printing fields including special printing such as photography, various printing, marking, and color filters.
  • Inkjet inks are water-based inks composed of water and a small amount of organic solvents, solvent-based inks that contain organic solvents but are substantially free of water, and are cured by polymerization and crosslinking by irradiation with actinic rays after printing.
  • There are a plurality of types of inks such as actinic ray curable ink containing a photopolymerizable compound as a liquid component, and these inks are properly used according to applications.
  • the liquid component of the ink evaporates or diffuses into the substrate, thereby forming an image of the color material on the substrate. Is done.
  • the liquid component is cured by irradiating the ink with actinic rays to form an image of the color material on the substrate.
  • Inkjet ink often contains various color materials including pigments and dyes.
  • the color material is selected based on conditions such as the type of inkjet ink and the appearance of the image to be formed. For example, when forming an image having a metallic luster, a pigment exhibiting a metallic luster is used as the color material.
  • Non-Patent Document 1 discloses that a polymer of thiophene having a substituent is an organic material having a metallic luster by crystallization, and has high weather resistance stability when the solution is naturally dried to form a film. To disclose. Non-Patent Document 1 discloses that the substituted thiophene polymer is dissolved in a solvent having a high boiling point (low evaporation rate) and the resulting solution is naturally dried (decreasing the amount of the solvent). It has been suggested that the appearance of the resulting film is closer to gold because dense intermolecular packing is formed by the orientation and crystallization of the coalescence.
  • Patent Document 1 describes a coating liquid containing a thiophene polymer having a substituent, and describes that this coating liquid is used as a paint, a gravure ink, and an inkjet ink.
  • Non-Patent Document 1 in order to develop a metallic luster with a crystalline organic material, it is desirable to crystallize the organic material over time. Therefore, as described in Patent Document 1, in order to develop more metallic luster in an image formed by an inkjet ink containing a crystalline organic material that exhibits metallic luster, ink droplets are used as a basis. It is preferable that the time during which the organic material is dispersed in the ink after landing on the material is longer.
  • the liquid component of the ink droplets that have landed on the substrate is evaporated, diffused into the substrate, or cured (hereinafter simply referred to as “evaporation”). It is necessary to lengthen the time until.
  • the present invention has been made in view of the above problems, and an inkjet ink capable of expressing a metallic luster with a crystalline organic material on various recording media and simultaneously forming a high-definition image, and such It is an object of the present invention to provide a method for forming an image using inkjet ink.
  • each R 1 is independently an atom or a functional group selected from the group consisting of a hydrogen atom, an alkoxy group, an amino group, and a hydroxyl group, and at least one R 1 is not a hydrogen atom, but n Is an integer from 3 to 100.
  • the reticulated organogel comprises dextrin fatty acid ester, sucrose fatty acid ester, inulin fatty acid ester, 1,2-hydroxystearic acid, metal soap, fumed silicic acid anhydride, glyceryl behenate, eicosane diacid glyceryl and organically modified clay
  • the inkjet ink according to [4] which is one or more compounds selected from the group consisting of minerals.
  • an inkjet ink capable of expressing a metallic luster with a crystalline organic material and simultaneously forming a high-definition image, and a method for forming an image using such an inkjet ink.
  • ink droplets containing a crystalline organic material capable of expressing a metallic luster further contain a gelling agent, thereby spreading the ink droplets. It was found that a high-definition image having a metallic luster can be formed by appropriately adjusting the image quality. Although the detailed mechanism is not clear, it is presumed as follows.
  • the gelling agent increases the viscosity of the ink droplets that have landed on the substrate and gels the ink droplets, so that the wetting and spreading of the ink droplets can be more easily adjusted.
  • Ink containing a gelling agent is ejected from an inkjet head with a low viscosity and becomes ink droplets. After landing on the substrate, the viscosity increases after moderately spreading, and no further wetting and spreading occur. Fixed.
  • the organic material is surrounded by the gelling agent together with the liquid component of the ink, thereby increasing the time until the liquid component of the ink evaporates to a certain extent. It is presumed that the material can move inside the droplet and be oriented and crystallized. Therefore, it is considered that the gelling agent can promote crystallization of the organic material regardless of the type of solvent used.
  • ink droplets that do not contain a gelling agent are landed on an ink-absorbing base material that has irregularities such as paper, for example, in water-based inks and solvent-based inks
  • the ink droplets become uneven on the base material.
  • the organic material also spreads along the unevenness of the base material, and it becomes easy to diffusely reflect light, so that the metallic luster is difficult to appear.
  • the ink droplet thickened by the gelling agent forms a somewhat smooth film in which the organic material is uniformly dispersed.
  • the gelling agent can sufficiently exhibit the metallic luster even when an image is formed on an ink-absorbing base material having irregularities.
  • the ink-jet ink containing the gelling agent and the crystalline organic material capable of expressing a metallic luster it can land on recording materials of various materials and surface states regardless of the type of solvent used. While appropriately adjusting the wetting and spreading of the ink droplets, the organic material can be crystallized before the liquid component evaporates or the like, and the metallic luster can be sufficiently developed.
  • the ink-jet ink is an ink-jet ink containing a crystalline organic material capable of exhibiting a metallic luster and a gelling agent (hereinafter, also simply referred to as “metallic glossy gel ink”).
  • Crystalline organic material capable of exhibiting metallic luster The above organic material is an organic material capable of exhibiting metallic luster by crystallization, and can be dissolved in inkjet ink by selecting an appropriate solvent If it is. Only one kind of the organic material may be contained in the metallic glossy gel ink, or two or more kinds thereof may be contained.
  • the surface of a thin film formed by applying a solution obtained by dissolving the organic material in a known solvent to a substrate and drying it is formed by a known minute angle incident X-ray diffraction (GIXD). Means that a diffraction peak corresponding to the organic material is observed.
  • GXD minute angle incident X-ray diffraction
  • the expression of metallic luster can be recognized visually as metallic luster, and the gloss of the thin film with an incident angle of 60 ° and a reflection angle of 60 ° is measured with a gloss meter (GM-60Plus manufactured by Konica Minolta Co., Ltd.). The glossiness obtained by measurement means 50 or more.
  • Examples of the organic material include an organic material having a structural unit represented by the following formula (1).
  • each R 1 is independently an atom or a functional group selected from the group consisting of a hydrogen atom, an alkoxy group, an amino group, and a hydroxyl group, and at least one R 1 is not a hydrogen atom, but n Is an integer from 3 to 100, preferably an integer from 3 to 40.
  • R 1 is preferably a hydrogen atom.
  • One of R 1 is preferably an alkoxy group.
  • the plurality of structural units represented by the formula (1) possessed by the organic material may all be structural units having the same R 1 , or structural units having different R 1 may be combined.
  • the alkoxy group that can be taken by R 1 preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • Examples of the structural unit represented by the formula (1) containing R 1 which is an alkoxy group include 3-methoxythiophene, 3-ethoxythiophene, 3-propoxythiophene, 3-isopropoxythiophene, 3-butoxythiophene, 3 , 4-dimethoxythiophene, 3,4-diethoxythiophene, 3-methoxy-4-ethoxythiophene, and 3,4-dipropoxythiophene derived structural units are included.
  • Examples of the structural unit represented by the formula (1) containing R 1 which is an amino group include 3-aminothiophene, 3,4-diaminothiophene, 3- (N-methylamino) thiophene, 3- (N, N-dimethylamino) thiophene, 3- (N-ethylamino) thiophene, 3- (N, N-diethylamino) thiophene, 3- (N, N-propylamino) thiophene, 3- (N, N-dibutylamino) Constituent units derived from thiophene, 3,4-bis (N, N-dimethylamino) thiophene, and 3,4-bis (N, N-diethylamino) thiophene are included.
  • Examples of the structural unit represented by the formula (1) having different R 1 include 3-amino-4-methylthiophene, 3-amino-4-hydroxythiophene, 3-methyl-4-hydroxythiophene, 3-methoxy Structural units derived from -4-aminothiophene, 3-methoxy-4-methylthiophene, and 3-methoxy-4-hydroxythiophene are included.
  • the polystyrene-converted weight average molecular weight of the organic material obtained by measurement by gel permeation chromatography is preferably 300 or more and 4000 or less, more preferably 500 or more and 3000 or less, and 800 or more. More preferably, it is 2500 or less.
  • the content of the organic material in the metallic glossy gel ink may be a range in which a desired metallic gloss appears in the formed image and the viscosity of the metallic glossy gel ink can be discharged from the nozzles of the inkjet head.
  • the content of the organic material is preferably 0.25% by mass to 20% by mass and more preferably 1.0% by mass to 10% by mass with respect to the total mass of the metallic glossy gel ink. preferable.
  • the gelling agent only needs to be able to make the metallic glossy gel ink droplets in a liquid state when discharged from the ink jet head and to increase the viscosity after landing on the base material.
  • the gelling agent may be a reversible sol-gel phase transition of the metallic glossy gel ink due to a temperature change.
  • Ink containing such a gelling agent can be ejected from an inkjet head by heating to lower the viscosity, and after ejection and landing on the substrate, it is cooled and thickened to spread the ink. Can be adjusted.
  • the gelling agent surrounds the organic material together with the liquid component of the ink, thereby increasing the time until the liquid component of the ink evaporates, and the organic material Makes it possible to move inside the droplet and to be oriented and crystallized.
  • Only one kind of gelling agent may be contained in the metallic glossy gel ink, or two or more kinds may be contained.
  • the gelling agent may be a reticulated organogel that can form a network-like structure in which colloidal particles and molecules are connected in a string by hydrogen bonds, etc., or a card house structure is formed by physically combining plate-like crystals.
  • An oil wax gel can be used.
  • the gelling agent is a reticulated organogel from the viewpoint of preventing whitening of the image due to the crystallized gelling agent and appropriately surrounding the organic material.
  • Preferred examples of the reticulated organogel include dextrin fatty acid ester, sucrose fatty acid ester, inulin fatty acid ester, 1,2-hydroxystearic acid, metal soap, fumed silicic acid anhydride, glyceryl behenate, eicosane diacid glyceryl and organic modification Contains clay minerals.
  • Examples of reticulated organogels other than the above include dibenzylidene sorbitol.
  • dextrin fatty acid ester examples include esters of dextrin and higher fatty acids having 8 to 24 carbon atoms, such as 2-ethylhexanoic acid dextrin, lauric acid dextrin, palmitic acid dextrin, myristic acid dextrin, oleic acid dextrin, Dextrin stearate and dextrin behenate, and mixtures thereof are included.
  • esters of dextrin and higher fatty acids having 14 to 18 carbon atoms for example, dextrin palmitate, dextrin myristate and dextrin stearate, and mixtures thereof are preferred.
  • sucrose fatty acid esters examples include esters of sucrose with higher fatty acids having 12 to 22 carbon atoms, such as sucrose palmitate, sucrose stearate, sucrose behenate, sucrose olein. Acid esters, and sucrose laurate esters, and mixtures thereof are included.
  • inulin fatty acid ester examples include inulin palmitate, inulin 2-ethylhexanoate, inulin stearate, inulin oleate, inulin isopalmitate, and isostearic acid, and mixtures thereof.
  • Examples of the metal soap include a salt of a metal and a higher fatty acid having 12 to 22 carbon atoms.
  • the metal include calcium, magnesium, zinc, barium, aluminum, lithium, sodium, and potassium.
  • Examples of the higher fatty acid include stearic acid, hydroxystearic acid, behenic acid, montanic acid, lauric acid, palmitic acid, and myristic acid.
  • Examples of the fumed silicic acid anhydride include fine amorphous silicic acid having a primary particle diameter of, for example, 5 nm to 50 nm.
  • Examples of the above organically modified clay minerals include distearyl dimonium hectorite, dimethyl distearyl ammonium hectorite, dimethyl distearyl ammonium bentonite, benzyl dimethyl stearyl ammonium hectorite, and distearyl dimethyl ammonium chloride treated aluminum magnesium silicate. It is.
  • dibenzylidene sorbitol examples include 1,3: 2,4-bis-O-benzylidene-D-glucitol and 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol. included.
  • oil wax gel examples include paraffin, long chain fatty acid ester, long chain fatty acid and higher alcohol.
  • long chain fatty acid esters examples include behenyl behenate, icosyl icosanoate, stearyl stearate, palmityl stearate, lauryl stearate, cetyl palmitate, stearyl palmitate, myristyl myristate, cetyl myristate, octyldodecyl myristate , Stearyl oleate, stearyl erucate, stearyl linoleate, behenyl oleate, and arachidyl linoleate, and mixtures thereof.
  • long chain fatty acids examples include behenic acid, arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, and erucic acid, and mixtures thereof.
  • Examples of the above higher alcohols include stearyl alcohol and behenyl alcohol and mixtures thereof.
  • the gelling agent should be a compound having a melting point lower than the liquid component of the ink.
  • the liquid component of the ink may be water when the metallic glossy gel ink is a water-based ink, an organic solvent when the ink is a solvent-based ink, and a melting point of a photopolymerizable compound when the ink is a sliding light curable ink. .
  • the gelling agent preferably has a hydrophilic portion.
  • reticulated organogels having hydrophilic sites include dextrin fatty acid ester, sucrose fatty acid ester, inulin fatty acid ester, 1,2-hydroxystearic acid, metal soap, fumed silicic acid anhydride, glyceryl behenate, glyceryl eicosane diacid , And organically modified clay minerals.
  • the oil wax gel having a hydrophilic portion include higher alcohols.
  • the content of the gelling agent in the metallic glossy gel ink may be within a range in which the ink droplets that have landed on the substrate spread to a desired dot diameter and the viscosity of the metallic glossy gel ink can be discharged from the nozzles of the inkjet head.
  • the content of the gelling agent is preferably 0.1% by mass or more and 15% by mass or less, and preferably 0.1% by mass or more and 10% by mass or less with respect to the total mass of the metallic glossy gel ink. More preferably, it is more preferably 0.5% by mass or more and 5% by mass or less.
  • the metallic glossy gel ink has a solvent and other components so that a desired metallic gloss can be expressed in the formed image and the viscosity of the metallic glossy gel ink can be discharged from the nozzles of the inkjet head. Can be contained.
  • the metallic glossy gel ink when it is a water-based ink, can further contain water and optionally a water-soluble organic solvent. Further, when it is a solvent-based ink, the metallic glossy gel ink can further contain an organic solvent. Further, when it is an actinic ray curable ink, the metallic glossy gel ink can further contain a photopolymerizable compound that is polymerized and cross-linked by irradiation with actinic rays and optionally a photopolymerization initiator.
  • the metallic glossy gel ink further includes a colorant, a dispersant for dispersing the organic material and other pigments, a fixing resin for fixing the organic material and other pigments to the base material, or a surfactant as necessary. You may contain.
  • the above other components may be included in the metallic glossy gel ink alone or in combination of two or more.
  • water-soluble organic solvent when the metallic glossy gel ink is a water-based ink examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol and alcohol containing t-butanol, ethylene glycol, diethylene glycol, Glycerin, hexanetriol, thiodiglycol, 1,2-butanediol, 1,3-butanediol, including ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, and pentanediol, Polyhydric alcohols containing 1,2-pentanediol, 1,2-hexanediol and 1,2-heptanediol, ethanolamine, diethano Contains ruamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanol
  • the content of the water-soluble organic solvent when the metallic glossy gel ink is a water-based ink can be, for example, 5.0% by mass or more and 30% by mass or less with respect to the total mass of the metallic glossy gel ink.
  • Examples of the organic solvent when the metallic glossy gel ink is a solvent-based ink include a water-soluble organic solvent and a water-insoluble organic solvent that can be used for the water-based ink.
  • water-insoluble organic solvent examples include pentane, hexane, i-hexane, heptane, i-heptane, octane, i-octane, and aliphatic hydrocarbons having 5 to 15 carbon atoms and cyclopentane.
  • the content of the water-insoluble organic solvent when the metallic glossy gel ink is a solvent-based ink can be, for example, 1.0% by mass or more and 98% by mass or less based on the total mass of the metallic glossy gel ink. It is more preferable to set it as mass% or more and 98 mass% or less, and it is further more preferable to set it as 80 mass% or more and 98 mass% or less.
  • Examples of the photopolymerizable compound when the metallic glossy gel ink is an actinic ray curable ink include a radical polymerizable compound and a cationic polymerizable compound.
  • the photopolymerizable compound may be any of a monomer, a polymerizable oligomer, a prepolymer, or a mixture thereof.
  • actinic rays examples include ultraviolet rays, electron beams, ⁇ rays, ⁇ rays and X rays. From the viewpoint of safety and from the viewpoint that the polymerization and crosslinking can be generated even with a lower energy amount, the actinic ray is preferably an ultraviolet ray or an electron beam.
  • the radical polymerizable compound is preferably an unsaturated carboxylic acid ester compound, and more preferably (meth) acrylate.
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acryl means acryl or methacryl.
  • Examples of monofunctional (meth) acrylates include isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isomustyl (meth) acrylate, isostearyl (Meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meta ) Acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxye (Meth) acrylate, t
  • polyfunctional (meth) acrylates include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Dimethylol-tricyclodecane di (meth) acrylate, PO adduct di (meth) acrylate of bisphenol A, neopentyl glycol di (meth) acrylate hydroxypivalate, polytetramethylene glycol di ( A) bifunctional (meth) acrylates including polyethylene acrylate, polyethylene glycol di (
  • the radical polymerizable compound preferably contains (meth) acrylate modified with ethylene oxide or propylene oxide (hereinafter also simply referred to as “modified (meth) acrylate”).
  • modified (meth) acrylate has higher photosensitivity. Further, the modified (meth) acrylate is more compatible with other ink components even at high temperatures. Furthermore, since the modified (meth) acrylate has less curing shrinkage, curling of the printed matter during image formation is less likely to occur.
  • Examples of the cationic polymerizable compound include an epoxy compound, a vinyl ether compound, and an oxetane compound.
  • the content of the photopolymerizable compound when the metallic glossy gel ink is an actinic ray curable ink can be, for example, 1.0% by mass or more and 97% by mass or less with respect to the total mass of the metallic glossy gel ink, It is preferable to set it to 30 to 95 mass%.
  • the photopolymerization initiator when the metallic glossy gel ink is an actinic ray curable ink may be any one that can initiate polymerization of the photopolymerizable oligomer and the photopolymerizable monomer.
  • the photopolymerization initiator when the metallic glossy gel ink has a radical polymerizable compound, can be a photoradical initiator, and when the metallic glossy gel ink has a cationic polymerizable compound, the photopolymerization initiator is a photocationic initiation.
  • Agent photoacid generator
  • the content of the photopolymerization initiator can be arbitrarily set within a range in which the ink is sufficiently cured by irradiation with actinic rays and does not lower the ink ejection properties.
  • it can be 0.1 mass% or more and 20 mass% or less, preferably 1.0 mass% or more and 12 mass% or less with respect to the total mass of the ink.
  • the color material examples include dyes and pigments. From the viewpoint of obtaining an image having good weather resistance, the color material is preferably a pigment.
  • the pigment can be selected from, for example, a yellow pigment, a red or magenta pigment, a blue or cyan pigment, and a black pigment depending on the color of the image to be formed.
  • the dispersant is capable of sufficiently dispersing the organic material and other pigments.
  • the dispersant 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 Nonylphenyl ether, and stearylamine acetate are included.
  • the content of the dispersant can be, for example, 20% by mass to 70% by mass with respect to the total mass of the organic material and other pigments.
  • the fixing resin examples include (meth) acrylic resin, epoxy resin, polysiloxane resin, maleic acid resin, vinyl resin, polyamide resin, nitrocellulose, cellulose acetate, ethyl cellulose, ethylene-vinyl acetate copolymer, urethane resin, Polyester resins and alkyd resins are included.
  • the content of the fixing resin can be, for example, 1.0% by mass or more and 10.0% by mass or less with respect to the total mass of the metallic glossy gel ink. Since the organic material can be crystallized to form a self-film, the metallic glossy gel ink does not need to contain a fixing resin substantially.
  • surfactants include anionic surfactants, including dialkyl sulfosuccinates, alkyl naphthalene sulfonates and fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols and poly (ethylene glycols).
  • anionic surfactants including oxyethylene / polyoxypropylene block copolymers, cationic surfactants including alkylamine salts and quaternary ammonium salts, silicone surfactants, and fluorine surfactants It is.
  • the content of the surfactant is preferably 0.001% by mass or more and less than 1.0% by mass with respect to the total mass of the metallic glossy gel ink.
  • the viscosity of the metallic glossy gel ink at 80 ° C. is preferably 3 mPa ⁇ s or more and 20 mPa ⁇ s or less.
  • the phase transition temperature of the metallic glossy gel ink is preferably 40 ° C. or higher and 70 ° C. or lower.
  • the phase transition temperature of the ink is 40 ° C. or higher, the ink quickly thickens after landing on the base material, so that the degree of wetting and spreading can be adjusted more easily.
  • the phase transition temperature of the ink is 70 ° C. or less, the ink is less likely to gel when ejected from the ejection head whose ink temperature is usually about 80 ° C., so that the ink can be ejected more stably.
  • the viscosity at 80 ° C., the viscosity at 25 ° C. and the phase transition temperature of the metallic glossy gel ink can be determined by measuring the temperature change of the dynamic viscoelasticity of the ink with a rheometer.
  • these viscosities and phase transition temperatures are values obtained by the following method.
  • the metal glossy gel ink was heated to 100 ° C., and the shear rate was measured while measuring the viscosity with a stress control type rheometer (manufactured by Anton Paar, Physica MCR301 (cone plate diameter: 75 mm, cone angle: 1.0 °)).
  • the ink is cooled to 20 ° C.
  • the viscosity at 80 ° C. and the viscosity at 25 ° C. are obtained by reading the viscosities at 80 ° C. and 25 ° C. in the temperature change curve of the viscosity, respectively.
  • the phase transition temperature is determined as a temperature at which the viscosity becomes 200 mPa ⁇ s in the temperature change curve of the viscosity.
  • a metallic glossy gel ink is obtained, for example, by stirring and mixing a crystalline organic material and a gelling agent capable of developing a metallic luster and the above-mentioned other components optionally used under heating. Can do. It is preferable to filter the obtained liquid mixture with a predetermined filter. At this time, a pigment dispersion in which the organic material and an optional pigment are dispersed in a liquid component together with the dispersant is prepared in advance, and the remaining components are added thereto and mixed while heating. Good.
  • the image forming method using the ink-jet ink includes a step of discharging a metallic glossy gel ink droplet from a nozzle of an ink-jet head and landing on a substrate (hereinafter also simply referred to as “landing step”).
  • An image forming method When the metallic glossy gel ink is an actinic ray curable ink, the image forming method includes a step of forming an image portion containing the organic material by evaporating the liquid component of the metallic glossy gel ink that has landed on the substrate (hereinafter referred to as an “image portion”). Or simply referred to as “evaporation step”).
  • the image forming method includes a step of bringing the base material and the molded body after the liquid component has evaporated or the like into close contact, or transferring the image portion from the base material to the molded body (hereinafter simply referred to as “decoration”). It may also be referred to as a “step”.
  • the ejection method from the inkjet head may be either an on-demand method or a continuous method.
  • On-demand inkjet heads include single-cavity, double-cavity, bender, piston, shear-mode, and shared wall types, as well as electro-mechanical conversion, thermal inkjet and bubble jet. Any of the electric-thermal conversion methods including Canon Inc. (registered trademark) type may be used.
  • the ink droplets are ejected from the inkjet head in a heated state.
  • the temperature of the ink when ejected is preferably 35 ° C. or more and 100 ° C. or less, and more preferably 35 ° C. or more and 80 ° C. or less from the viewpoint of further improving the ejection stability. From the above viewpoint, it is more preferable to emit at an ink temperature such that the viscosity of the ink is 7 mPa ⁇ s or more and 15 mPa ⁇ s or less, more preferably 8 mPa ⁇ s or more and 13 mPa ⁇ s or less.
  • the temperature of the metallic glossy gel ink when filled in the inkjet head is a temperature that is 10 ° C. or more and 30 ° C. or less higher than the gelation temperature of the ink. It is preferable to adjust so that.
  • the method for heating the ink to a predetermined temperature is not particularly limited.
  • at least one of an ink tank constituting a head carriage, an ink supply system including a supply pipe and a front chamber ink tank immediately before the head, a pipe with a filter, and a piezo head is heated by a panel heater, a ribbon heater, and heat retaining water. And heating to a predetermined temperature.
  • the droplet amount of the ejected ink is 2 pL or more and 20 pL or less.
  • Evaporation step In the evaporation step, the liquid component of the metallic glossy gel ink that has landed on the substrate is evaporated to form an image portion containing the organic material.
  • the metallic glossy gel ink is a water-based ink or a solvent-based ink
  • the liquid component of the ink is evaporated or diffused into the substrate, and the organic material is The image part to contain can be formed.
  • the substrate may be heated to promote evaporation of the liquid component.
  • the liquid component of the ink can be cured by irradiating the droplets of the metallic glossy gel ink landed on the substrate with an actinic ray.
  • the actinic rays include electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, and X-rays. Among these, it is preferable to irradiate ultraviolet rays from the viewpoint of easy handling and little influence on the human body.
  • the light source is preferably a light emitting diode (LED) from the viewpoint of suppressing the occurrence of ink curing failure due to melting of the metallic glossy gel ink by the radiant heat of the light source.
  • decorating process is a process in which the base material and the molded body after the liquid component evaporates are brought into close contact with each other, or the image portion is transferred from the base material to the molded body.
  • the adhesion may be performed by a method of heating and softening a base material having a hardened metallic glossy gel ink and then press-bonding it to a molded body that has already been molded (hereinafter also simply referred to as “thermal transfer method”). Alternatively, it may be carried out by a method in which a molten resin is injected into a mold on which a base material having a hardened metallic glossy gel ink is disposed and integrally molded (hereinafter also simply referred to as “integral molding method”).
  • thermal transfer method examples include a vacuum forming method or a pressure forming method in which the base material heated and softened by vacuum suction or pressurization with compressed air is pressure-bonded to a formed body.
  • integral molding method examples include a film insert molding method in which a material of a molten molded body is poured into a mold in which the base material is installed, and the base material and the molded body are welded in the mold.
  • the transfer can be performed by, for example, an in-mold molding method in which a material of a molten molded body is poured into a mold on which the substrate is placed, and an image formed on the substrate is transferred to the molded body.
  • Base material The base material should just be able to form an image with a metallic glossy gel ink.
  • substrates include polyethylene terephthalate, polyethylene naphthalate, and polyesters including polybutylene terephthalate, polyvinyl chloride, poly ⁇ -olefins including polyethylene and polypropylene, polyurethane, polymethyl methacrylate (PMMA) (meth) Includes acrylic resin, polycarbonate, polystyrene, and films containing acrylonitrile-butadiene-styrene (ABS) copolymer, metal, glass, and ink-absorbing paper (eg, coated paper for printing and coated paper B for printing) It is.
  • ABS acrylonitrile-butadiene-styrene
  • the substrate can be arbitrarily selected based on the type of ink and the use of the formed image.
  • the substrate is preferably the film.
  • the resulting solution was filtered with a Kiriyama funnel, and then the residue was washed with methanol five times to remove impurities. After washing 5 times, the obtained residue was vacuum-dried in an oven at 45 ° C. for 2 hours to obtain an organic material M1. The yield at this time was 70%, and the weight average molecular weight of the obtained organic material M1 was 1700.
  • the said weight average molecular weight is a weight average molecular weight of polystyrene conversion obtained by measuring by gel permeation chromatography (GPC). The same applies to the following organic material M2.
  • Organic material M2 Except for changing iron (III) perchlorate n hydrate to iron (III) chloride, the same procedure as in the production of the organic material M1 was performed to obtain an organic material M2. The yield at this time was 65%, and the weight average molecular weight of the obtained organic material M2 was 1400.
  • Organic solvent (B) The following organic solvents were used as B1 to B8.
  • B2 Ethylene glycol monobutyl ether acetate
  • B3 1,3-butanediol
  • B4 Propylene glycol
  • B5 Isopropyl alcohol
  • B6 Ethylene glycol hexyl ether
  • B7 Diethylene glycol butyl ether
  • B8 Propylene glycol propyl ether
  • C Gelling agent
  • C1 Dextrin fatty acid ester (dextrin palmitate (manufactured by Chiba Flour Milling Co., Ltd., Leopard KL (“Leopard” is a registered trademark of the company))
  • C2 Sucrose fatty acid ester (sucrose stearate (manufactured by Mitsubishi Chemical Foods, Ryoto Sugar Ester S-170 (“Ryoto” is a registered trademark of Mitsubishi Chemical Corporation))
  • C3 Inulin fatty acid ester (inulin stearate (manufactured by Chiba Flour Milling Co., Ltd., Leopard ISL2))
  • C4 1,2-hydroxystearic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • C5 Metal soap (sodium stearate (Tokyo Chemical Industry Co., Ltd.))
  • C6 Smoke-like silicic acid anhydride (Aerosil 200 manufactured
  • Photopolymerizable compound (D) The following photopolymerizable compounds were used as D1 to D4.
  • D1 Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DCP)
  • D2 Polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-400)
  • D3 Lauryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate LA (“Light acrylate” is a registered trademark of the company))
  • D4 Phenoxyethyl acrylate (Kyoeisha Chemical Co., Ltd., light acrylate PO-A)
  • Photopolymerization initiator (E) The following photopolymerization initiator was used as E1.
  • ink 2-1 Preparation of solvent-based ink (ink compositions 1 to 13, 20, 23 to 26) Each component was mixed according to the composition described in Table 1 and Table 2, and then heated to 60 ° C. and stirred. While maintaining the temperature of the obtained mixed liquid, it was filtered with a 3 ⁇ m membrane filter manufactured by ADVATEC (“Teflon” is a registered trademark of DuPont), and solvent-based ink compositions 1 to 13, 20 and 23 to 26 were filtered. Prepared.
  • Tables 1 and 2 indicate the composition ratio (unit: mass%) of the above components in each ink composition.
  • the description in the column of “ink category” in Tables 1 and 2 indicates whether each ink is a solvent-based ink, a water-based ink, or an actinic ray curable ink, and “solvent” indicates that the ink is a solvent “Water-based” indicates that the ink is a water-based ink, and “UV” indicates that the ink is an actinic ray curable ink.
  • the ink jet recording apparatus has an ink tank, an ink supply pipe, an ink supply tank immediately before the ink jet head, a filter, and a piezo type ink jet head in this order from the upstream side to the downstream side where the ink flows. It was.
  • the ink jet apparatus had an LED ultraviolet lamp (manufactured by GS Yuasa Corporation, LTD100) as an exposure system.
  • a temperature sensor is provided in the vicinity of the nozzles of the ink supply tank and the ink jet head, respectively, to insulate and heat the ink supply tank to the ink jet head part, and the temperature of the nozzle part is adjusted to the solvent-based ink (ink compositions 1 to 13, 20, 23 to 26), 60 ° C.
  • aqueous ink (ink compositions 14, 15 and 21) 70 ° C. ⁇ 2 ° C.
  • actinic ray curable ink (ink compositions 16 to 19 and 22) 80 ° C.
  • the temperature was controlled so as to be ⁇ 2 ° C.
  • the inkjet head was driven under the conditions of a droplet amount of 14 pl, a printing speed of 0.5 m / sec, an ejection frequency of 10.5 kHz, and a printing rate of 100% to discharge droplets of ink compositions 1 to 22.
  • the main scanning speed of the exposure system and the inkjet head is set to 0.1 seconds after the ink droplets land on the substrate. Later, adjustment was made so that irradiation of UV light condensed to an exposure surface illuminance of 1,200 mW / cm 2 started.
  • Table 3 and Table 4 show the results of the above evaluations for each ink composition and used base material.
  • the descriptions in the “ink category” column in Tables 3 and 4 are the same as those in Tables 1 and 2.
  • Examples 1 to 25 in which images were formed using ink compositions 1 to 19 containing a crystalline organic material capable of expressing metallic luster and a gelling agent, small letters were fine regardless of the type of substrate. The solid image was uniform and the gloss of the image was high.
  • Example 3 in which the content of the gelling agent is 10% by mass or less with respect to the total mass of the ink
  • Example 12 in which the content of the gelling agent exceeds 10% by mass.
  • the gloss of the image can be generally increased.
  • the gelling agent is dextrin fatty acid ester, sucrose fatty acid ester, inulin fatty acid ester, 1,2-hydroxystearic acid, metal soap, fumed silicic acid anhydride or organically modified clay mineral
  • Comparative Examples 1 to 7 in which an image was formed on a film using the ink compositions 20 to 26 containing no gelling agent, small characters were difficult to reproduce finely and the solid image was difficult to be uniform. This is thought to be because the wetting and spreading of the ink droplets could not be adjusted, and the area of the dots was easily expanded and the adjacent dots were easily united.
  • the ink composition contained the “solvent having a dot diameter adjusting function” described in Patent Document 1, but the reproducibility of small characters and the uniformity of solid images were low.
  • Examples 20 to 22 in which images were formed on paper using ink compositions 3, 14 and 16 containing a crystalline organic material capable of expressing metallic luster and a gelling agent did not contain a gelling agent.
  • the gloss of the image was higher than that of Comparative Examples 8 to 14 in which images were formed on paper using the ink compositions 20 to 26. This is because in Examples 20 to 22, the ink thickened on the base material to form a somewhat smooth film, so that the unevenness of the paper was difficult to be reflected on the surface of the image, but Comparative Examples 8, 9, 11 to No. 14 is reflected on the surface of the image on which the unevenness of the paper is formed, and in Comparative Example 10, the ink is not sufficiently thickened and spreads thinly so that the unevenness of the paper is reflected on the surface of the cured ink.
  • Example 23 to 25 in which an image was formed on glass using ink compositions 3, 14 and 16 containing a crystalline organic material capable of expressing metallic luster and a gelling agent, the gelling agent was not contained. Small characters were reproduced more finely and the solid image was uniform than in Comparative Examples 15 to 21 in which images were formed on paper using the ink compositions 20 to 26. This is considered to be because the wetting and spreading of the ink droplets was adjusted by the action of the gelling agent, and it was difficult for the dot area to expand and the adjacent dots to coalesce.
  • the ink jet recording method of the present invention it is possible to form an image with less bleeding with water-based ink.
  • the present invention is expected to expand the range of application of water-based ink by the ink jet method and contribute to the advancement and spread of technology in the same field.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne une encre pour jet d'encre qui comprend un matériau organique cristallin pouvant conférer un éclat métallique et un gélifiant. En outre, la présente invention concerne un procédé de formation d'image qui comprend une étape dans laquelle des gouttelettes d'encre pour jet d'encre sont éjectées de la buse d'une tête à jet d'encre pour distribuer les gouttelettes à une base. Conformément à l'encre pour jet d'encre et au procédé de formation d'image, il est possible de former des images présentant un éclat métallique en raison du matériau organique cristallin et qui ont une résolution élevée.
PCT/JP2016/085469 2016-01-13 2016-11-30 Encre pour jet d'encre et procédé de formation d'image Ceased WO2017122447A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP2020029499A (ja) * 2018-08-22 2020-02-27 国立大学法人千葉大学 金色の光沢を有する膜が形成される塗工液及びその膜
EP3838422A1 (fr) * 2019-12-13 2021-06-23 Fuji Xerox Co., Ltd Composition de formation d'un film à reflet métallique, film à reflet métallique, et article

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JP2005126508A (ja) * 2003-10-22 2005-05-19 Konica Minolta Holdings Inc インクジェット用インクとインクジェット記録方法
WO2010125854A1 (fr) * 2009-04-28 2010-11-04 コニカミノルタホールディングス株式会社 Encre pour jet d'encre durcissable sous l'action d'un rayonnement actif, et procédé de formation d'image par jet d'encre
JP2013119243A (ja) * 2011-12-08 2013-06-17 Konica Minolta Inc 光硬化型インクジェットインクを用いた画像形成方法
JP2013227410A (ja) * 2012-04-25 2013-11-07 Konica Minolta Inc 活性光線硬化型インクジェットインク
WO2015056591A1 (fr) * 2013-10-18 2015-04-23 Dic株式会社 Liquide de revêtement, article l'utilisant, et imprimés
JP2015101103A (ja) * 2013-11-25 2015-06-04 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ インクを吐出する方法

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JP2005126508A (ja) * 2003-10-22 2005-05-19 Konica Minolta Holdings Inc インクジェット用インクとインクジェット記録方法
WO2010125854A1 (fr) * 2009-04-28 2010-11-04 コニカミノルタホールディングス株式会社 Encre pour jet d'encre durcissable sous l'action d'un rayonnement actif, et procédé de formation d'image par jet d'encre
JP2013119243A (ja) * 2011-12-08 2013-06-17 Konica Minolta Inc 光硬化型インクジェットインクを用いた画像形成方法
JP2013227410A (ja) * 2012-04-25 2013-11-07 Konica Minolta Inc 活性光線硬化型インクジェットインク
WO2015056591A1 (fr) * 2013-10-18 2015-04-23 Dic株式会社 Liquide de revêtement, article l'utilisant, et imprimés
JP2015101103A (ja) * 2013-11-25 2015-06-04 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ インクを吐出する方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020029499A (ja) * 2018-08-22 2020-02-27 国立大学法人千葉大学 金色の光沢を有する膜が形成される塗工液及びその膜
JP7251752B2 (ja) 2018-08-22 2023-04-04 国立大学法人千葉大学 金色の光沢を有する膜が形成される塗工液及びその膜
EP3838422A1 (fr) * 2019-12-13 2021-06-23 Fuji Xerox Co., Ltd Composition de formation d'un film à reflet métallique, film à reflet métallique, et article
JP2021095426A (ja) * 2019-12-13 2021-06-24 富士フイルムビジネスイノベーション株式会社 金属光沢膜形成用組成物、金属光沢膜、及び物品
US11708450B2 (en) 2019-12-13 2023-07-25 Fujifilm Business Innovation Corp. Composition for forming metallic luster film, metallic luster film, and article

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