WO2016013644A1 - 箔画像形成方法 - Google Patents
箔画像形成方法 Download PDFInfo
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- WO2016013644A1 WO2016013644A1 PCT/JP2015/071063 JP2015071063W WO2016013644A1 WO 2016013644 A1 WO2016013644 A1 WO 2016013644A1 JP 2015071063 W JP2015071063 W JP 2015071063W WO 2016013644 A1 WO2016013644 A1 WO 2016013644A1
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- ink
- foil
- recording medium
- adhesive
- image forming
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- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/12—Coating on the layer surface on paper layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2327/00—Polyvinylhalogenides
- B32B2327/06—PVC, i.e. polyvinylchloride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2333/00—Polymers of unsaturated acids or derivatives thereof
- B32B2333/04—Polymers of esters
- B32B2333/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2607/00—Walls, panels
- B32B2607/02—Wall papers, wall coverings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/18—Particular kinds of wallpapers
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
- C09J2400/163—Metal in the substrate
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/26—Presence of textile or fabric
- C09J2400/263—Presence of textile or fabric in the substrate
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/28—Presence of paper
- C09J2400/283—Presence of paper in the substrate
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2427/00—Presence of halogenated polymer
- C09J2427/006—Presence of halogenated polymer in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to a foil image forming method.
- a foil image is known as an image having a sense of quality and high design.
- a foil image is an image formed by bonding a foil such as a metal foil in a desired shape to a recording medium such as paper or cloth.
- the foil image is generally formed by pressing a metal foil against a recording medium by hot stamping or the like.
- it is necessary to form a plate (stamp) in accordance with the shape of the foil image, and it is difficult to change the foil image for each small lot or to reduce the cost. Therefore, it has been required to form a foil image by digital printing or the like without using a plate.
- Such a decorative wallpaper is manufactured by laminating a decorative sheet layer on a backing paper or by directly decorating the backing paper (such as foil pressing).
- a vinyl chloride sheet or the like is known, and as the backing paper, a natural pulp base material, a mixed base material of natural pulp and synthetic resin (nonwoven wallpaper), or the like is known.
- a method of forming a foil image a method of forming a foil image on a recording medium by transferring a metal foil to the recording medium coated with an adhesive in a desired shape by thermocompression bonding has been proposed.
- an aqueous adhesive having microcapsules containing a thermoplastic resin is used (see, for example, Patent Document 1).
- Water-based adhesive is mainly composed of water. Water has a slower volatilization rate than organic solvents. For this reason, in the foil image forming method, the water-based adhesive landed on the recording medium as droplets has sufficiently high fluidity on the recording medium. Therefore, the landed water-based adhesive may bleed on a highly hydrophilic recording medium. Further, in a recording medium with low hydrophilicity, adjacent droplets of the landed water-based adhesive may be united and distributed more roughly and mottled. When such a phenomenon occurs, the fineness of the foil image tends to be impaired.
- the conventional foil image forming method using a water-based adhesive has a problem that the desired foil image may not be formed depending on the hydrophilicity of the recording medium.
- the present invention provides at least a method for forming a high-definition foil image regardless of the hydrophilicity of the recording medium.
- the first embodiment of the present invention relates to the following foil image forming method.
- Adhesive ink is applied to at least one of the recording medium and the foil sheet by an ink jet printing method in a shape corresponding to the foil image to be formed, and the recording medium and the foil of the foil sheet are heat-pressed and bonded.
- the resin is a copolymer of monomers including (meth) acrylic acid and (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, and is dispersed or dissolved in the adhesive ink.
- the acid value of the copolymer resin is 50 to 120 mg KOH / g, and the glass transition temperature of the copolymer resin is 30 to 110 ° C.
- the water-soluble organic solvent is one or more selected from the group consisting of glycol ethers, 1,2-alkanediols having 4 or more carbon atoms, and ⁇ -alkoxypropionamides.
- the wallpaper material includes a nonwoven fabric mixed with natural pulp and synthetic fibers.
- the second embodiment of the present invention relates to the following foil image forming method and laminate.
- An actinic ray curable inkjet ink containing a gelling agent, a photopolymerizable compound, and a photopolymerization initiator and undergoing a sol-gel phase transition depending on temperature is dropped onto a recording medium, and the actinic ray curable inkjet ink liquid is dropped.
- a step of forming an ink image composed of droplets a step of pressure-bonding a transfer surface of a transfer foil including a foil layer to the ink image, transferring the foil layer onto the ink image, and irradiating the ink image with actinic rays And curing the actinic radiation curable inkjet ink and fixing the foil layer on the recording medium, wherein the actinic radiation curable inkjet ink converts the gelling agent into the actinic radiation curable type.
- the temperature of the recording medium when the actinic ray curable ink-jet ink lands 0.5 to 10% by mass with respect to the total mass of the ink-jet ink, the temperature of the recording medium when the actinic ray curable ink-jet ink lands, The difference between the sol-gel phase transition temperature of the sexual ray curable inkjet ink is 30 ° C. or more, foil image forming method.
- R 1 —CO—R 2 (1)
- R 1 and R 2 each represent a linear or branched hydrocarbon group having 1 to 24 carbon atoms, of R 1 and R 2, either one is carbon Including a straight chain alkyl structure having a number of 12 or more
- R 3 —COO—R 4 (2) In the general formula (2), R 3 represents a linear or branched hydrocarbon group having 1 to 24 carbon atoms, and R 4 represents a hydrogen atom or a linear or branched chain having 1 to 24 carbon atoms. And any one of R 3 and R 4 includes a linear alkyl structure having 12 or more carbon atoms)
- a recording medium an adhesive layer formed in a pattern on the recording medium, and a foil layer formed on the adhesive layer, the adhesive layer comprising a gelling agent and a photopolymerizable compound And a laminate comprising a cured product of an actinic ray curable inkjet ink containing a photopolymerization initiator and undergoing a sol-gel phase transition depending on temperature.
- the recording medium is a wallpaper material.
- the adhesive ink according to the first embodiment of the present invention is a water-based adhesive, has an appropriate amphiphilic property (hydrophilicity and hydrophobicity), and rapidly thickens after landing on the recording medium. Therefore, sufficient adhesive force is expressed, and spread due to wetting on the recording medium is suppressed. Therefore, according to the first embodiment of the present invention, a high-definition foil image can be formed regardless of the hydrophilicity of the recording medium.
- the foil can be transferred to a pattern including thin lines, and a foil image can be formed on a recording medium having irregularities without any defects. Furthermore, the foil after transfer is hardly cracked or lifted.
- an embodiment for forming a foil image using a water-based adhesive (first embodiment) and an embodiment for forming a foil image using an actinic ray curable ink (second embodiment) ) Is included. These will be described separately.
- an adhesive ink is applied to at least one of a recording medium or a foil sheet in a shape corresponding to a foil image to be formed by an ink jet printing method, and the recording medium and the foil sheet are used. And the foil sheet is peeled off from the recording medium to form a foil image on the recording medium.
- an adhesive ink described later is used, an adhesive is applied to a recording medium by an ink jet printing method, and the foil is transferred by thermocompression bonding.
- the foil image forming method can be used.
- the adhesive ink contains water, a water-soluble organic solvent, and a copolymer resin. That is, the adhesive ink is a liquid composition in which water is the main solvent and the materials are uniformly mixed. When the adhesive ink further contains a water-insoluble additive, the liquid composition in which the additive is dispersed is used. It is. Hereinafter, the adhesive ink will be described.
- the copolymer resin is a copolymer of monomers including (meth) acrylic acid and (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms.
- the copolymer resin is, for example, a copolymer resin that can be dissolved in water by a neutralization reaction with a base, and is present by being dispersed or dissolved in the adhesive ink.
- (meth) acrylic acid means one or both of acrylic acid and methacrylic acid.
- the content of the (meth) acrylic acid in the monomer can be determined as appropriate as long as the acid value (50 to 120 mgKOH / g) of the copolymer resin described later is satisfied.
- the content of the (meth) acrylic acid in the monomer depends on other compounds in the monomer and cannot be generally specified, but may be selected from a range of 5 to 20% by mass, for example.
- the adhesive ink may contain only one kind or two or more kinds of the above (meth) acrylic acid alkyl ester.
- the (meth) acrylic acid alkyl ester is contained in the adhesive ink, appropriate hydrophobicity and flexibility are expressed by the alkyl chain, and the resulting foil image tends to have high abrasion resistance and adhesiveness.
- the content of the (meth) acrylic acid alkyl ester in the monomer is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass.
- the content of the (meth) acrylic acid alkyl ester having 6 to 12 carbon atoms in the alkyl group in the above monomer is from the viewpoint of the abrasion resistance and adhesion of the foil image. It is preferable that it is 5 mass% or more. On the other hand, from the viewpoint of ink repellency required for the periphery of the nozzle of the inkjet head, it is preferably 20% by mass or less, and more preferably 5 to 10% by mass.
- the content of the (meth) acrylic acid alkyl ester having 2 to 4 carbon atoms in the alkyl group in the monomer is 5 to 40% by mass from the above viewpoint. It is preferably 5 to 20% by mass.
- (meth) acrylic acid alkyl esters there are two types of alkyl (meth) acrylic acid alkyl ester having 6 to 12 carbon atoms and (meth) acrylic acid alkyl ester having 2 to 4 carbon atoms. Including the type is more preferable from the above viewpoint.
- Examples of (meth) acrylic acid alkyl esters having 2 to 4 carbon atoms in the alkyl group include ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and (meth) acrylate. ) T-butyl acrylate.
- Examples of the (meth) acrylic acid alkyl ester having 6 to 12 carbon atoms in the alkyl group include n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and (meth) acrylic. 2-ethylhexyl acid and lauryl (meth) acrylate are included.
- the monomer may further contain a monomer other than the above-described (meth) acrylic acid and the above (meth) acrylic acid alkyl ester as long as the effect of the present embodiment is obtained.
- the other monomers include other (meth) acrylic acid alkyl esters such as methyl methacrylate, acid monomers other than (meth) acrylic acid, (meth) acrylic acid esters other than alkyl esters, and styrene.
- the acid monomer include itaconic acid, maleic acid and maleic acid half ester.
- methyl methacrylate is preferable from the viewpoint of the abrasion resistance of the foil image. It is presumed that methyl methacrylate becomes a hard core that develops impact resistance in the copolymer resin that is an adhesive component. From the above viewpoint, the content of methyl methacrylate in the monomer is preferably 15 to 85% by mass, and more preferably 40 to 80% by mass.
- the acid value of the copolymer resin which is a copolymer of the above monomers, is 50 to 120 mgKOH / g.
- the acid value is less than 50 mgKOH / g, the affinity of the adhesive ink to the recording medium becomes insufficient, and when the acid value is greater than 120 mgKOH / g, the affinity of the adhesive ink to the foil becomes insufficient. In either case, the scratch resistance and adhesive strength of the foil image may be insufficient.
- the acid value of the copolymer resin is preferably 50 to 100 mgKOH / g.
- the acid value of the copolymer resin can be measured by a titration method. Moreover, the acid value of the copolymer resin can be increased by increasing the content ratio of (meth) acrylic acid to the (meth) acrylic acid alkyl ester in the monomer, for example.
- the glass transition temperature Tg of the copolymer resin is 30 to 110 ° C. When the Tg is in this range, sufficient and good abrasion resistance of the foil image can be obtained. This is thought to be because the thin layer of the adhesive ink formed between the foil and the recording medium maintains moderate flexibility without becoming brittle at room temperature even after thermocompression bonding. .
- the Tg can be measured by differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- the Tg can be appropriately adjusted by selecting the structure of the alkyl group of the (meth) acrylic acid alkyl ester in the monomer. Is possible.
- the weight average molecular weight Mw of the copolymer resin is preferably 20000 or more from the viewpoint of improving the abrasion resistance of the foil image, and is preferably 80000 or less, injectability of adhesive ink and maintainability with an inkjet head. From the viewpoint of enhancing the above.
- the Mw is more preferably 2500 to 70000 from the above viewpoint.
- the Mw can be measured by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- the Mw can be increased by increasing the concentration of the monomer during copolymerization of the copolymer resin.
- it can be made smaller by increasing the amount of the polymerization initiator.
- the content of the copolymer resin in the adhesive ink is 1 to 4 from the viewpoints of the viscosity of the adhesive ink, drying after landing on the recording medium, and adhesiveness, which are related to the dischargeability and maintainability of the inkjet head.
- the content is preferably 15% by mass, and more preferably 3 to 10% by mass.
- the content of the copolymer resin in the adhesive ink is 1 or more times the solid content of the pigment. This is preferable from the viewpoint of obtaining good abrasion resistance and adhesion of an image (latent image) formed on the recording medium. On the other hand, it is preferably 15 times or less from the viewpoint of not impairing the ejection property of the adhesive ink and the maintenance property.
- the content of the copolymer resin with respect to the pigment solid content is more preferably 1 to 10 times from the above viewpoint.
- the adhesive ink is preferably an aqueous solution containing the water, the water-soluble organic solvent, and the copolymer resin from the viewpoint of stabilizing the properties of the adhesive ink.
- the base include alkali metal-containing bases such as sodium hydroxide and potassium hydroxide, amines such as alkanolamine and alkylamine, and ammonia.
- the base is ammonia or an amine having a boiling point of 100 to 200 ° C. increases the solubility of the copolymer resin and increases the durability of the thin layer of the adhesive ink on the recording medium.
- ammonia, N, N-dimethylaminoethanol or 2-amino-2-methylpropanol is particularly preferable from the viewpoint of improving the injection stability of the adhesive ink.
- the amount added is preferably 0.8 to 3.0 equivalents relative to the acidic group of the copolymer resin.
- the addition amount can be determined by salt detection and quantification.
- the water-soluble organic solvent may be one kind or more.
- the water-soluble organic solvent is an organic solvent that dissolves at a concentration of 20% by mass or more with respect to water at room temperature.
- the content of the water-soluble organic solvent in the adhesive ink is from 1 to 2 from the viewpoints of controlling the wettability of the adhesive ink to the recording medium and suppressing ink mixing due to thickening accompanying drying of the landed adhesive ink.
- the content is preferably 50% by mass, and more preferably 10 to 40% by mass.
- water-soluble organic solvent examples include glycol ethers, 1,2-alkanediols having 4 or more carbon atoms, and ⁇ -alkoxypropionamides.
- glycol ethers examples include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether and tripropylene glycol. Monomethyl ether is included.
- 1,2-alkanediols examples include 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, and 1,2-heptanediol.
- Examples of the ⁇ -alkoxypropionamides include compounds represented by the following formula.
- R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms
- R 2 and R 3 are each a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Represents a group.
- R 2 and R 3 may be the same or different.
- Preferred examples of R 1 include a methyl group, an ethyl group and an n-butyl group
- preferred examples of R 2 and R 3 include a methyl group and an ethyl group.
- the compound represented by the above formula is preferable from the viewpoint of increasing the solubility of the copolymer resin in the adhesive ink, having good permeability to a recording medium, and increasing the compatibility of the copolymer resin with water.
- the content of the compound represented by the above formula in the adhesive ink is preferably 1.0 to 40% by mass.
- the water-soluble organic solvent contains the compound represented by the above formula and one or both of the glycol ethers and the 1,2-alkanediols, so that the adhesive ink can be applied to a recording medium with low hydrophilicity. It is preferable from the viewpoint of suppressing the coalescence of droplets when the droplets land and obtaining a high-definition foil image. This is presumably because the glycol ethers and the 1,2-alkanediols both have a relatively low surface tension.
- the adhesive ink is composed mainly of water except for the copolymer resin and the water-soluble organic solvent described above.
- the water content in the adhesive ink is not particularly limited, but is, for example, 10% by mass or more.
- the adhesive ink may further contain components other than the above-described copolymer resin and water-soluble organic solvent within the range where the effects of the present embodiment are exhibited.
- other components include surfactants, other organic solvents, other resins and pigments.
- the adhesive ink may contain only one kind of surfactant or more than one kind.
- the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, a silicone-based surfactant, and a fluorine-based surfactant.
- anionic surfactant examples include dialkylsulfosuccinates, alkylnaphthalenesulfonates and fatty acid salts.
- nonionic surfactant examples include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, and polyoxyethylene / polyoxypropylene block copolymers.
- Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts.
- silicone surfactant examples include a polyether-modified polysiloxane compound, and commercially available products such as KF-351A and KF-642 manufactured by Shin-Etsu Chemical Co., Ltd., BYK345, BYK347 and BYK348 manufactured by Big Chemie, etc. Is mentioned.
- the above-mentioned fluorosurfactant means one obtained by substituting a part or all of hydrogen bonded to carbon of the hydrophobic group of a normal surfactant with fluorine.
- the fluorosurfactant preferably has a perfluoroalkyl group in the molecule.
- the above-mentioned fluorosurfactant is, for example, a product name of MEGAFAC (registered trademark) from DIC Corporation, and a product name of SURFFLON (registered trademark of AGC Seimi Chemical Co., Ltd.) from Asahi Glass Co., Ltd.
- MEGAFAC registered trademark
- SURFFLON registered trademark of AGC Seimi Chemical Co., Ltd.
- Fluorad FC Minnesota Mining and Manufacturing Company
- Monfloor from Imperial Chemical Industry
- EI Dupont Nemeras and It is commercially available under the trade name Zonyls from the company company and under the trade name Licovet VPF from Park Berke Hoechst.
- the fluorosurfactant is classified into anionic, cationic, and nonionic types depending on the type of hydrophilic group, and is preferably a nonionic fluorosurfactant.
- Preferred examples of the nonionic fluorosurfactant include Megafac F-144D manufactured by DIC Corporation and Surflon S-141 and 145 manufactured by Asahi Glass Co., Ltd.
- Examples of amphoteric fluorosurfactants include Surflon S-131 and 132 manufactured by Asahi Glass Co., Ltd.
- the surfactant is preferably a silicone surfactant or a fluorine surfactant from the viewpoint of adjusting the wettability of the adhesive ink to the recording medium.
- the above-mentioned surfactant is preferable for the recording medium having low hydrophilicity so that the droplets of the adhesive ink are wet without being repelled, and for the recording medium having high hydrophilicity. It is preferable to prevent ink droplets from spreading too much.
- the silicone-based surfactant or fluorine-based surfactant is particularly preferably used in combination with the above-mentioned glycol ethers or 1,2-alkanediols, which are water-soluble organic solvents having a low surface tension.
- the content of the surfactant in the adhesive ink is preferably 0.1 to 2% by mass from the viewpoint of obtaining both the effect of the present embodiment and the effect of the surfactant described above. It is more preferably 2 to 1% by mass.
- the above-mentioned other organic solvents may be one kind or more.
- examples of such other organic solvents include swellable organic solvents, monohydric alcohols, polyhydric alcohols, amines and amides. Content of the said other organic solvent in the said adhesive ink can be suitably determined from the range with which the effect of this embodiment is acquired.
- the swellable organic solvent is a solvent that can dissolve, soften, or swell a recording medium (for example, a recording medium made of resin such as vinyl chloride).
- the swellable organic solvent is preferable from the viewpoint of increasing the adhesiveness of the adhesive sheet to the recording medium and from the viewpoint of increasing the abrasion resistance of the foil image.
- swellable organic solvent examples include heterocyclic compounds containing nitrogen or sulfur atoms, cyclic esters, lactic acid esters, alkylene glycol diethers, alkylene glycol monoether monoesters, and dimethyl sulfoxide.
- heterocyclic compounds containing a nitrogen atom examples include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, Cyclic amide compounds such as methyl caprolactam and 2-azacyclooctanone are included.
- heterocyclic compound containing a sulfur atom examples include 5- to 7-membered compounds such as sulfolane.
- Examples of the cyclic ester include ⁇ -butyrolactone and ⁇ -caprolactone, and examples of the lactic acid ester include butyl lactate and ethyl lactate.
- Examples of the alkylene glycol diether include diethylene glycol diethyl ether, and examples of the alkylene glycol monoether monoester include diethylene glycol monoethyl monoacetate.
- Examples of the monohydric alcohol include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol and tertiary butanol.
- Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol and thiodiglycol. included.
- Examples of the amine include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, Pentamethyldiethylenetriamine and tetramethylpropylenediamine are included.
- Examples of the amide include formamide, N, N-dimethylformamide and N, N-dimethylacetamide.
- the above other resin may be one kind or more.
- the other resin can be appropriately selected according to its function, and the content of the other resin in the adhesive ink can be appropriately determined within a range in which the effect of the present embodiment can be obtained.
- the content of the copolymer resin in the resin in the adhesive ink is 50 to 100% by mass.
- the pigment may be one kind or more.
- Conventionally known organic and inorganic pigments can be used as the pigment.
- the content of the pigment in the adhesive ink can be appropriately determined within a range in which the effect of the present embodiment can be obtained.
- examples of such pigments include azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments; phthalocyanine pigments, perylene and perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, Polycyclic pigments such as quinophthalone pigments; dye lakes such as basic dye type lakes and acid dye type lakes; organic pigments such as nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments; and inorganic pigments such as carbon black Is included.
- azo pigments such as azo lakes, insoluble azo pigments, condensed azo
- the surface tension of the adhesive ink is preferably 15 mN / m or more from the viewpoint of preventing the discharge performance from being lowered due to the wetness around the nozzles of the inkjet head. From the viewpoint of suppressing the spread of droplets landed on a recording medium having a surface energy lower than that of a normal paper recording medium, such as a coated paper or a resin recording medium, it is 35 mN / m or less. Preferably there is.
- the surface tension can be measured using a known measuring device, for example, CBVP-Z type (manufactured by Kyowa Interface Science Co., Ltd.).
- the surface tension can be adjusted, for example, by controlling the composition ratio, steric balance, etc. of the hydrophobic substituent and the hydrophilic substituent in the molecular structure of the copolymer resin.
- the viscosity of the adhesive ink is preferably 5 to 20 mPa ⁇ s from the viewpoint of enhancing the ejection stability in ejection by an inkjet head, that is, ejection of droplets by a thermal or piezo-type head.
- the viscosity can be measured using a known viscometer, for example, an E-type viscometer “V-25 type” (manufactured by Toki Sangyo Co., Ltd.). Moreover, the said viscosity can be adjusted with content or molecular weight of copolymer resin, for example.
- the foil image forming method according to the present embodiment can be performed using, for example, the apparatus shown in FIG.
- the foil image forming apparatus 10 includes an inkjet head 11, a heating roller 12, a support roller 13, a peeling member 14, and a take-up roller 15.
- the inkjet head 11 is, for example, an on-demand inkjet head, and accommodates the above-described adhesive ink so that it can be discharged.
- the heating roller 12 is, for example, a rubber roller having a heater therein, and is opposed to the support roller 13 with a gap that is the same as or slightly smaller than the sum of the thicknesses of the recording medium 21 and the foil sheet 30, for example. Is arranged.
- the support roller 13 is, for example, a roller that is rotatably fixed at a position facing the heating roller 12.
- the peeling member 14 is fixed at a position downstream of the support roller 13 in the moving direction of the recording medium and in contact with the foil sheet (base sheet 31) on the recording medium.
- the take-up roller 15 is rotatably arranged at a position downstream and higher than the peeling member 14.
- the adhesive ink 22 is applied from the inkjet head 11 to the recording medium 21 that is conveyed in the direction of the arrow X in FIG. 1 through the nip portion between the heating roller 12 and the support roller 13.
- the adhesive ink 22 is applied to the recording medium 21 in a shape corresponding to the foil image to be formed by the ink jet printing method.
- the recording medium 21 is a member on which a foil image is to be formed, for example, a sheet.
- the material of the recording medium 21 can be determined as appropriate, and is, for example, paper, cloth, resin, metal, glass, or the like.
- paper recording media include plain paper from thin paper to thick paper, high-quality paper, coated printing paper such as art paper and coated paper, commercially available printing paper such as Japanese paper and postcard paper, And wallpaper material.
- the wallpaper material includes, for example, a nonwoven fabric obtained by mixing natural pulp and synthetic fiber.
- the adhesive ink does not cause wetting and spreading after landing, and has amphiphilic properties, and therefore is applied to the formation of a foil image on the wallpaper material.
- the foil sheet 30 includes, for example, a base sheet 31 and a foil 32 disposed on the base sheet 31.
- a release layer may be further disposed between the base sheet 31 and the foil 32.
- the foil sheet 30 is, for example, a long strip-shaped sheet wound up on a roll, but may be an independent sheet.
- the base sheet 31 is, for example, a resin sheet or a paper sheet.
- the release layer is, for example, a thin layer of a fluorine-based resin or a silicone-based resin, or a mixture of these resins and other resins.
- the foil 32 is adhered to the recording medium in order to form a metallic character or glossy character or design that is difficult to express by general printing or a transparent character or design having a transparent feeling on the recording medium.
- the foil 32 is a material that causes optical interference, such as a colored layer containing a colorant such as a pigment, a metal layer made of a metal material, a transparent resin layer, or a laminate of a hologram layer and a metal layer. Composed of layers.
- the foil 32 can be produced, for example, directly on the base sheet 31 by a known method.
- the foil 32 of the foil sheet 30 is thermocompression bonded to the recording medium 21 to which the adhesive ink 22 has been applied.
- the foil sheet 30 is guided to the nip portion from above the upstream side of the support roller 13 in the moving direction of the recording medium 21 and is conveyed in the X direction.
- the recording medium 21 and the foil sheet 30 are pressed against each other by the elasticity of the heating roller 12 at the nip portion.
- the foil sheet 30 is pressure-bonded to the recording medium 21 with the foil 32 facing the recording medium 21.
- the recording medium 21 and the foil sheet 30 are heated by the heating roller 12 while being pressed so that, for example, the temperature of the foil 32 is 0 to 50 ° C. higher than the Tg of the copolymer resin in the adhesive ink.
- the foil sheet 30 is peeled off from the recording medium 21.
- the recording medium 21 and the foil sheet 30 that are pressure-bonded to each other are conveyed to the peeling member 14 along the arrow X direction.
- the foil 32 of the foil sheet 30 is bonded to the recording medium 21 at a desired shape.
- the recording medium 21 is conveyed in the arrow X direction.
- the foil sheet 30 is pulled upward by the take-up roller 15, but since the upward movement is restricted by the peeling member 14, the foil sheet 30 is conveyed in the direction of the arrow X1 by the take-up roller 15 on the downstream side of the peeling member 14.
- Rolled up Due to the peeling of the foil sheet 30 from the recording medium 21, only the portion of the foil 32 bonded to the recording medium 21 is separated from the foil sheet 30. Thus, a foil image is formed on the recording medium 21.
- the adhesive ink 22 is applied to the recording medium 21 by the droplets landing on the recording medium 21.
- the copolymer resin of the adhesive ink 22 has a sufficient amount of alkyl groups of a specific length introduced by the monomer (meth) acrylic acid alkyl ester.
- the adhesive ink 22 contains the water-soluble organic solvent, and the copolymer resin has an appropriate Tg. For this reason, it is considered that the solvent (water) is volatilized after the droplets of the adhesive ink 22 have landed, so that the viscosity is quickly increased and the expansion and deformation of the ink dots are suppressed.
- the copolymer resin has an appropriate acid value, depending on the hydrophilicity of the recording medium 21 and the foil 32, the acidic group or the alkyl group in the copolymer resin has the recording medium 21 and the foil 32, respectively.
- the copolymer resin portion also enters into the fine irregularities on the surfaces of the recording medium 21 and the foil 32, and develops strong adhesion to the recording medium 21 and the foil 32, respectively. it is conceivable that.
- the alkyl group in the copolymer resin is considered to impart flexibility to the cured product of the adhesive ink. For this reason, even if stress due to strong rubbing or bending is applied to the recording medium 21 after formation of the foil image, the adhesive layer of the cured adhesive ink is deformed according to the stress, and the crack or peeling of the foil in the foil image is performed. It is thought that etc. are suppressed.
- the alkyl group suppresses intrusion of moisture due to its hydrophobicity, and as a result, improves the water resistance of the adhesive layer.
- the adhesive ink 22 has a low viscosity when stored, it rapidly thickens after landing on the recording medium 21 as a droplet, behaves as a semi-solid state, and further exhibits the above-mentioned good adhesiveness when heated. It is thought to do. As a result, the adhesion between the foil 32 and the recording medium 21 in ink dot units is improved. For this reason, a high-definition foil image is formed.
- the adhesive layer has the appropriate flexibility, for example, even when a wallpaper having a foil image using a wallpaper material for the recording medium 21 is used, the foil is prevented from peeling off during the construction of the wallpaper. be able to. Furthermore, since the water resistance of the adhesive layer is improved, peeling of the foil due to the intrusion of moisture into the adhesive layer in the foil image over time can also be prevented.
- the foil image forming method according to the present embodiment may further include other steps than the steps described above as long as the effects of the present embodiment can be obtained.
- Examples of the other steps include a step of preheating the recording medium.
- the recording medium before the adhesive ink is applied is heated to bring the temperature of the recording medium to 35 to 100 ° C.
- the temperature of the recording medium may be, for example, the temperature of the surface of the recording medium on which the foil image is to be formed, or the temperature of the opposite surface (back surface).
- the preheating can be performed by a known heating device such as a planar heater, a warm air heater, or a heating furnace.
- the step of preheating the recording medium is preferable from the viewpoint of suppressing the spread of the adhesive ink on the surface of the recording medium.
- the foil image forming method applies adhesive ink to at least one of the recording medium or the foil sheet in a shape corresponding to the foil image to be formed by the ink jet printing method.
- a foil image forming method in which the foil of the recording medium and the foil sheet is heated and pressure-bonded, and the foil sheet is peeled off from the recording medium to form a foil image on the recording medium.
- the acid value of the copolymer resin is 50 to 120 mg KOH / g, and is dispersed or dissolved in the adhesive ink.
- the glass transition temperature of the resin is 30 ⁇ 110 ° C.. Therefore, a high-definition foil image can be formed regardless of the hydrophilicity of the recording medium.
- the content of the (meth) acrylic acid alkyl ester in the monomer is 5 to 50% by mass due to appropriate hydrophobicity and flexibility due to the long-chain alkyl group in the (meth) acrylic acid alkyl ester. This is more effective from the viewpoint of the abrasion resistance and adhesiveness of the foil image presumed to be developed.
- the water-soluble organic solvent is one or more selected from the group consisting of glycol ethers, 1,2-alkanediols having 4 or more carbon atoms, and ⁇ -alkoxypropionamides. This is even more effective from the viewpoint of controlling the wettability of the adhesive ink to the medium and suppressing ink mixing due to thickening accompanying drying of the landed adhesive ink.
- the adhesive ink further containing a surfactant is more effective from the viewpoint of controlling the wettability of the adhesive ink to the recording medium.
- the foil image forming method further includes a step of heating the recording medium before application of the adhesive ink to 35 to 100 ° C., thereby suppressing spreading due to wetting of the adhesive ink on the surface of the recording medium. It is much more effective from the viewpoint of
- the recording medium is a wallpaper material
- the above-described effects of the present embodiment are more remarkably exhibited.
- the wallpaper material includes a nonwoven fabric obtained by mixing natural pulp and synthetic fibers, This is preferable because the above-described effects are more remarkably exhibited.
- FIG. 2A An example of the foil image forming method of this embodiment is shown in FIG.
- an actinic ray curable inkjet ink is applied in a pattern on the recording medium 1 to form an ink image 2.
- the transfer surface (foil layer 5) of the transfer foil 3 including the support material 4 and the foil layer 5 is brought into intimate contact with the ink image 2 and is subjected to pressure bonding.
- the transfer foil 3 is removed. At this time, the foil layer 5 that has been pressure-bonded to the ink image remains on the ink image 2.
- the foil layer 5 that has not been pressure-bonded to the ink image 2 is removed together with the support material 4. That is, the foil layer 5 ′ remains in the pattern of the ink image 2 on the recording medium 1, and this becomes a foil image. Then, as shown in FIG. 2D, the ink image 2 is irradiated with an actinic ray from the light source 131 to cure the actinic ray curable inkjet ink, and the foil layer 5 ′ is fixed on the recording medium 1. .
- an ink image is formed with an actinic ray curable ink jet ink that undergoes a sol-gel phase transition depending on temperature.
- the ink is in a sol state when ejected from the ink jet apparatus.
- it gels quickly after landing on the recording medium. Therefore, the ink droplet after landing on the recording medium does not spread and the ink image including a fine pattern can be formed.
- the actinic ray curable ink jet ink that has landed on the recording medium quickly gels. Therefore, it is difficult for ink droplets that have landed on the recording medium to enter the irregularities of the recording medium. Therefore, the thickness of the obtained ink image is likely to be uniform, and defects are hardly generated in the obtained foil image.
- the foil image forming method of the present embodiment includes the following three steps. (1) A step of dropping an actinic ray curable inkjet ink that undergoes a sol-gel phase transition onto a recording medium to form an ink image comprising droplets of the actinic ray curable inkjet ink. (2) A transfer foil including a foil layer A step of pressure-bonding a transfer surface to the ink image, and transferring the foil layer onto the ink image. (3) irradiating the ink image with an actinic ray to cure the actinic ray curable inkjet ink, Step of fixing on the recording medium Each step will be described below.
- (1.1) Ink Image Forming Step In the ink image forming step, as shown in FIG. 2, an actinic ray curable ink jet ink that undergoes a sol-gel phase transition is dropped onto the recording medium 1, and the actinic ray curable ink jet ink is added. Ink image 2 composed of the droplets is formed. The ink image 2 is formed in the same pattern as the foil image (image consisting of a foil layer) to be finally obtained.
- the actinic ray curable ink-jet ink is ejected from the ink-jet apparatus in a sol state. Then, after the ink droplets have landed on the recording medium, the temperature of the recording medium is set to 30 ° C. or lower than the sol-gel phase transition temperature of the ink so that the ink gels quickly. Thereby, the ink droplets that have landed on the recording medium do not spread and are pinned to a desired position.
- the recording medium to which the actinic ray curable inkjet ink is applied is not particularly limited as long as the adhesive layer obtained by curing the ink can be adhered.
- the droplets of the actinic ray curable inkjet ink according to the present embodiment hardly enter the recesses even if the substrate has irregularities. Therefore, according to the foil image forming method of this embodiment, it is possible to form a foil image on a recording medium having irregularities.
- the recording medium is appropriately selected depending on the application, for example, various plastic substrates, metal substrates, glass substrates, stone substrates, cloth substrates, natural pulp substrates, fleece substrates obtained by mixing natural pulp and synthetic fibers, It can be a Japanese paper base material.
- the recording medium is a natural pulp base material, a fleece base material obtained by mixing natural pulp and synthetic fiber, a wallpaper material made of Japanese paper base material, etc. It can be.
- the recording medium may be a sheet-like sheet or a long sheet wound in a roll shape.
- the molded body of various resin may be sufficient.
- the active inkjet ink (hereinafter also simply referred to as “ink”) used in this step undergoes a sol-gel phase transition. That is, it is liquid (sol state) at a high temperature (for example, about 80 ° C.) and gels when cooled.
- the sol-gel phase transition temperature of the ink in the present embodiment is a temperature at which gelation occurs and fluidity decreases in the process of cooling the ink in the sol state.
- the sol-gel phase transition temperature of such actinic ray curable inkjet ink is preferably 40 ° C. or higher and 70 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower. In the case where the injection temperature from the ink jet apparatus is around 80 ° C., if the sol-gel phase transition temperature of the ink exceeds 70 ° C., gelation tends to occur at the time of injection, and the injection property is lowered.
- sol-gel phase transition temperature is less than 40 ° C.
- the viscosity of the ink at a high temperature (sol state) is not more than a certain value.
- the viscosity of the actinic ray curable inkjet ink at 80 ° C. is preferably 3 to 20 mPa ⁇ s.
- the viscosity of the ink after landing on the recording medium (gel state) is a certain level or more.
- the viscosity at 25 ° C. of the actinic ray curable inkjet ink is preferably 1000 mPa ⁇ s or more.
- the viscosity at 80 ° C., the viscosity at 25 ° C., and the sol-gel phase transition temperature of the ink 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 20 ° C. under conditions of a shear rate of 11.7 (/ s) and a temperature decrease rate of 0.1 ° C./s. And the viscosity in 80 degreeC and the viscosity in 25 degreeC can be calculated
- the sol-gel phase transition 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 ink contains at least a gelling agent, a photopolymerizable compound, and a photopolymerization initiator, and may contain a non-polymerizable resin or the like as necessary.
- the gelling agent contained in the actinic ray curable inkjet ink has a function of reversibly changing the sol-gel phase of the ink depending on the temperature.
- a gelling agent must be at least 1) soluble in a photopolymerizable compound at a temperature higher than the sol-gel phase transition temperature, and 2) crystallized at a temperature below the sol-gel phase transition temperature. .
- the type of the gelling agent is not particularly limited, but when crystallizing in the ink, a plate crystal which is a crystallized product of the gelling agent forms a space three-dimensionally surrounded by the photopolymerizable compound.
- a gelling agent is preferable.
- the structure in which the photopolymerizable compound is encapsulated in the space three-dimensionally surrounded by the plate crystal is sometimes referred to as “card house structure”.
- the photopolymerizable compound is held in the card house structure and the ink droplets are pinned. That is, the ink droplets after landing on the recording medium are difficult to spread and the ink image can be formed in a fine pattern.
- the photopolymerizable compound dissolved in the ink and the gelling agent are preferably compatible. Furthermore, from the viewpoint of stably discharging ink droplets from the ink jet recording apparatus, it is important that the compatibility between the photopolymerizable compound and the gelling agent is good in the sol-like ink (at a high temperature). is there.
- gelling agents include An aliphatic ketone compound; Aliphatic ester compounds; Petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam; Plant waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba solid wax, and jojoba ester; Animal waxes such as beeswax, lanolin and whale wax; Mineral waxes such as montan wax and hydrogenated wax; Hydrogenated castor oil or hydrogenated castor oil derivative; Modified waxes such as montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives or polyethylene wax derivatives; Higher fatty acids such as behenic acid, arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, and erucic acid; Higher alcohols such as stearyl alcohol and behenyl alcohol; Hydroxystearic acid such as 12-hydroxystearic acid; 12-hydroxystearic acid derivative
- N-substituted fatty acid amides such as N-stearyl stearamide and N-oleyl palmitate amide
- Special fatty acid amides such as N, N′-ethylenebisstearylamide, N, N′-ethylenebis-12-hydroxystearylamide, and N, N′-xylylenebisstearylamide
- Higher amines such as dodecylamine, tetradecylamine or octadecylamine
- Nomucoat series, etc. Amide compounds such as N-lauroyl-L-glutamic acid dibutylamide and N- (2-ethylhexanoyl) -L-glutamic acid dibutylamide (available from Ajinomoto Fine-Techno); Dibenzylidene sorbitols such as 1,3: 2,4-bis-O-benzylidene-D-glucitol (available from Gelol D Shin Nippon Chemical); And low molecular oil gelling agents described in JP-A-2005-126507, JP-A-2005-255821 and JP-A-2010-11117.
- Amide compounds such as N-lauroyl-L-glutamic acid dibutylamide and N- (2-ethylhexanoyl) -L-glutamic acid dibutylamide (available from Ajinomoto Fine-Techno); Dibenzylidene sorbitols such as 1,3: 2,4-bis-O
- a linear alkyl structure having 12 or more carbon atoms is contained in the molecule of the gelling agent contained in the actinic ray curable inkjet ink for the foil image forming method of the present embodiment.
- the straight-chain alkyl structure having 12 or more carbon atoms refers to a structure composed of a straight-chain alkyl group and having 12 or more carbon atoms contained in the straight-chain portion.
- the foil image transferred by the conventional method has problems such as deterioration of the foil due to moisture absorbed by the adhesive layer and cracking of the foil without sufficiently following the swelling of the adhesive layer.
- the gelling agent contains a linear alkyl structure having 12 or more carbon atoms
- the highly hydrophobic gelling agent tends to gather near the ink droplet surface in the ink droplet after dropping. Therefore, the adhesive layer obtained by curing such ink droplets tends to have a high surface hydrophobicity, and the adhesive layer is difficult to absorb moisture. That is, a foil image obtained by curing and piercing an inkjet ink containing the gelling agent is not easily affected by moisture and is not easily deteriorated over a long period of time.
- the linear alkyl structure having 12 or more carbon atoms is included in the molecule of the gelling agent, the above-mentioned card house structure is likely to be formed.
- Specific examples of the gelling agent having such a structure include aliphatic ketone compounds, aliphatic ester compounds, higher fatty acids, higher alcohols, fatty acid amides and the like having a linear alkyl group having 12 or more carbon atoms. .
- the gelling agent is an aliphatic ketone represented by the following general formula (1) or the general formula (2) from the viewpoint that the hydrophobicity of the adhesive layer made of a cured product of the ink is likely to increase.
- the fatty acid or aliphatic ester (2) represented is preferred.
- R 1 —CO—R 2 each represent a linear or branched hydrocarbon group having 1 to 24 carbon atoms, more preferably a linear hydrocarbon having 1 to 24 carbon atoms. More preferably a straight-chain hydrocarbon group having 8 to 22 carbon atoms.
- either one of R 1 and R 2 includes a linear alkyl structure having 12 or more carbon atoms, and preferably both include a linear alkyl structure having 12 or more carbon atoms.
- the linear alkyl structure preferably has 12 to 24 carbon atoms. If the linear alkyl structure has 12 or more carbon atoms, the crystallinity of the gelling agent tends to increase. Furthermore, in the above-described card house structure, the photopolymerizable compound can be easily included, and an ink image can be easily formed densely. On the other hand, when the carbon number of the linear alkyl structure is 24 or less, the melting point of the gelling agent does not increase excessively, and the gelling agent is sufficiently dissolved in the ink.
- Examples of the aliphatic ketone compound represented by the general formula (1) include dilignoceryl ketone (C24-C24), dibehenyl ketone (C22-C22, melting point 88 ° C.), distearyl ketone (C18-C18, 84 ° C.), dieicosyl ketone (C20-C20), dipalmityl ketone (C16-C16, melting point 80 ° C.), dimyristyl ketone (C14-C14), dilauryl ketone (C12-C12, melting point 68 ° C.) , Lauryl myristyl ketone (C12-C14), lauryl palmityl ketone (C12-C16), myristyl palmityl ketone (C14-C16), myristyl stearyl ketone (C14-C18), myristyl behenyl ketone (C14-C22), palmityl Stearyl ket
- Examples of commercially available compounds represented by the general formula (1) include 18-Pentriacontanon (Alfa Aeser), Hentriacontan-16-on (Alfa Aeser), Kao Wax T1 (Kao Corporation), etc. Is included.
- the actinic ray curable ink-jet ink may contain only one kind of aliphatic ketone represented by the general formula (1) or two or more kinds.
- R 3 represents a linear or branched hydrocarbon group having 1 to 24 carbon atoms, more preferably a linear hydrocarbon group having 1 to 24 carbon atoms, More preferably, it is a linear hydrocarbon group having 8 to 22 carbon atoms.
- R 4 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 24 carbon atoms, more preferably a linear hydrocarbon group having 1 to 24 carbon atoms, A straight-chain hydrocarbon group having 8 to 22 carbon atoms is preferred.
- one of R 3 and R 4 includes a linear alkyl structure having 12 or more carbon atoms, and preferably both include a linear alkyl structure having 12 or more carbon atoms.
- the linear alkyl structure preferably has 12 to 24 carbon atoms. If the linear alkyl structure has 12 or more carbon atoms, the crystallinity of the gelling agent tends to increase. Furthermore, in the above-mentioned card house structure, the photopolymerizable compound can be sufficiently included, and an ink image can be easily formed in a dense pattern. On the other hand, if the carbon number of the linear alkyl structure is 24 or less, the melting point of the gelling agent is not excessively increased, and the gelling agent is sufficiently dissolved in the ink.
- Examples of the fatty acid or aliphatic ester represented by the general formula (2) include behenic acid, behenyl behenate (C21-C22, melting point 70 ° C.), icosyl icosanoate (C19-C20), stearyl stearate (C17- C18, melting point 60 ° C.), palmitic acid stearate (C17-C16), lauryl stearate (C17-C12), cetyl palmitate (C15-C16, melting point 54 ° C.), stearyl palmitate (C15-C18), myristyl myristate (C13-C14, melting point 43 ° C.), cetyl myristate (C13-C16, melting point 50 ° C.), octyldodecyl myristate (C13-C20), stearyl oleate (C17-C18), stearyl erucate (C21-C18) , Stearyl
- Examples of commercially available aliphatic esters represented by the general formula (2) include Unistar M-2222SL (manufactured by NOF Corporation), EXCEPARL SS (manufactured by Kao Corporation, melting point 60 ° C.), EMALEXCC-18 (Japan) Emulsion Co., Ltd.), Amreps PC (manufactured by Higher Alcohol Industry Co., Ltd.), Exepal MY-M (Kao Co., Ltd.), Spam Acechi (Nissho Co., Ltd.), EMALEX® CC-10 (Nihon Emulsion Co., Ltd.) included. Since these commercial products are often a mixture of two or more types, they may be separated and purified as necessary.
- the actinic ray curable inkjet ink may contain only one kind or two or more kinds of the fatty acid or aliphatic ester compound.
- the amount of the gelling agent contained in the actinic ray curable inkjet ink is 0.5 to 10.0% by mass, preferably 1 to 7% by mass with respect to the total amount of the ink. If it is less than 0.5% by mass, the ink droplet cannot be gelled (sol-gel phase transition due to temperature), and if it exceeds 10% by mass, it cannot be sufficiently dissolved in the ink, and the ink droplet is ejected. This is because the sex is lowered.
- a photopolymerizable compound is a compound which bridge
- the actinic rays are, for example, electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, and X-rays, and are preferably ultraviolet rays.
- the photopolymerizable compound is a radical polymerizable compound or a cationic polymerizable compound, and preferably a radical polymerizable compound.
- the radically polymerizable compound may be a compound (monomer, oligomer, polymer or mixture thereof) having a radically polymerizable ethylenically unsaturated bond.
- the actinic ray curable inkjet ink may contain only one kind of radically polymerizable compound or two or more kinds thereof.
- Examples of compounds having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids and salts thereof, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid urethane compounds, unsaturated carboxylic acid amide compounds and anhydrides thereof, Acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, unsaturated urethane and the like are included.
- 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 more preferably an unsaturated carboxylic acid ester compound, and more preferably a (meth) acrylate compound.
- the (meth) acrylate compound may be not only a monomer but also an oligomer, a mixture of a monomer and an oligomer, a modified product, an oligomer having a polymerizable functional group, or the like.
- “(meth) acrylate” refers to both and / or “acrylate” and “methacrylate”
- (meth) acryl” refers to both and / or “acryl” and “methacryl”.
- the molecular weight of the (meth) acrylate compound is preferably in the range of 280 to 1500, and more preferably in the range of 300 to 800.
- the ink viscosity at the ejection temperature be between 7 and 14 mPa ⁇ s.
- An ink containing a (meth) acrylate compound having a molecular weight of 280 or more and a gelling agent has a small change in the viscosity of the ink before and after the discharge temperature, and it is easy to adjust the ink viscosity within the above range.
- the (meth) acrylate compound having a molecular weight of 280 or more has little odor, the odor of the actinic ray curable inkjet ink and its cured product is reduced.
- the molecular weight is set to 1500 or less, the sol viscosity of the ink is easily within a desired range.
- the (meth) acrylate compound is preferably (1) a trifunctional or higher functional methacrylate or acrylate having 3 to 14 structures represented by (—C (CH 3 ) H—CH 2 —O—) in the molecule.
- Compound (2) A bifunctional or higher functional methacrylate or acrylate compound having a cyclic structure in the molecule.
- a trifunctional or higher functional methacrylate or acrylate compound having 3 to 14 structures represented by (—C (CH 3 ) H—CH 2 —O—) in the molecule includes, for example, 3 or more A hydroxyl group of a compound having a hydroxyl group is modified with propylene oxide, and the resulting modified product is esterified with (meth) acrylic acid.
- this compound include 3PO-modified trimethylolpropane triacrylate Photomer 4072 (molecular weight 471, manufactured by Cognis), 3PO-modified trimethylolpropane triacrylate Miramer M360 (molecular weight 471, manufactured by Miwon), and the like.
- the bifunctional or higher functional methacrylate or acrylate compound having a cyclic structure in the molecule is obtained by esterifying the hydroxyl group of a compound having two or more hydroxyl groups and tricycloalkane with (meth) acrylic acid. It is possible. Specific examples of this compound include tricyclodecane dimethanol diacrylate NK ester A-DCP (molecular weight 304), tricyclodecane dimethanol dimethacrylate NK ester DCP (molecular weight 332), and the like.
- the photopolymerizable compound may be a (meth) acrylate compound other than the above.
- examples of other (meth) acrylate compounds include 1,10-decanediol dimethacrylate, NK ester DOD-N (molecular weight 310, manufactured by Shin-Nakamura Chemical Co., Ltd.), 4EO-modified hexanediol diacrylate (CD561, manufactured by Sartomer, Molecular weight 358); 3EO modified trimethylolpropane triacrylate (SR454, manufactured by Sartomer, molecular weight 429); 4EO modified pentaerythritol tetraacrylate (SR494, manufactured by Sartomer, molecular weight 528); 6EO modified trimethylolpropane triacrylate (SR499, Sartomer) Manufactured by Co., Ltd., molecular weight 560); caprolactone acrylate (SR495B, manufactured by Sartomer); polyethylene glycol diacrylate (SR4
- the photopolymerizable compound may be a polymerizable oligomer other than the unsaturated carboxylic acid ester compound.
- the polymerizable oligomer include epoxy acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, polyester acrylate, linear acrylic oligomer, and the like.
- the amount of the photopolymerizable compound contained in the actinic ray curable inkjet ink is preferably 10 to 40% by mass with respect to the total mass of the ink.
- the amount of the photopolymerizable compound is 10% by mass or more, the solubility of the gelling agent is lowered and the sol-gel phase transition may not be sufficiently performed.
- the amount of the photopolymerizable compound exceeds 40% by mass, the solubility of the photopolymerization initiator in the ink may be insufficient. As a result, ink ejection from the ink jet recording apparatus may become unstable, or shrinkage may occur when ink droplets are cured, and the foil image may be wrinkled.
- Photopolymerization initiator The actinic ray curable inkjet ink further contains a photopolymerization initiator.
- Photopolymerization 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 -Hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4 Acetophenones such as -thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 2 , 4,6-Trimethylbenzoindiphenylphosphine Acylphosphine oxide, such as Kishido; as benzyl and
- intramolecular hydrogen abstraction type photopolymerization initiators 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's ketone, 4,4'-diethylaminobenzophenone; 10-Butyl-2-chloroaclide
- the photopolymerization initiator is acyl phosphine oxide or acyl phosphonate
- the sensitivity is good.
- bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like are preferable.
- the content of the photopolymerization initiator in the actinic ray curable ink-jet ink is preferably 0.1% by mass to 10% by mass, although it depends on the light irradiated at the time of ink curing and the type of the photopolymerizable compound. More preferably, it is 2 to 8% by mass.
- the actinic ray curable ink-jet ink may contain a photoacid generator as required.
- photoacid generators include chemically amplified photoresists and compounds used for photocationic polymerization (Organic Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), 187. See page 192).
- the actinic ray curable ink-jet 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 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
- Non-polymerizable resin The actinic ray curable ink jet ink has a resin that is inert to actinic rays as necessary; that is, has a group (photopolymerizable group) that crosslinks or polymerizes upon irradiation with actinic rays. Non-polymerizable resins may be included.
- non-polymerizable resin contained in the actinic ray curable inkjet ink examples include a polyester resin or a ketone resin having at least one polar functional group in the molecule.
- the gelling agent tends to be deposited on the surface of the droplet after the ink has landed on the recording medium due to the polar functional group.
- the relatively weak polar site (ester site or ketone site) of the polyester resin or ketone resin has an affinity for the gelling agent. That is, the gelling agent is easily mixed uniformly in the sol ink.
- the polar functional group possessed by the polyester resin or ketone resin is preferably a group selected from —OH group, —COOH group, —NH 2 group, —NO 2 group, and —CN group.
- the polyester resin or the ketone resin has these polar functional groups, the gelling agent tends to precipitate on the surface of the ink after landing on the recording medium.
- the polyester resin or ketone resin preferably has both —OH groups and —COOH. If the polyester resin or the ketone resin has these, the adhesiveness is likely to be increased regardless of the functional group present on the surface of the recording medium.
- the amount of the polar functional group possessed by the polyester resin or ketone resin is not particularly limited, but is preferably in the range where the acid value or base value of the polyester resin or ketone resin is 10 to 350 mgKOH / g.
- the acid value or base value of the polyester resin or ketone resin is more preferably 10 to 65 mgKOH / g.
- the acid value or base value of the polyester resin or ketone resin is 10 mgKOH / g, the adhesion between the adhesive layer and the recording medium or foil layer is not sufficiently increased, and the ink does not sufficiently undergo sol-gel phase transition.
- the number average molecular weight of the polyester resin or ketone resin having a polar functional group is preferably 1000 to 5000, and more preferably 1200 to 3000.
- the number average molecular weight of the polyester resin or the ketone resin is less than 1000, the compatibility of the gelling agent is increased and the gelling agent is hardly precipitated.
- the number average molecular weight of the polyester resin or the ketone resin is larger than 5000, the viscosity of the actinic ray curable inkjet ink is increased, and the ejection stability of the ink from the inkjet recording apparatus is lowered.
- the number average molecular weight is a value measured in terms of polystyrene by gel permeation chromatography (GPC).
- polyester resin having a hydroxyl group and a hydroxyl group include a special ester resin (TEGOAddBond series (LTH, LTW, 1270, 2440, 3350UV) manufactured by EVONIK INDUSTRIES, all of which have an average molecular weight of 1500 to 3000 and an acid value of 15 to 65 mgKOH. / G, base number of 10 to 50 mgKOH / g).
- TEGOAddBond series LTH, LTW, 1270, 2440, 3350UV
- ketone resin having a hydroxyl group examples include a ketone resin manufactured by degussa (TEGO VARIPLUS SK (average molecular weight 1000 to 2000, acid value about 0 mgKOH / g, base number about 300 mgKOH / g)).
- ketone resin having a urethane group examples include a ketone resin (TEGO VARIPLUS PZZ-1201) manufactured by degussa.
- the amount of the polar resin-containing polyester resin or ketone resin contained in the actinic ray curable ink jet is 1.0 to 15.0% by mass, preferably 3.0 to 10.0%, based on the total mass of the ink. % By mass.
- the total amount thereof is within the above range. If the amount of the polyester resin or ketone resin having a polar functional group is less than 2.0% by mass, the gelling agent may not be sufficiently precipitated (crystallized) in the ink after landing.
- the method for preparing the polyester resin having a polar functional group is not particularly limited.
- it can be obtained by preparing a polyester resin from a polyhydric alcohol having a polar functional group, a polyvalent carboxylic acid, a cyclic lactone or the like.
- a polyester resin having a polar functional group can be prepared by performing the following reaction.
- the acid value and base value of the polyester resin are adjusted by the number of functional groups such as polyhydric alcohol, polycarboxylic acid, hydroxycarboxylic acid, and polar group-containing cyclic lactone as raw materials.
- a ketone resin having a polar functional group can be prepared by reacting an aromatic ketone compound such as acetophenone with a compound having a polar functional group.
- a ketone resin having an —OH group can be prepared by reacting an aromatic ketone compound such as acetophenone with an aldehyde compound such as formaldehyde and hydrogenating the obtained ketone resin.
- the acid value and base value of the ketone resin are adjusted by the amount of the compound to be reacted with the ketone compound, the kind of the compound, and the like.
- the actinic ray curable inkjet ink may further contain other components as necessary.
- the other components can be color materials, various additives, other resins, and the like.
- the additive include a dispersion aid, a surfactant, a leveling additive, a matting agent, an ultraviolet absorber, 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 cured products of ink, that is, resins for adjusting the physical properties of the adhesive layer, such as polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, And waxes.
- the actinic ray curable inkjet ink is obtained by mixing the above-mentioned gelling agent, photopolymerizable compound, photoinitiator, non-polymerizable resin and the like by a known method while heating.
- the ink image is formed by dropping the above-mentioned actinic ray curable inkjet ink from an inkjet recording apparatus.
- the amount of droplets ejected from each nozzle of the ink jet recording head is preferably 0.5 to 10 pl, although it depends on the resolution of the foil image. In order to form a foil image with high definition, More preferably, it is 0.5 to 2.5 pl.
- the temperature of the recording medium at the time of applying the actinic ray curable ink jet ink is set to a temperature 30 ° C. or more lower than the sol-gel phase transition temperature of the ink.
- the temperature of the recording medium is preferably 30 to 70 ° C. lower than the sol-gel phase transition temperature of the ink, and particularly preferably 30 to 50 ° C. lower than the phase transition temperature.
- the temperature of the recording medium refers to the surface temperature of the recording medium on which the ink lands, and the entire recording medium may not be the above temperature.
- the surface temperature of the recording medium is measured with an infrared radiation thermometer or the like.
- the temperature adjustment of the recording medium is performed by heating or cooling the recording medium by a known method.
- the heating method and the cooling method are not particularly limited, and can be performed by various heaters, chillers, Peltier elements, or the like.
- the average thickness of the ink image formed in this step is preferably about 0.1 to 1000 ⁇ m, more preferably about 1 to 300 ⁇ m.
- the adhesive strength between the foil layer of the transfer foil and the ink image is likely to be sufficiently increased in the foil layer forming step described later.
- the average thickness is measured by observing a cross section of the ink image with an SEM.
- (1.2) Foil layer forming step The transfer surface of the transfer foil including the foil layer is brought into contact with the ink image formed of the ink droplets of the actinic ray curable inkjet ink applied in the above-described ink image forming step, and is pressure-bonded. . Then, the foil layer is transferred only onto the ink image by peeling off the transfer foil.
- the transfer foil brought into contact with the adhesive layer includes at least the support material 4 and the foil layer 5.
- the transfer foil is separated between the support material 4 and the foil layer 5.
- a mold layer (not shown) may be formed.
- an adhesive layer or the like may be formed on the transfer surface of the transfer foil.
- a colored layer (not shown) for coloring the foil layer 5 may be included between the foil layer 5 and the support material 4. In this case, the colored layer is transferred onto the ink image 2 together with the foil layer 5.
- a transfer foil 3 may be a sheet-like sheet or a long sheet wound in a roll shape.
- the foil layer 5 included in the transfer foil 3 imparts a metallic character or a glossy character or pattern, which is difficult to express by normal printing, or a transparent character or pattern having a transparent feeling on the substrate.
- the foil layer 5 can be, for example, a metal foil, a metal vapor deposition film, a hologram film, a pearl tone film, a iridescent film, a white / black film, a color film, a clear film, or the like.
- the foil may be a layer made of a composite material of a plastic film and a metal for the purpose of improving strength.
- the foil layer 5 may also be a layer in which a regular pattern is applied to the metal film by a known processing method such as water-washed celite processing, etching processing, or laser processing.
- the thickness of the foil layer 5 is appropriately selected depending on the type of the foil layer, but is usually about 10 to 100 nm.
- the support material 4 included in the transfer foil 3 may be any member that can indicate the foil layer 5, for example, a film or sheet made of a flexible resin or the like, or a paper sheet.
- the resin constituting the support material 4 include known resins such as polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, polypropylene (PP) resin, polyethersulfone resin, and polyimide resin.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PP polypropylene
- polyethersulfone resin polyimide resin.
- the support material 4 may have a single layer structure or a multilayer structure.
- the transfer foil 3 may include a release layer (not shown).
- the release layer is a layer for ensuring the peelability of the foil layer 5 from the support material 4.
- the release layer can be, for example, a layer made of a thermosetting resin using melamine or isocyanate as a curing agent, a layer containing a known wax such as a fluorine-based or silicon-based monomer or polymer, or the like.
- the transfer foil 3 may further include an adhesive layer (not shown).
- the adhesive layer can be a layer that exhibits adhesiveness to an ink image by heating.
- the adhesive layer can be, for example, a layer made of a heat-sensitive adhesive called a so-called hot melt type.
- the heat-sensitive adhesive include an adhesive containing acrylic resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, ethylene-vinyl alcohol copolymer, and the like.
- the ink image 2 and the transfer surface of the transfer foil 3 are brought into contact with each other and are subjected to pressure bonding.
- a method for press-bonding the transfer foil 3 and the recording medium 1 ′ on which the ink image is formed is not particularly limited.
- the plate 41 having a flat plate shape or a desired shape may be pressed in a state where the recording medium 1 ′ on which an ink image (not shown) is formed and the transfer foil 3 are laminated.
- the transfer foil 3 and the recording medium 1 ′ on which an ink image (not shown) is formed are passed between the pair of transfer rolls 42a and 42b in a laminated state. There may be.
- a method of applying pressure by the transfer roll 43 or the like from the support material side of the transfer foil 3 or the recording medium 1 ′ may be used.
- the force (crimping force) for press-bonding the ink image 2 and the transfer foil 3 is preferably 100 to 800 kPa, more preferably 200 to 600 kPa as the nip surface pressure.
- the pressure bonding time is preferably 0.1 to 30 seconds, and more preferably 0.5 to 10 seconds.
- the pressure bonding between the ink image 2 and the transfer foil 3 may be performed while heating.
- the heating can be performed, for example, by heating a transfer roll or a plate.
- the heating temperature at this time is preferably 30 to 90 ° C., more preferably 40 to 60 ° C.
- the foil layer 5 is easily peeled off from the transfer foil 3, and the foil layer 5 can be transferred in a short time.
- the heating temperature is preferably in the above range.
- the transfer foil 3 After pressing the transfer foil 3 and the ink image 2, the transfer foil 3 is removed from the recording medium 1. At this time, the ink image 2 and the pressed foil layer 5 remain on the ink image 2. On the other hand, the foil layer 5 in the region not in contact with the ink image 2 is removed together with the support material. That is, a foil image (foil layer 5 ′) is formed on the recording medium 1 in the same pattern as the ink image 2.
- the method for irradiating the ink image 2 with light is not particularly limited, and actinic rays may be irradiated from above the foil layer 5. Further, when the recording medium 1 is transmissive to active light, the ink image 2 may be irradiated with active light from the recording medium 1 side.
- the actinic ray irradiated in this step is not particularly limited, and is appropriately selected according to the type of photopolymerization initiator contained in the actinic ray curable inkjet ink.
- it may be an electron beam, an ultraviolet ray, an ⁇ ray, a ⁇ ray, an X-ray or the like, preferably an ultraviolet ray, and particularly preferably an ultraviolet ray from an LED light source.
- LED devices that can be irradiated with ultraviolet light include 395 nm, water-cooled LED manufactured by Phoseon Technology.
- the ultraviolet light source a metal halide lamp is generally used.
- the LED is a light source
- the radiant heat from the light source can be reduced. That is, the viscosity of the ink is reduced by radiant heat and the shape of the ink image 2 is prevented from changing.
- the foil layer 5 ′ is sufficiently fixed by the adhesive layer 2 ′ made of a cured product of the ink image 2.
- the peak illuminance of active rays (peak illuminance of ultraviolet rays of 370 to 410 nm) on the ink image surface is 0.5 to 10 W / cm 2 . It is preferably 1 to 5 W / cm 2 .
- the amount of actinic rays applied to the ink is preferably less than 350 mJ / cm 2 .
- the laminate obtained by the foil image forming method of this embodiment includes a recording medium 1 and an adhesive layer 2 ′ (active) formed in a pattern on the recording medium.
- the foil layer 5 ′ is not easily affected by moisture, and hardly deteriorates over time.
- the foil image forming method of this embodiment can be applied when forming a foil image on various products; for example, decorative wallpaper, packaging materials, books, stationery, machines, equipment, electrical appliances, clothing, fabrics, Applicable to the production of paintings.
- foil image forming apparatus 200 As shown in FIG. 6, all the steps can be performed by one apparatus.
- An example of the foil image forming apparatus will be described below, but the foil image forming apparatus is not limited to this aspect.
- the foil image forming apparatus 200 includes an ink application unit 101 for forming an ink image, a foil transfer unit 102 for transferring the foil layer of the transfer foil, and the ink image is cured. And an actinic ray irradiation unit 103 for the purpose.
- the ink application unit 101 performs the above-described ink image forming process
- the foil transfer unit 102 performs the above-described foil layer forming process.
- the actinic ray irradiation unit 103 performs the above-described ink image curing step.
- the foil image forming apparatus 200 may further include an image forming unit 104 for forming an image other than the foil image or coloring the foil image.
- the ink application unit for applying the actinic ray curable ink jet ink described above includes the ink jet recording means 113 for applying the actinic ray curable ink jet ink described above, and temperature control for controlling the temperature of the recording medium 1. Means 119 are included.
- the inkjet recording means 113 may be a line recording method (single pass recording method) or a serial recording method. These may be selected according to the required resolution and recording speed of the ink image, but from the viewpoint of high-speed recording, it is preferable to use a line recording method (single-pass recording method).
- a line recording method single-pass recording method
- the inkjet recording unit 113 of the line recording system single pass recording system
- the inkjet recording unit 113 is not limited thereto.
- the ink jet recording unit 113 includes a head carriage 116 that houses a plurality of ink jet recording heads 114, an ink channel 117 connected to the head carriage 116, and an ink tank 118 that stores ink supplied through the ink channel 117. It is.
- the ink tank 118 is connected to the head carriage 116 via the ink flow path 117.
- the ink flow path 117 is a path for supplying the ink in the ink tank 118 to the head carriage 116.
- the head carriage 116 is fixedly disposed so as to cover the entire width of the recording medium 1 and accommodates a plurality of ink jet recording heads 114.
- the actinic ray curable inkjet ink is supplied to the inkjet recording head 114.
- a plurality of inkjet recording heads 114 are arranged in the conveyance direction of the recording medium 1, and the number of inkjet recording heads 114 arranged in the conveyance direction of the recording medium 1 is set according to the nozzle density of the inkjet recording head 114 and the resolution of the print image. Is done. For example, when an image having a resolution of 1440 dpi is formed using the inkjet recording head 114 having a droplet amount of 2 pl and a nozzle density of 360 dpi, the four inkjet recording heads 114 are arranged so as to be shifted with respect to the conveyance direction of the recording medium 1.
- dpi represents the number of ink droplets (dots) per 2.54 cm.
- the ink of the ink tank 118, the ink flow path 117, the head carriage 116, and the ink jet recording head 114 is provided with temperature adjusting means (not shown), and the actinic radiation curable ink jet ink described above is in a sol state.
- the temperature is controlled so that
- the temperature control means 119 is arranged so as to cover the entire width of the recording medium 1.
- the temperature control means 119 includes a temperature detection unit (not shown) for detecting the surface temperature of the recording medium 1, a temperature adjustment unit (not shown) such as a heater and a chiller, and the like.
- the temperature control unit 119 is disposed on the lower surface of the recording medium 1, but the temperature control unit 119 is an ink application unit depending on the thickness or shape of the recording medium 1. 101 is arranged at an arbitrary location.
- the recording medium 1 is transported between the head carriage 116 of the inkjet recording means 113 and the temperature control means 119. Then, the temperature control means 119 adjusts the temperature of the recording medium 1 to a temperature that is 30 ° C. or more lower than the sol-gel phase transition temperature of the actinic ray curable inkjet ink. Next, high-temperature ink droplets are ejected from the inkjet recording head 114 of the head carriage 116 and adhere (land) on the recording medium 1. At this time, the ink droplets that have landed on the recording medium 1 are quickly gelled to form an ink image in a desired shape.
- the foil transfer unit 102 includes a pair of rollers (foil transfer nip roller 120) that sandwich the recording medium 1, a foil feed spool 121 that supplies the transfer foil 3 between the pair of nip rollers 120, and a foil layer after transfer.
- a take-up spool 122 for collecting the transfer foil 3 is included.
- the ink image formed by the ink application unit 101 described above and the transfer surface of the transfer foil 3 are pressed against each other by the nip roller 120.
- the foil layer of the transfer foil is transferred onto the ink image to form a foil image.
- the transfer foil 3 after being pressed against the recording medium 1 is collected by the take-up spool 122.
- the actinic ray irradiation unit 103 includes a light irradiation unit (light source) 131.
- the light irradiation unit (light source) 131 is installed so as to cover the entire width of the recording medium 1.
- the actinic ray irradiation unit 103 the actinic ray curable inkjet ink (ink image) described above is cured, and the foil image is fixed on the recording medium.
- the image forming unit 104 is a unit for applying ink of each color to a recording medium, and its installation position is not particularly limited.
- the image forming unit 104 can be installed upstream of the ink application unit 101 and the foil transfer unit 102.
- the image forming unit 104 is disposed downstream of the ink application unit 101 and the foil transfer unit 102.
- the ink applied by the image forming unit 104 is an actinic ray curable ink
- the ink is applied between the actinic ray irradiation unit 103 and the foil transfer unit 102 and applied by the image forming unit 104.
- the ink may be cured by the actinic ray irradiation unit 103 described above.
- the image forming unit 104 includes a plurality of colors of ink jet recording means.
- Each ink jet recording means stores a head carriage 116 ′ that accommodates a plurality of ink jet recording heads 114 ′, an ink channel 117 ′ connected to the head carriage 116 ′, and ink supplied through the ink channel 117 ′. And an ink tank 118 ′.
- the ink jet recording head 114 ′, the head carriage 116 ′, the ink flow path 117 ′, and the ink tank 118 ′ of the image forming unit can be the same as each configuration of the ink application unit 101.
- each color ink is applied.
- yellow (Y), magenta (M), cyan (C), and black (K) inks are applied to the recording medium 1 from each ink jet recording unit to form various images.
- the type of ink applied by the image forming unit 104 is not particularly limited, and may be actinic ray curable ink or solvent-based ink as described above.
- Example of first aspect [Synthesis of copolymer resin P-1] A flask equipped with a dropping funnel, a reflux tube, a nitrogen introduction tube, a thermometer and a stirrer was charged with 186 parts by mass of 2-propanol and heated to reflux while bubbling with nitrogen. There, the monomer solution of the following composition was dripped in the flask over 2 hours from the dropping funnel. After the dropwise addition, the mixture was further heated under reflux for 5 hours, then allowed to cool, and 2-propanol was distilled off under reduced pressure to obtain a copolymer resin P-1.
- the following polymerization initiator is azobisisobutyronitrile (AIBN). Methyl methacrylate 70 parts by weight Ethyl acrylate 10 parts by weight 2-ethylhexyl acrylate 10 parts by weight Methacrylic acid 10 parts by weight Polymerization initiator 0.5 parts by weight
- the Tg of the copolymer resin P-1 was 75 ° C.
- the Tg of the copolymer resin P-1 is 10-30 ° C./min in the nitrogen gas stream within the range of ⁇ 30 to 100 ° C. or 0 to 130 ° C., then cooled, and again 10
- the temperature was measured by differential scanning calorimetry (DSC) when the temperature was raised at ° C / min.
- the acid value (Acid Value, hereinafter also referred to as “AV”) of the copolymer resin P-1 was measured.
- the AV of the copolymer resin P-1 was 65 mgKOH / g.
- the AV of copolymer resin P-1 was obtained by dissolving 10 g of copolymer resin P-1 in about 50 mL of solvent, adding a phenolphthalein indicator to the resulting solution, Titration with a potassium hydroxide ethanol solution was performed according to the following formula from the amount of the potassium hydroxide ethanol solution used for the titration.
- AV (B ⁇ f ⁇ 5.611) / S
- B is a drop amount (mL) of the potassium hydroxide ethanol solution
- f is a factor of the potassium hydroxide ethanol solution
- S is a mass (g) of the copolymer resin P-1
- 5.611 is It is a value (56.11 / 10) of 1/10 of the formula amount of potassium hydroxide.
- Mw of the copolymer resin P-1 was 35000.
- Mw of copolymer resin P-1 was determined by gel permeation chromatography under the following measurement conditions. Column: TSKgel G40000H XL , G2500H XL and G2000H XL (manufactured by Tosoh Corporation) Column temperature: 40 ° C Eluent: Tetrahydrofuran Eluent flow rate: 1.0 mL / min Detector: RI Calibration curve: Standard polystyrene
- Copolymer resins P-2 to P-18 and R-1 to R were the same as copolymer resin P-1, except that the types and amounts of monomers in the monomer solution were changed as shown in Tables 1 and 2. Each of -4 was synthesized. Further, Tg, AV and Mw of P-2 to P-18 and R-1 to R-4 were determined in the same manner as copolymer resin P-1.
- Tables 1 and 2 show the monomer compositions, Tg, AV and Mw of copolymer resins P-1 to P-18 and R-1 to R-4.
- MMA represents methyl methacrylate
- EA represents ethyl acrylate
- BA represents butyl acrylate
- i-BA represents isobutyl acrylate
- 2- EHA
- n-HA is n-hexyl acrylate
- CH cyclohexyl acrylate
- LA lauryl acrylate
- SA is stearyl acrylate
- MA represents methacrylic acid
- AA represents acrylic acid.
- ink K-1 is a silicone surfactant manufactured by Shin-Etsu Chemical Co., Ltd.
- Aqueous solution of copolymer resin P-1 45 parts by weight Deionized water 29.5 parts by weight Dipropylene glycol propyl ether 10 parts by weight 3-methoxy-N, N-dimethylpropionamide 15 parts by weight KF-351A 0.5 parts by weight
- inks K-2 to K-21 were prepared in the same manner as ink K-1, except that the types of bases and ink materials in the aqueous solution were changed as shown in Table 3.
- the quantity of the base compound in the aqueous solution of copolymer resin is 1.05 equivalent of the acidic group of copolymer resin.
- the copolymer resin R-4 was not dissolved in the aqueous ammonia solution in the preparation of the aqueous solution of the copolymer resin, and the aqueous ammonia solution became clouded. Therefore, the ink containing the copolymer resin R-4 (K-22) ) was not prepared.
- Table 3 shows the types of bases and ink materials of inks K-1 to K-21.
- B-1 represents ammonia
- B-2 represents N, N-dimethylaminoethanol
- B-3 represents 2-amino-2-methylpropanol.
- PO-1 represents dipropylene glycol propyl ether
- PO-2 represents diethylene glycol monobutyl ether
- PO-3 represents 1,2-hexanediol.
- A-1 is 3-methoxy-N, N-dimethylpropionamide
- A-2 is 3-butoxy-N, N-dimethylpropionamide
- A-3 is 3- Ethoxy-N, N-diethylpropionamide is represented respectively.
- SA-1 is a silicone surfactant KF-351A (manufactured by Shin-Etsu Chemical Co., Ltd.)
- SA-2 is a silicone surfactant BYK-347 (manufactured by BYK Chemie)
- SA-3 represents a fluorosurfactant FC-430 (manufactured by 3M).
- Ink K-1 was loaded into one of the heads of an on-demand type ink jet printer equipped with four rows of piezo heads having a nozzle diameter of 28 ⁇ m, a driving frequency of 18 kHz, a nozzle number of 512, a minimum droplet amount of 12 pL, and a nozzle density of 180 dpi.
- the printer has a contact-type heater that can arbitrarily heat the recording medium from the back surface (the surface opposite to the surface facing the head), and the ink storage position and blade-wipe maintenance unit at the head storage position. It is comprised so that head cleaning can be performed at arbitrary frequency.
- An image including a second fine line image portion arranged vertically and horizontally at a width interval of 5 mm was printed with ink K-1.
- the foil image forming apparatus as shown in FIG. 1 directs the foil of the foil sheet downward, and the ink K-1 is ejected from the inkjet head toward the recording medium for the image. Then, the fleece wallpaper material and the foil sheet were sandwiched between the heating roller and the supporting roller and passed therethrough to form a foil image latent image.
- thermocompression bonding was heated (preheated) from the back surface with the heater so that the surface temperature of the recording medium during thermocompression bonding was 50 ° C.
- the surface temperature of the recording medium was measured using a non-contact thermometer (IT-530N type, manufactured by HORIBA, Ltd.).
- the recording medium and the foil sheet were passed while being pressed between the heating roller and the supporting roller whose temperature was set to 100 ° C., and then the foil sheet was separated from the recording medium.
- the foil was transferred onto the recording medium corresponding to the latent image portion formed with the ink K-1.
- the recording medium was heated to 80 ° C. with a heat drying apparatus and dried to obtain a foil image.
- the obtained foil images were evaluated for the following items.
- the first fine line image part and the second fine line image part are visually observed with a magnifying glass with a magnification of 10 times, and there is no excess foil between the fine lines.
- the following criteria were used to evaluate the presence or absence of omissions.
- A, B, and C were accepted and D was rejected.
- B A minute part on the thin line image having a width of 0.5 mm Deficiency was observed, but at a level that was not a problem with the naked-eye observation.
- C It was recognized by the naked-eye observation that an extra foil was partially left between the thin lines, but it was within a practically acceptable range.
- D Those lines that cannot be completely reproduced can be confirmed with the naked eye
- a foil image is wrapped around a 3mm diameter stainless steel rod with the foil image facing outward, and the occurrence of defects such as floating, peeling, and cracking of the foil in the foil image is visually confirmed.
- the bending resistance was evaluated according to the following criteria. A: No floating, peeling or cracking caused by winding. B: Mild floating, peeling or cracking is observed by winding more than 10 times. C: Mild lifting or peeling by winding more than 2 times but less than 10 times. Cracks are observed. D: Clear floating, peeling, and cracking occur after winding once.
- a foil image was formed and evaluated in the same manner as described above except that each of the inks K-2 to K-21 was used instead of the ink K-1.
- Table 4 shows the evaluation results for each ink.
- the foil images using the inks K-1 to K-18 all have sufficient fine line reproducibility, abrasion resistance, adhesive strength, and bending resistance.
- the inks K-1 to K-18 all contain water and a water-soluble organic solvent, and any of the copolymer resins P-1 to P-18 includes (meth) acrylic acid and carbon.
- the foil image using the ink K-20 was insufficient in abrasion resistance and adhesive strength. This is presumably because the ratio of the (meth) acrylic acid alkyl ester in the copolymer resin R-2 was too high, and as a result, the Tg of the copolymer resin R-2 was too low.
- the foil image using ink K-21 was insufficient in abrasion resistance. This is presumably because the alkyl group of the (meth) acrylic acid alkyl ester in the copolymer resin R-3 was too long, and the ink K-21 did not sufficiently reach the fine irregularities on the surface of the recording medium or foil.
- Example of Second Embodiment The following materials were used as materials for the actinic ray curable inkjet ink.
- Photomer 4072 (manufactured by Cognis): 3PO-modified trimethylolpropane triacrylate: molecular weight 471 Miramer M360 (manufactured by Miwon): trimethylolpropane PO-modified triacrylate: molecular weight 471 NK ester DOD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.): 1,10-decanediol dimethacrylate: molecular weight 310 NK ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.): tricyclodecane dimethanol diacrylate: molecular weight 304 NK ester A-400 (manufactured by Shin-Nakamura Chemical Co., Ltd.): polyethylene glycol diacrylate CD561 (manufactured by Sartomer): alkoxylated hexanediol diacrylate SR499 (
- TEGO AddBond LTH manufactured by EVONIK, polyester resin containing hydroxyl group and carboxyl group, acid value 16 mgKOH / g, base number 25 mgKOH / g, number average molecular weight 2000 to 3000
- TEGO VARIPLUSK SK manufactured by degussa, hydroxyl group-containing ketone resin, acid value less than 3 mgKOH / g, base value 325 mgKOH / g, number average molecular weight 1000-1500
- Example 2-1 Application of actinic ray curable inkjet ink The actinic ray curable inkjet ink prepared in Synthesis Example 1 was filled in the ink tank 118 of the ink application unit of the foil image forming apparatus shown in FIG.
- the actinic ray curable ink-jet ink is applied to a recording medium made of vinyl chloride (base paper for vinyl chloride cloth manufactured by KJ Special Paper Co., Ltd., thickness: 1000 ⁇ m) with a droplet amount of 14 pl, a printing speed of 0.5 m / sec, an ejection frequency of 10.5 kHz, and printing. Continuous discharge (driving) was performed under conditions where the rate was 100%.
- the temperature of the recording medium upon landing of the actinic ray curable inkjet ink was adjusted to 25 ° C.
- an infrared radiation thermometer “IR0510” manufactured by Minolta was used.
- nip roller 120 on the transfer foil side a roll was used in which a silicone rubber layer having a thickness of 1.5 mm was arranged on an aluminum substrate having a length of 357 mm, an outer diameter of 62 mm, and a thickness of 5 mm.
- nip roller 120 on the recording medium 1 side a roll in which a silicone rubber layer having a thickness of 1.5 mm is disposed on an aluminum substrate having a length of 357 mm, an outer diameter of 52 mm, and a thickness of 5 mm was used. .
- the nip width between the heating roller and the pressure roller was 7 mm.
- the surface pressure at the nip was 290 kPa.
- the sheet passing speed in the foil fixing device was 100 mm / sec.
- a peeling roller having a roll diameter of 10 mm was used as the peeling device.
- the temperature of the heating roller was 45 ° C.
- Example 2-2 to 2-5 The recording medium was changed to the recording medium shown in Table 6 or the temperature of the recording medium upon landing of the actinic ray curable ink jet ink was changed to the temperature shown in Table 6 as in Example 2-1. A foil image was formed.
- an actinic radiation curable inkjet ink containing 3% by mass of a gelling agent is used, and the difference between the temperature of the recording medium upon landing of the ink and the sol-gel phase transition temperature of the ink is 30 ° C. or more.
- the fine line reproducibility of the foil image was good.
- the difference between the temperature of the recording medium upon landing of the ink and the sol-gel phase transition temperature of the ink is 35 ° C. (Examples 2-1 to 2-4)
- fine line reproduction is possible with any recording medium. The property was good. This is presumably because the gelation speed of the ink on the recording medium was increased and it was difficult for the ink to wet and spread.
- the adhesiveness of the solid image was high. If the ink contains such a gelling agent, the ink tends to stay on the surface of the recording medium, and it is assumed that sufficient adhesion was obtained. On the other hand, when the ink does not contain a gelling agent, it is presumed that, in a recording medium or the like having irregularities, the ink easily enters the concave portions and it is difficult to obtain sufficient adhesiveness.
- the ink contains a gelling agent having a linear hydrocarbon group having 12 or more carbon atoms (Examples 2-1 to 2-5 and Comparative Example 2-6)
- the water resistance of the foil image is increased. It was easy.
- the ink contains such a gelling agent, the alkyl chain tends to be oriented on the surface of the ink droplet after landing on the recording medium. That is, in the adhesive layer obtained by curing the ink droplet, the surface of the layer contains many alkyl chains. As a result, it is assumed that the adhesive layer is less likely to swell due to external moisture.
- Examples 2-7 to 2-15 and Comparative Examples 2-7 to 2-8 A foil image was formed in the same manner as in Example 2-1, except that the temperature of the actinic ray curable inkjet ink or the recording medium upon landing of the actinic ray curable inkjet ink was changed to the type shown in Table 7.
- an actinic ray curable inkjet ink containing 0.5 to 10% by mass of a gelling agent was used, and the difference between the temperature of the recording medium upon landing of the ink and the sol-gel phase transition temperature of the ink was 30.
- the temperature was higher than or equal to ° C. (Examples 2-7 to 2-15), the fine line reproducibility of the foil image was good.
- the present invention it is possible to form a highly durable foil image by the inkjet image forming method regardless of the hydrophilicity of the recording medium. Therefore, according to the present invention, it is expected to contribute to the spread of foil images using a recording medium, which has been difficult to form foil images, and the further spread of foil images having high design properties.
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Abstract
Description
[1]記録媒体または箔シートの少なくとも一方に、形成すべき箔画像に応じた形状に、インクジェットプリント法によって接着性インクを塗布し、上記記録媒体および上記箔シートの箔を加熱圧着し、上記記録媒体から上記箔シートを剥がして、上記記録媒体に箔画像を形成する箔画像形成方法であって、前記接着性インクは、水、水溶性有機溶剤および共重合樹脂を含有し、前記共重合樹脂は、(メタ)アクリル酸、および、炭素数が2~12のアルキル基を有する(メタ)アクリル酸アルキルエステル、を含むモノマーの共重合体であり、前記接着性インクにおいて分散または溶解しており、前記共重合樹脂の酸価は、50~120mgKOH/gであり、前記共重合樹脂のガラス転移温度は、30~110℃である、箔画像形成方法。
[3]前記水溶性有機溶剤は、グリコールエーテル類、炭素数が4以上である1,2-アルカンジオール、および、β-アルコキシプロピオンアミド類、からなる群から選ばれる一以上である、[1]または[2]に記載の箔画像形成方法。
[4]前記接着性インクは、界面活性剤をさらに含有する、[1]~[3]のいずれかに記載の箔画像形成方法。
[6]前記記録媒体は、壁紙材である、[1]~[5]のいずれかに記載の箔画像形成方法。
[7]前記壁紙材は、天然パルプおよび合成繊維を混抄した不織布を含む、[6]に記載の箔画像形成方法。
[8]記録媒体上に、ゲル化剤、光重合性化合物、及び光重合開始剤を含み、温度によりゾルゲル相転移する活性光線硬化型インクジェットインクを滴下し、前記活性光線硬化型インクジェットインクの液滴からなるインク画像を形成する工程と、箔層を含む転写箔の転写面を前記インク画像と圧着し、前記インク画像上に前記箔層を転写する工程と、前記インク画像に活性光線を照射して、前記活性光線硬化型インクジェットインクを硬化させ、前記箔層を前記記録媒体上に定着させる工程と、を含み、前記活性光線硬化型インクジェットインクが、前記ゲル化剤を前記活性光線硬化型インクジェットインクの全質量に対して0.5~10質量%含み、前記活性光線硬化型インクジェットインクが着弾する際の前記記録媒体の温度と、前記活性光線硬化型インクジェットインクのゾルゲル相転移温度との差が30℃以上である、箔画像形成方法。
[10]前記ゲル化剤が、下記一般式(1)または(2)で表される、[8]または[9]に記載の箔画像形成方法。
R1-CO-R2 (1)
(一般式(1)において、R1及びR2は、それぞれ炭素数1~24の直鎖状または分岐鎖状の炭化水素基を表し、R1及びR2のうち、いずれか一方は、炭素数が12以上の直鎖アルキル構造を含む)
R3-COO-R4 (2)
(一般式(2)において、R3は、炭素数1~24の直鎖状または分岐鎖状の炭化水素基を表し、R4は水素原子または炭素数1~24の直鎖状または分岐鎖状の炭化水素基を表し、R3及びR4のうち、いずれか一方は、炭素数が12以上の直鎖アルキル構造を含む)
[12]前記壁紙材が、天然パルプと合成繊維とを混抄した不織布を含む、[11]に記載の箔画像形成方法。
[14]前記記録媒体が、壁紙材である、[13]に記載の積層体。
以下、本発明の第一の実施態様を説明する。
本実施態様に係る箔画像形成方法は、記録媒体または箔シートの少なくとも一方に、形成すべき箔画像に応じた形状に、インクジェットプリント法によって接着性インクを塗布し、上記記録媒体および上記箔シートの箔を加熱圧着し、上記記録媒体から上記箔シートを剥がして、記録媒体に箔画像を形成する。上記箔画像形成方法は、後述する接着性インクを用いる以外は、インクジェットプリント法によって接着剤を記録媒体に塗布し、加熱圧着によって箔を転写する、例えば特許文献1に記載されているような公知の箔画像形成方法によって行うことが可能である。
以下、本発明の第二の実施態様について説明する。
本実施態様の箔画像形成方法の一例を図2に示す。本実施態様の箔画像の形成方法では、図2(a)に示されるように、活性光線硬化型インクジェットインクを、記録媒体1上にパターン状に塗布し、インク画像2を形成する。そして、図2(b)に示されるように、当該インク画像2に、支持材4及び箔層5を含む転写箔3の転写面(箔層5)を密着させて、圧着する。その後、図2(c)に示されるように、転写箔3を除去する。このとき、インク画像と圧着された箔層5は、インク画像2上に残る。一方、インク画像2と圧着されなかった箔層5は、支持材4と共に除去される。つまり、記録媒体1上には、インク画像2のパターン状に箔層5’が残存し、これが箔画像となる。そして、図2(d)に示されるように、インク画像2に活性光線を光源131から照射して、活性光線硬化型インクジェットインクを硬化させて、箔層5’を記録媒体1上に定着させる。
(1)記録媒体上に、ゾルゲル相転移する活性光線硬化型インクジェットインクを滴下し、前記活性光線硬化型インクジェットインクの液滴からなるインク画像を形成する工程
(2)箔層を含む転写箔の転写面を前記インク画像と圧着し、前記インク画像上に前記箔層を転写する工程
(3)前記インク画像に活性光線を照射し、前記活性光線硬化型インクジェットインクを硬化させ、前記箔層を前記記録媒体上に定着させる工程
以下、各工程について説明する。
インク画像形成工程では、図2に示されるように、記録媒体1上に、ゾルゲル相転移する活性光線硬化型インクジェットインクを滴下し、前記活性光線硬化型インクジェットインクの液滴からなるインク画像2を形成する。インク画像2は、最終的に得ようとする箔画像(箔層からなる画像)と同一のパターンに形成する。
本工程で、活性光線硬化型インクジェットインクが塗布される記録媒体は、当該インクを硬化させて得られる接着層が接着可能な材料であれば特に制限されない。前述のように、本実施態様の活性光線硬化型インクジェットインクの液滴は、基材に凹凸があっても凹部に入り込み難い。したがって、本実施態様の箔画像形成方法によれば、凹凸を有する記録媒体にも箔画像を形成可能である。
本工程に用いられる活性インクジェットインク(以下、単に「インク」とも称する)は、ゾルゲル相転移する。つまり、高温(例えば80℃程度)では液体(ゾル状態)であり、冷却されるとゲル化する性質を有する。そして、本実施態様でいう、インクのゾルゲル相転移温度とは、ゾル状態にあるインクを冷却する過程において、ゲル化して流動性が低下するときの温度とする。
活性光線硬化型インクジェットインクに含まれるゲル化剤は、インクを温度により可逆的にゾルゲル相転移させる機能を有する。そのようなゲル化剤は、少なくとも1)ゾルゲル相転移温度よりも高い温度で、光重合性化合物等に溶解すること、2)ゾルゲル相転移温度以下の温度では結晶化すること、が必要である。
脂肪族ケトン化合物;
脂肪族エステル化合物;
パラフィンワックス、マイクロクリスタリンワックス、ペトロラクタム等の石油系ワックス;
キャンデリラワックス、カルナウバワックス、ライスワックス、木ロウ、ホホバ油、ホホバ固体ロウ、およびホホバエステル等の植物系ワックス;
ミツロウ、ラノリンおよび鯨ロウ等の動物系ワックス;
モンタンワックス、および水素化ワックス等の鉱物系ワックス;
硬化ヒマシ油または硬化ヒマシ油誘導体;
モンタンワックス誘導体、パラフィンワックス誘導体、マイクロクリスタリンワックス誘導体またはポリエチレンワックス誘導体等の変性ワックス;
ベヘン酸、アラキジン酸、ステアリン酸、パルミチン酸、ミリスチン酸、ラウリン酸、オレイン酸、およびエルカ酸等の高級脂肪酸;
ステアリルアルコール、ベヘニルアルコール等の高級アルコール;
12-ヒドロキシステアリン酸等のヒドロキシステアリン酸;
12-ヒドロキシステアリン酸誘導体;
ラウリン酸アミド、ステアリン酸アミド、ベヘン酸アミド、オレイン酸アミド、エルカ酸アミド、リシノール酸アミド、12-ヒドロキシステアリン酸アミド等の脂肪酸アミド(例えば日本化成社製 ニッカアマイドシリーズ、伊藤製油社製 ITOWAXシリーズ、花王社製 FATTYAMIDシリーズ等);
N-ステアリルステアリン酸アミド、N-オレイルパルミチン酸アミド等のN-置換脂肪酸アミド;
N,N'-エチレンビスステアリルアミド、N,N'-エチレンビス-12-ヒドロキシステアリルアミド、およびN,N'-キシリレンビスステアリルアミド等の特殊脂肪酸アミド;
ドデシルアミン、テトラデシルアミンまたはオクタデシルアミンなどの高級アミン;
ステアリルステアリン酸、オレイルパルミチン酸、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、プロピレングリコール脂肪酸エステル、エチレングリコール脂肪酸エステル、ポリオキシエチレン脂肪酸エステル等の脂肪酸エステル化合物(例えば日本エマルジョン社製 EMALLEXシリーズ、理研ビタミン社製 リケマールシリーズ、理研ビタミン社製 ポエムシリーズ等);
ショ糖ステアリン酸、ショ糖パルミチン酸等のショ糖脂肪酸のエステル(例えばリョートーシュガーエステルシリーズ 三菱化学フーズ社製);
ポリエチレンワックス、α-オレフィン無水マレイン酸共重合体ワックス等の合成ワックス(Baker-Petrolite社製 UNILINシリーズ等);
ダイマー酸;
ダイマージオール(CRODA社製 PRIPORシリーズ等);
ステアリン酸イヌリン等の脂肪酸イヌリン;
パルミチン酸デキストリン、ミリスチン酸デキストリン等の脂肪酸デキストリン(千葉製粉社製 レオパールシリーズ等);
ベヘン酸エイコサン二酸グリセリル;
ベヘン酸エイコサンポリグリセリル(日清オイリオ社製 ノムコートシリーズ等);
N-ラウロイル-L-グルタミン酸ジブチルアミド、N-(2-エチルヘキサノイル)-L-グルタミン酸ジブチルアミド等のアミド化合物(味の素ファインテクノより入手可能);
1,3:2,4-ビス-O-ベンジリデン-D-グルシトール(ゲルオールD 新日本理化より入手可能)等のジベンジリデンソルビトール類;
特開2005-126507号公報、特開2005-255821号公報および特開2010-111790号公報に記載の低分子オイルゲル化剤;等が含まれる。
一般式(1)において、R1及びR2は、それぞれ炭素数1~24の直鎖状または分岐鎖状の炭化水素基を表し、より好ましくは炭素数1~24の直鎖状の炭化水素基であり、さらに好ましくは炭素数8~22の直鎖状の炭化水素基である。ただし、R1及びR2のうち、いずれか一方は、炭素数が12以上の直鎖アルキル構造を含み、好ましくは両方が、炭素数が12以上の直鎖アルキル構造を含む。
一般式(2)において、R3は、炭素数1~24の直鎖状または分岐鎖状の炭化水素基を表し、より好ましくは炭素数1~24の直鎖状の炭化水素基であり、さらに好ましくは炭素数8~22の直鎖状の炭化水素基である。一方、R4は水素原子または炭素数炭素数1~24の直鎖状または分岐鎖状の炭化水素基を表し、より好ましくは炭素数1~24の直鎖状の炭化水素基であり、さらに好ましくは炭素数8~22の直鎖状の炭化水素基である。ただし、R3及びR4のうち、いずれか一方は、炭素数が12以上の直鎖アルキル構造を含み、好ましくは両方が、炭素数が12以上の直鎖アルキル構造を含む。
光重合性化合物は、活性光線の照射により架橋又は重合する化合物である。活性光線は、例えば電子線、紫外線、α線、γ線、およびエックス線等であり、好ましくは紫外線である。光重合性化合物は、ラジカル重合性化合物又はカチオン重合性化合物であり、好ましくはラジカル重合性化合物である。
活性光線硬化型インクジェットインクには、光重合開始剤がさらに含まれる。光重合開始剤は、分子内結合開裂型と分子内水素引き抜き型とがある。
活性光線硬化型インクジェットインクには、必要に応じて活性光線に対して不活性な樹脂;すなわち、活性光線の照射により、架橋または重合する基(光重合性基)を有さない、非重合性の樹脂が含まれてもよい。
(i)2官能以上の多価アルコール、及び2官能以上の多価カルボン酸の直接エステル化反応
(ii)2官能以上のポリエステル、及び2官能以上の多価アルコールのエステル交換反応
(iii)2官能以上の多価アルコール、及び酸無水物のエステル化反応
(iv)1分子中に水酸基とカルボキシル基をそれぞれ1つ以上有するヒドロキシカルボン酸の直接エステル化反応
(v)極性官能基が環に結合した環状ラクトンの開環重合
活性光線硬化型インクジェットインクには、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、色材や、各種添加剤や他の樹脂等でありうる。添加剤の例には、分散助剤、界面活性剤、レベリング添加剤、マット剤、紫外線吸収剤、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、インクの硬化物、つまり接着層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、ゴム系樹脂、およびワックス類等が含まれる。
活性光線硬化型インクジェットインクは、前述のゲル化剤、光重合性化合物、光開始剤、非重合性樹脂等を、加熱しながら公知の方法で混合して得られる。
インク画像の形成は、前述の活性光線硬化型インクジェットインクを、インクジェット記録装置より滴下して行う。このとき、インク液滴の射出性を高めるためには、インクジェット記録ヘッド内のインクの温度を、インクのゾルゲル相転移温度より10~30℃高い温度に設定することが好ましい。インクジェット記録ヘッド内のインク温度が、ゾルゲル相転移温度+10℃未満であると、インクジェット記録ヘッド内もしくはノズル表面でインクがゲル化して、インク液滴の射出性が低下しやすい。一方、インクジェット記録ヘッド内のインクの温度が、ゾルゲル相転移温度+30℃を超えると、インクが高温になりすぎるため、インク成分が劣化することがある。
前述のインク画像形成工程で塗布された活性光線硬化型インクジェットインクのインク液滴からなるインク画像に、箔層を含む転写箔の転写面を接触させて圧着する。そして、転写箔を剥離することにより、インク画像上にのみ、箔層を転写する。
前述の箔層形成後、記録媒体1と箔層5との間のインク画像2に活性光線を照射し、活性光線硬化型インクジェットインク(インク画像2)に含まれる光重合性化合物を架橋又は重合させて硬化させる。これにより、箔層5が記録媒体1上に定着される。
前述の箔画像形成方法の各工程は、異なる装置によりそれぞれ行ってもよい。一方、図6に示されるような、箔画像形成装置200であれば、全ての工程を一つの装置で行うことができる。箔画像形成装置の一例を、以下説明するが、箔画像形成装置は、当該態様に限定されない。
前述の活性光線硬化型インクジェットインクを塗布するためのインク塗布ユニットには、前述の活性光線硬化型インクジェットインクを塗布するためのインクジェット記録手段113と、記録媒体1の温度を制御するための温度制御手段119とが含まれる。
箔転写ユニット102には、記録媒体1を挟み込むローラー対(箔転写ニップローラー120)と、当該ニップローラー120のローラー対の間に転写箔3を供給する箔送り出しスプール121と、箔層転写後の転写箔3を回収する巻き取りスプール122とが含まれる。
活性光線照射ユニット103には、光照射部(光源)131が含まれる。光照射部(光源)131は、記録媒体1の全幅を覆うように設置される。活性光線照射ユニット103では、前述の活性光線硬化型インクジェットインク(インク画像)が硬化し、箔画像が記録媒体に定着される。
画像形成ユニット104は、各色のインクを記録媒体に塗布するためのユニットであり、その設置位置は特に制限されない。例えば、画像形成ユニット104で、箔画像以外の画像を形成する場合には、インク塗布ユニット101及び箔転写ユニット102より上流側に設置することができる。一方で、画像形成ユニット104で、箔画像を着色する場合には、インク塗布ユニット101及び箔転写ユニット102より下流側に配置される。なお、画像形成ユニット104で塗布するインクが、活性光線硬化型のインクである場合には、前述の活性光線照射ユニット103と箔転写ユニット102との間に設置し、画像形成ユニット104で塗布したインクを、前述の活性光線照射ユニット103で硬化させてもよい。
[共重合樹脂P-1の合成]
滴下ロート、還流管、窒素導入管、温度計および攪拌装置を備えたフラスコに186質量部の2-プロパノールを収容し、窒素でバブリングしながら加熱還流した。そこへ、下記組成のモノマー溶液を滴下ロートより2時間かけてフラスコ内に滴下した。滴下後、さらに5時間加熱還流を続け、次いで放冷し、減圧下で2-プロパノールを留去して、共重合樹脂P-1を得た。なお、下記重合開始剤は、アゾビスイソブチロニトリル(AIBN)である。
メタクリル酸メチル 70質量部
アクリル酸エチル 10質量部
アクリル酸2-エチルヘキシル 10質量部
メタクリル酸 10質量部
重合開始剤 0.5質量部
AV=(B×f×5.611)/S
カラム:TSKgel G40000HXL、G2500HXLおよびG2000HXL(東ソー株式会社製)
カラム温度:40℃
溶離液:テトラヒドロフラン
溶離液の流速:1.0mL/分
検出器:RI
較正曲線:標準ポリスチレン
モノマー溶液中のモノマーの種類および量を表1および表2に示すように変更した以外は共重合樹脂P-1と同様にして、共重合樹脂P-2~P-18およびR-1~R-4のそれぞれを合成した。また、共重合樹脂P-1と同様にして、P-2~P-18およびR-1~R-4のそれぞれのTg、AVおよびMwを求めた。
下記組成の液体を加熱し、70℃にて攪拌して共重合樹脂P-1を溶解し、樹脂固形分が20質量%の共重合樹脂P-1の水溶液を得た。なお、アンモニア水中のアンモニアの量は、共重合樹脂P-1の酸性基の1.05当量である。
共重合樹脂P-1 10質量部
イオン交換水 39.35質量部
アンモニア水 0.65質量部
共重合樹脂P-1の水溶液 45質量部
イオン交換水 29.5質量部
ジプロピレングリコールプロピルエーテル 10質量部
3-メトキシ-N,N-ジメチルプロピオンアミド 15質量部
KF-351A 0.5質量部
上記水溶液の中の塩基の種類およびインクの材料の種類を表3に示すように変更した以外は、インクK-1と同様にして、インクK-2~K-21のそれぞれを調製した。なお、共重合樹脂の水溶液における塩基化合物の量は、共重合樹脂の酸性基の1.05当量である。また、共重合樹脂R-4は、共重合樹脂の水溶液の調製においてアンモニア水溶液中で溶解せず、当該アンモニア水溶液が白濁してしまったため、共重合樹脂R-4を含有するインク(K-22)は調製しなかった。
ノズル口径28μm、駆動周波数18kHz、ノズル数512、最小液滴量12pL、ノズル密度180dpiであるピエゾ型ヘッドを四列搭載したオンデマンド型インクジェットプリンタのヘッドの一つに、インクK-1を装填した。当該プリンタは、記録媒体をその裏面(ヘッドと対向する面とは反対の面)から任意に加温可能な接触式ヒータを有し、ヘッド格納ポジションにインク空打ちポジションとブレードワイプ式のメンテナンスユニットを備え、任意の頻度でヘッドクリーニングができるように構成されている。
第一細線画像部および第二細線画像部を肉眼で、また倍率10倍のルーペにより目視で観察し、細線間に余分な箔が存在しないことと、細線上における箔の欠落の有無とを、以下の基準で評価した。なお、以下、A、BおよびCを合格とし、Dを不合格とした。
A:二つの細線画像とも細線間に余分な箔が存在せず、かつ、細線上に箔の欠落がないことがルーペでの観察により認められる
B:幅0.5mmの細線画像上に微小な欠落が見られたが、肉眼観察では問題のないレベルである
C:部分的に細線間に余分な箔が残存していることが肉眼観察で認められたが、実用上許容範囲内である
D:細線間が完全に再現できないものが肉眼で確認される
30℃、80%RHの環境下に12時間放置した後の箔画像の箔部を、乾いた木綿の布(カナキン3号)で400gの荷重をかけて擦り、当該箔部の擦った面の状態を目視および倍率10倍のルーペで観察し、下記の基準に従って耐擦性を評価した。
A:50回以上擦っても、ルーペ観察で確認可能な微細な傷の発生や剥離が生じない
B:50回擦った段階で、ルーペ観察で確認可能な微細な傷の発生や剥離が生じるが、肉眼では問題ないレベルである
C:21~50回擦る間に、肉眼で確認可能な微細な傷の発生や剥離を起こしたものが確認されるが、実用上許容範囲内である
D:20回以下擦る間に、肉眼で剥離を確認される
30℃、80%RHの環境下に12時間放置した後に、箔画像における5cm×10cmのサイズのベタ画像部にテープ(住友スリーエム株式会社製「スコッチイメンディングテープ MP-18」)を貼り付け、その後、そのテープを手で剥がし、当該箔画像のテープを剥がした後の部分の状態を、肉眼および倍率10倍のルーペで観察し、以下の基準で接着強度を評価した
A:ルーペ観察で確認可能な微細な剥離が生じない
B:ルーペ観察で確認可能な微細な剥離が生じるものがあるが、肉眼では問題ないレベルである
C:肉眼観察で確認可能な微細な剥離が生じるものがあるが、実用上許容範囲内である
D:肉眼で剥離が確認できるものがある
3mm径のステンレス棒に箔画像を、箔画像を外側に向けて巻き付け、そのときの箔画像における箔の浮き、剥離、ひび割れなどの欠陥の発生具合を目視にて確認し、下記の基準により耐折り曲げ性を評価した。
A:巻き付けによる浮き、剥離、ひび割れが全く発生しない
B:10回以上巻き付けにより、軽度の浮き、剥離、ひび割れの発生が認められる
C:2回以上10回未満の巻き付けにより、軽度の浮き、剥離、ひび割れの発生が認められる
D:一度の巻き付けにより、明らかな浮き、剥離、ひび割れが発生する
活性光線硬化型インクジェットインクの材料として、以下のものを用いた。
ジステアリルケトン(カオーワックスT1、花王社製)、(18-Pentatriacontanone、試薬(Arfa Aeser)社製)
ベヘニン酸ベヘニル(ユニスター M-2222SL、日油社製)
ステアリン酸ステアリル(エキセパールSS、花王社製)、(ユニスター M-9676、日油社製)、(EMALEX CC-18、日本エマルジョン社製)、(アムレプスSS、高級アルコール工業社製)
ベヘニン酸(ルナックBA、花王社製)
ベヘニルアルコール(カルコール 220-80、花王社製)
パルミチン酸セチル(アムレプスPC、高級アルコール工業社製)
Photomer 4072(コグニス社製):3PO変性トリメチロールプロパントリアクリレート:分子量471
Miramer M360(Miwon社製):トリメチロールプロパンPO変性トリアクリレート:分子量471
NKエステルDOD-N(新中村化学社製):1,10-デカンジオールジメタクリレート:分子量310
NKエステルA-DCP(新中村化学社製):トリシクロデカンジメタノールジアクリレート:分子量304
NKエステルA-400(新中村化学社製):ポリエチレングリコールジアクリレート
CD561(Sartomer社製):アルコキシ化ヘキサンジオールジアクリレート
SR499(Sartomer社製):6EO変性トリメチロールプロパントリアクリレート
SR494(Sartomer社製):4EO変性ペンタエリスリトールテトラアクリレート
DAROCURE TPO(BASF社製)
ITX(DKSHジャパン社製)
TEGO AddBond LTH (EVONIK社製、水酸基とカルボキシル基含有ポリエステル樹脂、酸価16mgKOH/g、塩基価25mgKOH/g、数平均分子量2000~3000)
TEGO VARIPLUS SK (degussa社製、水酸基含有ケトン樹脂、酸価3mgKOH/g未満、塩基価325mgKOH/g、数平均分子量1000~1500)
下記表5の組成(質量比)に従い、各成分を混合し、これを80℃に加熱して攪拌した。得られた溶液の温度を保持したまま、ADVATEC社製テフロン(登録商標)3μmメンブランフィルターで濾過し、活性光線硬化型インクジェットインク1を調製した。
表5に示す組成とした以外は、合成例1と同様の方法で活性光線硬化型インクジェットインク2~12を調製した。
・活性光線硬化型インクジェットインクの塗布
合成例1で調製した活性光線硬化型インクジェットインクを、図6に示される箔画像形成装置のインク塗布ユニットのインクタンク118に充填した。当該活性光線硬化型インクジェットインクを、塩化ビニルからなる記録媒体(KJ特殊紙社製塩ビクロス用ベース紙、厚み1000μm)に液滴量14pl、印字速度0.5m/sec、射出周波数10.5kHz、印字率100%となる条件で連続吐出(駆動)させた。活性光線硬化型インクジェットインクの着弾時の記録媒体の温度は、25℃に調整した。温度の測定には、赤外線放射温度計「IR0510」(ミノルタ社製)を使用した。
図6に示されるような箔画像形成装置の箔転写ユニットの、箔送りだしスプール121に、転写箔(村田金箔社製BL2.8 2号金)をセットした。転写箔側のニップローラ(加熱ローラ)120には、長さ357mm、外径62mm、厚さ5mmのアルミニウム製基体上に厚さ1.5mmのシリコーンゴム層を配置したロールを使用した。
一方、記録媒体1側のニップローラ(加圧ローラ)120には、長さ357mm、外径52mm、厚さ5mmのアルミニウム製基体上に厚さ1.5mmのシリコーンゴム層を配置したロールを使用した。加熱ローラと加圧ローラのニップ幅は7mmとした。ニップにおける面圧は290kPaとした。
箔定着装置における通紙速度は、100mm/secとした。
剥離装置には、ロール径が10mmである剥離ローラを使用した。
加熱ローラの温度は、45℃とした。
記録媒体を、表6に示される記録媒体に変更、もしくは活性光線硬化型インクジェットインク着弾時の記録媒体の温度を、表6に示される温度に変更した以外は、実施例2-1と同様に箔画像を形成した。
活性光線硬化型インクジェットインクを、表6に示されるものに変更、もしくは記録媒体を、表6に示されるものに変更、もしくは活性光線硬化型インクジェットインク着弾時の記録媒体の温度を、表6に示される温度に変更した以外は、実施例2-1と同様に箔画像を形成した。
実施例2-1~2-5、及び比較例2-1~2-6で作製した箔層の細線再現性、接着強度、及び耐水性を以下のように評価した。評価結果を表6に示す。
幅2mmの線画を1.0mm幅間隔で通紙方向に対し縦(垂直)と横(平行)になるように配置した箔画像、及び、幅1mmの線画を0.5mm幅間隔で縦と横に配置した箔画像の二種類の細線画像を作成した。肉眼及び倍率10倍のルーペにより目視観察し、細線間に余分な箔が存在しないことと、細線上における箔の欠落の有無とを、以下の基準で評価した。◎、○、及び△を合格とし、×を不合格とした。
◎:2つの細線画像とも細線間に余分な箔が存在せず、かつ、細線上に箔の欠けがないことがルーペ観察で認められた
○: 幅0.5mmの細線画像上に微小な欠けが見られたが、肉眼観察では問題のないレベルであった
△:部分的に細線間に余分な箔が残存していることが肉眼観察で認められたが、実用上許容範囲内である
×:細線間が完全に再現できないものが肉眼で確認できた。実用上許容範囲外である
5cm×10cmの大きさに形成した箔画像(ベタパッチ画像)にテープを貼り付けた後、手でそのテープを剥がす。テープを剥がしたときの箔画像の状態を肉眼及び倍率10倍のルーペで観察して以下の基準で評価した。なお、テープには「スコッチメンディングテープ MP-18(住友スリーエム(株)製)」を使用した。
◎:ルーペ観察で確認可能な微細な剥離を起こしたものはなかった
○:ルーペ観察で確認可能な微細な剥離を起こしたものがあるが、肉眼では問題ないレベルと判断した
△;肉眼観察で確認可能な微細な空隙や剥離を起こしたものが確認できるものがあるが、実用上許容範囲内である
×;肉眼で剥離を確認できるものがあった。実用上許容範囲外である
5cm×10cmの大きさに形成した箔画像(ベタパッチ画像)を湿度80%Rh、温度40℃の環境下に5日間放置した。そして、当該環境から取り出した箔画像の表面を、肉眼及び倍率10倍のルーペにより目視観察して、箔画像表面における箔の欠落の有無を以下の基準で評価した。
◎:ルーペ観察で確認可能な微細な傷の発生や剥離を起こしたものはなかった
○:ルーペ観察で確認可能な微細な傷の発生や剥離を起こしたものがあるが、肉眼では問題ないレベルと判断した
△:肉眼で確認可能な微細な傷の発生や剥離を起こしたものが確認できるものがあるが、実用上許容範囲内である
×:肉眼で剥離を確認できるものがあった。実用上許容範囲外である
また特に、インク着弾時の記録媒体の温度とインクのゾルゲル相転移温度との差が35℃であると(実施例2-1~2-4)、いずれの記録媒体であっても、細線再現性が良好であった。記録媒体上でのインクのゲル化速度が高まり、インクが濡れ広がり難かったためと推察される。
活性光線硬化型インクジェットインク、もしくは活性光線硬化型インクジェットインク着弾時の記録媒体の温度を、表7に示される種類に変更した以外は、実施例2-1と同様に箔画像を形成した。
実施例2-7~2-15、及び比較例2-7~2-8で作製した箔層の細線再現性、接着強度、及び耐水性を以下のように評価した。評価結果を表7に示す。
2 インク画像
2’ 接着層
3 転写箔
4 支持材
5 箔層
5’ 箔層
10 箔画像形成装置
11 インクジェットヘッド
12 加熱ローラ
13 支持ローラ
14 剥離部材
15 巻き取りローラ
21 記録媒体
22 接着性インク
30 箔シート
31 ベースシート
32 箔
Claims (14)
- 記録媒体または箔シートの少なくとも一方に、形成すべき箔画像に応じた形状に、インクジェットプリント法によって接着性インクを塗布し、前記記録媒体および前記箔シートの箔を加熱圧着し、前記記録媒体から前記箔シートを剥がして、前記記録媒体に箔画像を形成する箔画像形成方法であって、
前記接着性インクは、水、水溶性有機溶剤、および共重合樹脂を含有し、
前記共重合樹脂は、(メタ)アクリル酸、および、炭素数が2~12のアルキル基を有する(メタ)アクリル酸アルキルエステル、を含むモノマーの共重合体であり、前記接着性インクにおいて分散または溶解しており、
前記共重合樹脂の酸価は、50~120mgKOH/gであり、
前記共重合樹脂のガラス転移温度は、30~110℃である、
箔画像形成方法。 - 前記モノマーにおける前記(メタ)アクリル酸アルキルエステルの含有量は、5~50質量%である、請求項1に記載の箔画像形成方法。
- 前記水溶性有機溶剤は、グリコールエーテル類、炭素数が4以上である1,2-アルカンジオール、および、β-アルコキシプロピオンアミド類、からなる群から選ばれる一以上である、請求項1または2に記載の箔画像形成方法。
- 前記接着性インクは、界面活性剤をさらに含有する、請求項1~3のいずれか一項に記載の箔画像形成方法。
- 前記接着性インクを塗布する前の前記記録媒体を35~100℃に加熱する工程をさらに含む、請求項1~4のいずれか一項に記載の箔画像形成方法。
- 前記記録媒体は、壁紙材である、請求項1~5のいずれか一項に記載の箔画像形成方法。
- 前記壁紙材は、天然パルプおよび合成繊維を混抄した不織布を含む、請求項6に記載の箔画像形成方法。
- 記録媒体上に、ゲル化剤、光重合性化合物、及び光重合開始剤を含み、温度によりゾルゲル相転移する活性光線硬化型インクジェットインクを滴下し、前記活性光線硬化型インクジェットインクの液滴からなるインク画像を形成する工程と、
箔層を含む転写箔の転写面を前記インク画像と圧着し、前記インク画像上に前記箔層を転写する工程と、
前記インク画像に活性光線を照射して、前記活性光線硬化型インクジェットインクを硬化させ、前記箔層を前記記録媒体上に定着させる工程と、を含み、
前記活性光線硬化型インクジェットインクが、前記ゲル化剤を前記活性光線硬化型インクジェットインクの全質量に対して0.5~10質量%含み、
前記活性光線硬化型インクジェットインクが着弾する際の前記記録媒体の温度と、前記活性光線硬化型インクジェットインクのゾルゲル相転移温度との差が30℃以上である、箔画像形成方法。 - 前記活性光線硬化型インクジェットインクが着弾する際の前記記録媒体の温度と、前記活性光線硬化型インクジェットインクのゾルゲル相転移温度との差が30℃以上70℃以下である、請求項8に記載の箔画像形成方法。
- 前記ゲル化剤が、下記一般式(1)または(2)で表される、請求項8または9に記載の箔画像形成方法。
R1-CO-R2 (1)
(一般式(1)において、R1及びR2は、それぞれ炭素数1~24の直鎖状または分岐鎖状の炭化水素基を表し、R1及びR2のうち、いずれか一方は、炭素数が12以上の直鎖アルキル構造を含む)
R3-COO-R4 (2)
(一般式(2)において、R3は、炭素数1~24の直鎖状または分岐鎖状の炭化水素基を表し、R4は水素原子または炭素数1~24の直鎖状または分岐鎖状の炭化水素基を表し、R3及びR4のうち、いずれか一方は、炭素数が12以上の直鎖アルキル構造を含む) - 前記記録媒体が、壁紙材である、請求項8~10のいずれか一項に記載の箔画像形成方法。
- 前記壁紙材が、天然パルプと合成繊維とを混抄した不織布を含む、請求項11に記載の箔画像形成方法。
- 記録媒体と、前記記録媒体上にパターン状に形成された接着層と、前記接着層上に形成された箔層とを有し、
前記接着層が、ゲル化剤、光重合性化合物、及び光重合開始剤を含み、温度によりゾルゲル相転移する活性光線硬化型インクジェットインクの硬化物からなる、積層体。 - 前記記録媒体が、壁紙材である、請求項13に記載の積層体。
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