WO2018066474A1 - Support d'enregistrement, enregistrement, et procédé de formation d'image - Google Patents

Support d'enregistrement, enregistrement, et procédé de formation d'image Download PDF

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Publication number
WO2018066474A1
WO2018066474A1 PCT/JP2017/035495 JP2017035495W WO2018066474A1 WO 2018066474 A1 WO2018066474 A1 WO 2018066474A1 JP 2017035495 W JP2017035495 W JP 2017035495W WO 2018066474 A1 WO2018066474 A1 WO 2018066474A1
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WIPO (PCT)
Prior art keywords
fatty acid
acid ester
pigment
recording medium
ink
Prior art date
Application number
PCT/JP2017/035495
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English (en)
Japanese (ja)
Inventor
牛久　正幸
金子　学
Original Assignee
コニカミノルタ株式会社
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Priority to JP2018543873A priority Critical patent/JP7028180B2/ja
Publication of WO2018066474A1 publication Critical patent/WO2018066474A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings

Definitions

  • the present invention relates to an inkjet recording medium, a recorded matter, and an image forming method.
  • a water-based ink applied by an ink-jet method containing water and a coloring material (hereinafter sometimes abbreviated as “ink” or “ink-jet ink”) is suitable for printing on a water-absorbing substrate such as paper.
  • a non-water-absorbing substrate such as a film has a problem that the adhesion is low, and the printed material has low resistance.
  • Patent Document 1 discloses that a fixing resin is contained in the ink in order to bring the water-based ink into close contact with a non-water-absorbing substrate such as a film.
  • sorbitan fatty acid ester or the like is included in the treatment liquid applied to the substrate before application of the inkjet ink.
  • Patent Document 2 describes that a sorbitan fatty acid ester may be included in a treatment liquid for improving the wettability of the surface of a recording medium.
  • Patent Document 3 also describes a pretreatment liquid containing sorbitan fatty acid ester.
  • the ink containing the fixing resin as described in Patent Document 1 has a great influence on the ink ejection characteristics in the ink jet method, and the nozzle is likely to be clogged by drying, so that frequent maintenance of the ink jet head is performed. It is necessary to take measures such as
  • the inventors of the present invention reduce or eliminate the fixing resin to be contained in the ink by recording on a recording medium pre-coated with a treatment liquid containing resin fine particles on a non-water-absorbing substrate by an inkjet method. Tried to consider.
  • the non-water-absorbing base material does not have an anchoring effect that allows the resin in the treatment liquid to penetrate into the base material, it is difficult to improve image adhesion.
  • the thickness of the recording layer is limited depending on the application, such as the resin layer formed by the resin fine particles in the processing solution affects the feel and rigidity.
  • a problem has been found in which cracks caused by storage under high temperature or high humidity and cracks caused by bending (hereinafter sometimes abbreviated as “cracking”) occur.
  • Patent Documents 2 and 3 describe that the base material is pre-coated with a treatment liquid, but nothing is mentioned about cracks and creases that are peculiar to the thin base material.
  • an object of the present invention is to provide an ink jet recording medium or recorded matter that can obtain image adhesion with less cracking and cracking defects on a non-water-absorbing substrate, and an image that can produce such a recorded matter. It is to provide a forming method.
  • a recording medium in which a recording layer containing at least resin fine particles is formed on a non-water-absorbing substrate, and the thickness of the recording layer after drying is 0.3 ⁇ m or more and 3.0 ⁇ m or less,
  • the recording medium further comprises at least one of glycerin fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid ester in the recording layer.
  • the recording medium according to [1] wherein the recording layer further contains a compound that causes the pigment to aggregate.
  • the compound that aggregates the pigment is water-soluble.
  • an ink jet recording medium or recorded matter that has no defect of cracking or folding with respect to a non-water-absorbing substrate and can provide image adhesion.
  • the recording medium of the present invention is a recording layer formed from a treatment liquid containing at least resin fine particles formed on a non-water-absorbent substrate, and after applying the treatment liquid by a method such as a roll coater, It can be created by drying the treatment liquid using hot air or an infrared heater.
  • Image recording can be performed by an ink application process in which an ink containing at least a pigment is applied onto the recording layer by an inkjet method, and an ink drying process in which the applied ink is dried and recorded.
  • the recording medium of the present invention is a recording medium in which a recording layer made of a treatment liquid containing at least resin fine particles is formed on a non-water-absorbing substrate, and the film thickness after drying of the recording layer is 0.3 ⁇ m or more, It is 3.0 ⁇ m or less, and the recording layer further contains at least one of glycerin fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid ester.
  • the recording medium of the present invention has an effect of obtaining good adhesion with few defects due to cracks and cracks.
  • the non-water-absorbing substrate in the present invention is not particularly limited as long as it is a substrate that does not substantially absorb water, such as plastic, plastic film, glass, and metal.
  • a plastic film hereinafter abbreviated as “film”
  • cracks accompanying deformation due to heat or the like are likely to occur, and the present invention can be applied more effectively.
  • the resin constituting the film is not particularly limited, but preferred examples include plastics such as polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate, polyamides such as nylon, and the like.
  • the film may be an unstretched film or a stretched film.
  • the surface of the film may be subjected to surface treatment such as corona treatment.
  • a treatment liquid containing at least resin fine particles is applied on the non-water-absorbing substrate.
  • the resin constituting the resin fine particles in the treatment liquid is not particularly limited.
  • a resin having a polyurethane structure hereinafter, sometimes abbreviated as a polyurethane resin or simply a urethane resin
  • a resin having a polyolefin structure e.g., a polyurethane resin having a polyolefin structure
  • an acrylic resin And so on e.g., acrylic resin having a polyurethane structure
  • resin fine particles made of a resin having a polyurethane structure for example, cationic or nonionic polyurethane resin fine particles can be preferably used.
  • cationic or nonionic polyurethane resin fine particles are given below.
  • the cationic polyurethane resin fine particles include “Superflex 620” and “Superflex 650” (“Superflex” is a registered trademark of the company) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “ “Permarin UC-20” (“Permarin” is a registered trademark of the company), “Parasurf UP-22” manufactured by Ohara Palladium Chemical Co., Ltd., and the like.
  • nonionic polyurethane resin fine particles include “Superflex 500M” and “Superflex E-2000” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • resin fine particles it is also preferable to use a resin having a polyolefin structure as the resin fine particles.
  • a resin having a polyolefin structure it is preferable to use in combination resin fine particles containing a resin having a polyurethane structure and resin fine particles containing a resin having a polyolefin structure.
  • Preferred examples of the resin fine particles containing a resin having a polyolefin structure include polypropylene resin fine particles.
  • resin fine particles containing a resin having a polyolefin structure particularly polypropylene resin fine particles, the effect of further improving the adhesion of a printed image to a hydrophobic substrate such as polyethylene or polypropylene can be obtained.
  • a polar group such as chlorine or a carboxyl group may be introduced into the resin having a polyolefin structure.
  • the average particle size of the resin fine particles is preferably in the range of 10 nm to 10 ⁇ m, more preferably in the range of 10 nm to 1 ⁇ m, further preferably in the range of 10 nm to 500 nm, and more preferably in the range of 10 nm to 300 nm. Is more preferable, and a range of 10 nm to 200 nm is more preferable.
  • the average particle size can be measured by a commercially available particle size measuring instrument using a dynamic light scattering method, an electrophoresis method, etc., but the measurement by the dynamic light scattering method is simple and the particle size region is Accurate measurement.
  • Resin fine particles may be used alone or in combination of two or more.
  • the content of the resin fine particles in the treatment liquid is preferably in the range of 5% by mass to 40% by mass, and more preferably in the range of 10% by mass to 30% by mass with respect to the mass of the treatment liquid.
  • the recording layer of the present invention is characterized by further containing at least one of glycerin fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid ester.
  • the glycerin fatty acid ester, polyglycerin fatty acid ester or sorbitan fatty acid ester promotes the transfer of the resin or the pigment flocculant described later to the vicinity of the pigment contained in the ink applied by the inkjet method, and the interface strength between the recording layer and the pigment It is presumed that the effect of increasing In particular, when the recording layer contains a pigment flocculant, the recording layer tends to be less flexible and the recording layer tends to be brittle, but the compound functions as a plasticizer and softens the recording layer. Conceivable.
  • the method for containing the glycerin fatty acid ester, polyglycerin fatty acid ester or sorbitan fatty acid ester in the recording layer is not particularly limited, and it may be contained in the recording layer.
  • a method of applying and drying a treatment liquid containing these to a non-water-absorbing substrate, a method of applying and drying a treatment liquid containing resin fine particles, and then overcoating a liquid containing these by a spray or ink jet method For example, a method in which these are added in advance to the film base and the bleed out from the base into the recording layer after application and drying of the treatment liquid can be suitably used.
  • the range of the total preferable content (attachment amount) of glycerin fatty acid ester, polyglycerin fatty acid ester or sorbitan fatty acid ester is 0.01 g / m 2 or more and 0.5 g / m 2 or less in terms of mass per square meter in the recording layer. . Since in order to obtain the effect of the present invention preferably contains 0.01 g / m 2 or more, it is possible to maintain the wettability of the ink during ink jet recording good by a 0.5 g / m 2 or less, uniform Easy image formation is facilitated.
  • the total content of glycerin fatty acid ester, polyglycerin fatty acid ester or sorbitan fatty acid ester is preferably 0.01 g / m 2 or more and 0.4 / m 2 or less.
  • the content of glycerin fatty acid ester, polyglycerin fatty acid ester or sorbitan fatty acid ester in the recording layer can be measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the compound include the following compounds, but are not limited thereto.
  • glycerin fatty acid ester stearic acid monoglyceride, palmitic acid monoglyceride, oleic acid monoglyceride, polyglycerin fatty acid ester as polyglycerin lauric acid ester, polyglycerin stearic acid ester, polyglycerin oleic acid ester, sorbitan fatty acid ester as monolaurin
  • Examples include sorbitan acid, sorbitan monostearate, sorbitan monooleate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monostearate.
  • the recording layer preferably further contains a compound that aggregates the pigment contained in the ink applied by the subsequent inkjet method (hereinafter also referred to as a pigment flocculant). Accordingly, it is possible to effectively suppress bleeding that occurs particularly during inkjet recording at high speed.
  • a pigment flocculant when an aqueous inkjet ink is used, it is preferable to use a water-soluble pigment flocculant. It is estimated that the water-soluble pigment flocculant increases the diffusion rate of the flocculant near the pigment.
  • the pigment contained in the ink is an anionic dispersion pigment
  • an acid or a cationic compound can be preferably used as the pigment flocculant, for example.
  • Acid can agglomerate the anionic disperse pigment in the ink by pH fluctuation.
  • the acid include formic acid, acetic acid, propionic acid, isobutyric acid, oxalic acid, fumaric acid, malic acid, citric acid, malonic acid, succinic acid, maleic acid, benzoic acid, 2-pyrrolidone-5-carboxylic acid, and lactic acid.
  • Acrylic acid or a derivative thereof, methacrylic acid or a derivative thereof, acrylamide or a derivative thereof, a sulfonic acid derivative, phosphoric acid or a derivative thereof can be preferably exemplified.
  • an organic acid can be preferably used rather than an inorganic acid. By using an organic acid, compatibility with other components such as a resin constituting the coating liquid can be improved. Further, even when the coating layer formed by the coating liquid is dried, it does not easily become a salt. Excellent effects can also be obtained.
  • the cationic compound can aggregate the anionic dispersed pigment in the ink by salting out.
  • the cationic compound include polyvalent metal salts, cationic surfactants, and cationic resins.
  • Preferred examples of the polyvalent metal salt include water-soluble salts such as calcium salts, magnesium salts, aluminum salts, and zinc salts.
  • the cationic surfactant also referred to as cationic surfactant
  • aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts and the like are preferable.
  • the cationic resin include polyallylamine, polyvinylamine, polyethyleneimine, and polydiallyldimethylammonium chloride.
  • Particularly preferred pigment flocculants are polyvalent metal salts or organic acids, and when the ink contains a polyvalent metal salt or organic acid, it is possible to suitably suppress bleeding that tends to occur particularly in high-speed printing in ink jet recording.
  • a pigment flocculant may be used alone or in combination of two or more.
  • the range of the content (attachment amount) of the pigment flocculant in the treatment liquid is not particularly limited, but in the case of a polyvalent metal salt, it is preferably 0.1 g / m 2 or more and 20 g / m 2 or less. In order to effectively suppress bleeding, it is preferable to contain 0.1 g / m 2 or more, and by setting it to 20 g / m 2 or less, folding can be effectively suppressed. In the case of using an acid, it is necessary to add an amount of acid that adjusts the pH of the treatment liquid below the neutralization equivalent of the anion component contained in the ink jet recording ink.
  • the first dissociation constant of the acid used in the treatment liquid is preferably 3.5 or less.
  • the content of the pigment flocculant in the recording layer can be measured by a known method.
  • the content can be measured by ICP emission analysis, and when the pigment flocculant is an acid, the content can be measured by high performance liquid chromatography (HPLC).
  • HPLC high performance liquid chromatography
  • the treatment liquid preferably contains water as a solvent, and can contain other known organic solvents.
  • the solvent can be removed by a subsequent recording layer drying step.
  • the treatment liquid can contain a surfactant.
  • a surfactant include a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.
  • Preferred examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
  • amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like.
  • nonionic surfactants include polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene Preferred examples include castor oil, hydrogenated castor oil, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, alkylamine oxide, acetylene glycol, and acetylene alcohol.
  • a cross-linking agent such as a cross-linking agent, an antifungal agent, and a bactericidal agent can be appropriately blended within the range not impairing the effects of the present invention.
  • the method for applying the treatment liquid onto the non-water-absorbing substrate is not particularly limited, but preferred examples include a roller coating method, a curtain coating method, a spray coating method, and an ink jet method.
  • the processing liquid applied on the film substrate is dried to form the recording layer.
  • the incomplete film formation state is a state where the resin fine particles remain or a state before the resin is completely mixed even if the resin fine particles are melted.
  • a recording layer in an incomplete film formation state is a sparse state in which there are relatively many gaps (boundaries) between resin polymers.
  • An incomplete film-formation precoat layer can be suitably formed by drying at a low temperature or in a short time rather than a condition in which resin fine particles melt and the resin is completely mixed.
  • An incomplete film formation state can be confirmed by using, for example, a polarizing microscope.
  • a non-contact heating type drying device such as a drying furnace or a hot air blower may be used, or a contact heating type drying device such as a hot plate or a heat roller is used. Also good.
  • the film thickness of the recording layer after drying is in the range of 0.3 ⁇ m to 3.0 ⁇ m.
  • the effect of the present invention is remarkably exhibited when the thickness of the recording layer is in the above conditions.
  • the film thickness is 0.3 ⁇ m or more, it is possible to suppress the adhesion of an ink jet recorded image and bleeding during high-speed recording while suppressing cracks and cracks.
  • the upper limit of the film thickness is not limited, but when it is thicker than 3.0 ⁇ m, it is difficult to cause cracks and creases, which is a problem, and the present application is used for applications in which the film thickness of the recording layer is thin as described above. The improvement method with respect to the subject of this is provided.
  • the film thickness of the recording layer is more preferably in the range of 0.3 ⁇ m or more and 2.0 ⁇ m or less in that the texture can be suitably prevented from changing.
  • “after drying” means a state in which resin fine particles do not clearly remain even when observed with a polarizing microscope or the like, and film formation does not proceed even after drying.
  • the film thickness of the recording layer can be measured by cross-sectional observation with an electron microscope (SEM, TEM, etc.) or an optical interference film thickness meter.
  • a recording product obtained by applying an ink containing at least a pigment to the recording layer of the recording medium of the present invention thus formed by an ink jet method and drying the applied ink is a non-water-absorbing group.
  • the material includes at least a region (A) where the resin fine particles and the color material are attached, and a region (B) where the resin fine particles are attached but does not substantially contain the color material.
  • Region (A) is a region to which the ink is applied, and region (B) is a portion in which the configuration of the recording medium is left without being applied with the ink.
  • the recording layer formed as described above is left at least in the region (B), and at least one of glycerin fatty acid ester, polyglycerin fatty acid ester, and sorbitan fatty acid ester is adhered.
  • Region (A) is probably the interface between the recording layer and the pigment because the glycerin fatty acid ester, polyglycerin fatty acid ester or sorbitan fatty acid ester facilitates the migration of the resin or pigment flocculant to the vicinity of the pigment contained in the ink. It is estimated that the strength is increasing.
  • the region (A) may contain at least one of the glycerin fatty acid ester, the polyglycerin fatty acid ester and the sorbitan fatty acid ester. May not be included.
  • the ink constituting the recorded matter will be described.
  • a coloring material particularly a pigment can be preferably used, and an ink containing at least an organic solvent and water can be preferably used.
  • a dye, a pigment, or a mixture thereof can be used as a color material. It is preferable to use a pigment in applications where water resistance of the recorded matter is required.
  • Examples of the dye include water-soluble dyes and disperse dyes.
  • Examples of water-soluble dyes include acid dyes, direct dyes, and basic dyes.
  • Examples of disperse dyes include colored polymers and colored waxes.
  • pigments conventionally known pigments can be used without particular limitation, and any of water-dispersible pigments, solvent-dispersible pigments and the like can be used.
  • organic pigments such as insoluble pigments and lake pigments, titanium oxide and carbon black Inorganic pigments such as can be preferably used. These pigments can be used, for example, in the state of being dispersed in the ink by a pigment dispersant.
  • the insoluble pigment is not particularly limited. , Diketopyrrolopyrrole and the like are preferable.
  • the organic pigment is not particularly limited, but the following can be preferably exemplified.
  • pigments used for yellow or orange include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 15: 3, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, C.I. I. And CI Pigment Yellow 155.
  • pigments used for magenta or red include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I.
  • Pigment red 166 C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 202, C.I. I. Pigment red 222, C.I. I. Pigment violet 19 and the like.
  • pigments used for cyan or green include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.
  • pigments used for black and the like include C.I. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7 and the like.
  • titanium oxide is an example of a pigment used for white.
  • the volume average particle diameter of the pigment dispersed in the ink is preferably in the range of 50 nm to 200 nm. Thereby, the dispersion stability of the pigment can be improved, and the storage stability of the ink can be improved.
  • the particle size of the pigment can be determined by a commercially available particle size measuring instrument using a dynamic light scattering method, an electrophoresis method, etc., but the measurement by the dynamic light scattering method is simple and the particle size region is Accurate measurement.
  • the pigment can be used after being dispersed by a disperser together with a pigment dispersant and other additives necessary for various desired purposes.
  • the disperser a conventionally known ball mill, sand mill, line mill, high-pressure homogenizer, or the like can be used. Among them, it is preferable to disperse the pigment by a sand mill because the particle size distribution becomes sharp.
  • the material of the beads used for sand mill dispersion is not particularly limited, but zirconia or zircon is preferable from the viewpoint of preventing generation of bead fragments and contamination of ionic components. Further, the bead diameter is preferably 0.3 mm or more and 3.0 mm or less.
  • the pigment content in the ink is not particularly limited.
  • the inorganic pigment is preferably in the range of 7% by mass to 18% by mass, and the organic pigment is in the range of 0.5% by mass to 7% by mass. It is preferable that
  • an anionic dispersion pigment As the pigment.
  • the anionic dispersed pigment include a pigment having an anionic group introduced on the surface, a pigment dispersed with a pigment dispersant having an anionic group, and the like.
  • Preferred examples of the anionic group include a carboxyl group and a sulfonic acid group.
  • the anionic group is preferably neutralized with alkali.
  • alkali that neutralizes the anionic group include metal base compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide, organic amines such as ammonia, triethylamine, pyridine, morpholine, and monoethanol.
  • metal base compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide
  • organic amines such as ammonia, triethylamine, pyridine, morpholine, and monoethanol.
  • alkanolamines such as amines.
  • a polymer dispersant having an acid value (also referred to as a resin dispersant) can be preferably used.
  • the acid value is not particularly limited, but is preferably in the range of 50 mgKOH / g to 250 mgKOH / g.
  • an acrylic dispersant can be preferably used.
  • the acrylic dispersant one or more selected from poly (meth) acrylic acid and (meth) acrylic acid copolymers can be suitably used.
  • the acrylic dispersant contains (meth) acrylic acid as a monomer component.
  • an acrylic dispersant a copolymer of (meth) acrylic acid (ie, poly (meth) acrylic acid) or a copolymer obtained by copolymerizing other monomer components such as styrene as needed (ie, (meth)) (Acrylic acid copolymer) can be preferably used.
  • acrylic dispersant examples include “Joncrill 819” manufactured by BASF (“Johncrill” is a registered trademark of the company) (acid value 75 mgKOH / g), “Johncrill 67” (acid value 213 mgKOH / g), and the like. Commercial products can be used.
  • a pigment dispersant may be used alone or in combination of two or more.
  • an organic solvent to be contained in the ink it is preferable to contain an organic solvent to be contained in the ink, and for example, a water-soluble organic solvent can be preferably used.
  • water-soluble organic solvent examples include monohydric alcohols, glycols (dihydric alcohols), trihydric alcohols, glycol ethers, acetates, amines, amides, and the like.
  • Preferred examples of monohydric alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, and tertiary butanol.
  • glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having 5 or more ethylene oxide groups, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and propylene oxide groups.
  • Polypropylene glycol, butylene glycol, thiodiglycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,2-hexanediol 1,2-heptanediol, 3-methyl-2,4-pentanediol and the like can be preferably exemplified.
  • trihydric alcohols include glycerin and hexanetriol.
  • glycol ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipro Lenglycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether
  • acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol diacetate and the like.
  • amines examples include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, Preferable examples include pentamethyldiethylenetriamine and tetramethylpropylenediamine.
  • amides include 2-pyrrolidinone, dimethylimidazolidinone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide and the like.
  • the solvents may be used alone or in combination of two or more.
  • the resin contained in the recording layer in the recording medium is a polyolefin resin or a copolymer resin having a polyolefin component
  • the most solvent contained in the ink is glycols. Swelling and dissolution of the resin can be suppressed, and good adhesion can be obtained.
  • the most solvent contained in the ink refers to a solvent having the largest blending amount (mass basis) in the ink if the ink contains a plurality of kinds of solvents, and the ink is a single solvent alone. If it is contained, it refers to the solvent.
  • the ink preferably contains a surfactant in order to improve dischargeability and wettability.
  • the surfactant is not particularly limited, and examples thereof include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant.
  • Preferred examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
  • anionic surfactant examples include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl- ⁇ -alanine salt, N-acyl glutamate, acylated peptide, alkyl sulfonic acid Salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfoacetate, ⁇ -olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol sulfate, secondary Higher alcohol sulfate, alkyl ether sulfate, secondary higher alcohol ethoxysulfate, polyoxyethylene alkylphenyl ether sulfate, monoglyculate, fatty acid alkylolamide sulfate, alkyl ether phosphate ester, alkyl Preferred examples include phosphoric acid ester salts
  • amphoteric surfactant examples include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like.
  • nonionic surfactant examples include polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene.
  • Glycerin fatty acid ester polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanol Amides, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, alkylamines Kisaido, acetylene glycol can be exemplified preferably acetylene alcohol.
  • surfactants may be used alone or in combination of two or more.
  • the content of the surfactant in the ink is not particularly limited, but is preferably in the range of 0.1% by mass to 5.0% by mass.
  • the ink does not substantially contain the resin fine particles described for the precoat liquid. “Substantially not contained” means that the content of the resin fine particles is 5% by mass or less with respect to the ink mass. The content of the resin fine particles is more preferably 3% by mass or less, and most preferably 2% by mass or less based on the ink mass. As a result, it is possible to stabilize ink ejection characteristics in the ink jet method and to effectively prevent nozzle clogging.
  • an ink containing at least a pigment is applied to the recording medium by an ink jet method.
  • the ink applied on the recording layer is dried.
  • a non-contact heating type drying device such as a drying furnace or a hot air blower may be used, or a contact heating type drying device such as a hot plate or a heat roller may be used. Good.
  • the ink jet method used when applying the ink described above to the recording medium is not particularly limited, and a printer including an ink jet head loaded with ink can be used. Specifically, it is possible to perform printing by ejecting ink as droplets from the nozzles of an inkjet head based on digital signals and landing them on a precoat layer of a recording medium.
  • the inkjet head may be either an on-demand system or a continuous system.
  • an electro-mechanical conversion method for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.
  • an electro-thermal conversion method for example, any system such as a thermal ink jet type or a bubble jet (“Bubble Jet” is a registered trademark of Canon Inc.) may be used.
  • an ink jet head (also referred to as a piezo ink jet head) using a piezoelectric element as the electro-mechanical conversion element used in the electro-mechanical conversion system is suitable.
  • the non-water-absorbing substrate When using a film as the non-water-absorbing substrate, it is preferable to use a single-pass inkjet image forming method in view of the fact that many common films are distributed in roll form.
  • the effect of the present invention is particularly remarkable in the single-pass inkjet image forming method. That is, when the single-pass inkjet image forming method is used, the above-described cracks and creases are particularly likely to occur due to the pigment flocculant used to suppress ink bleeding, but according to the present invention, Even in this case, it is possible to achieve both high-definition image formation and suppression of cracks and cracks.
  • ink droplets are applied to all pixels where dots should be formed in one pass.
  • a line head type ink jet head as means for achieving a single pass type ink jet image forming method.
  • the line head type inkjet head refers to an inkjet head having a length longer than the width of the printing range.
  • a single head having a width larger than the print range may be used, or a plurality of heads may be combined so as to be larger than the width of the print range.
  • the recording medium, recorded matter, and image forming method of the present invention can be suitably used for various uses for printing on a recording medium comprising a non-water-absorbing substrate by an ink jet method.
  • the application of the present invention is not particularly limited.
  • a packaging film for packaging food, beverages, and the like can be preferably exemplified.
  • (Test 1) Formation of recording medium (1) Preparation of treatment liquid Polypropylene resin fine particles (solid content concentration 24.8% by mass, “Supercron E-415” manufactured by Nippon Paper Industries Co., Ltd.) 17.3 parts by mass, cationic resin having polyurethane structure 33.4 parts by weight of fine particles (solid content concentration 30.0% by weight, “Superflex 620” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), sorbitan fatty acid ester (“Reodol TW-L120” (“Reodol” manufactured by Kao Corporation) (Registered trademark of the company)) 0.86 parts by mass, ion-exchanged water (remainder: the total amount is 100 parts by mass) was added sequentially with stirring, and then filtered through a 5.0 ⁇ m filter to obtain a treatment solution. It was. There was no substantial change in composition before and after filtration.
  • a wire bar is used on a biaxially stretched polypropylene film (abbreviated as OPP film) (“Furamura Polypropylene Film FO # 50-FOS” manufactured by Framura Chemical Co., Ltd.), which is a non-water-absorbing substrate. Application was performed under conditions of a wet film thickness of 7 ⁇ m.
  • OPP film biaxially stretched polypropylene film
  • Process liquid drying process The process liquid apply
  • Two independent drive inkjet heads (360 dpi, discharge amount 14 pL) manufactured by Konica Minolta Co., Ltd. were arranged in parallel so that the nozzles were staggered, and a head module capable of printing a 720 dpi ⁇ 720 dpi image by a single pass method was created.
  • Two such head modules were prepared and arranged in parallel along the transport direction of the transport stage for transporting the recording medium. Each head module was installed so as to intersect the transport direction (moving axis of the transport stage). In this way, when the recording medium is passed once, a printing rate of 200%, that is, an ink amount for two colors (22.5 cc / m 2 ) can be printed. Ink 1 was used as the ink.
  • a recording medium was stuck on the conveying stage, and the recording medium was conveyed at a speed of 60 m / min, 30 m / min, and 5 m / min, and an image was printed by a single pass method when the recording medium passed under the head.
  • an image was printed in which a letter of size 6 points was placed in a 7 cm square solid with an ink application amount of 22.5 cc / m 2 .
  • Test 2 The sorbitan fatty acid ester used in the treatment liquid in Test 1 was changed to another 10% ethanol solution of “Emazole O-10V” (“Emazole” is a registered trademark of the company) manufactured by Kao Corporation as another sorbitan fatty acid ester. Test 2 was conducted in the same manner except that the amount was 8.6 parts by mass.
  • Test 3 The sorbitan fatty acid ester used in the treatment liquid in Test 1 was changed to a 10% ethanol solution of glycerin fatty acid ester (“Excel O-95R” manufactured by Kao Corporation (“Excel” is a registered trademark of the company)) The test 3 was conducted in the same manner except that 8.6 parts by mass.
  • Test 4 The test was performed in the same manner except that the sorbitan fatty acid ester used in the treatment liquid in Test 1 was changed to polyglycerin fatty acid ester ("Poem J-0081HV" manufactured by Riken Vitamin Co., Ltd. ("Poem” is a registered trademark of the company)). 4 was done.
  • Test 5 was conducted in the same manner except that the sorbitan fatty acid ester used in the treatment liquid in Test 1 was not used.
  • Test 6 was carried out in the same manner except that 4.3 parts by mass of calcium acetate monohydrate was added to the treatment liquid as a compound for aggregating the pigment in Test 1, and the amount of ion-exchanged water was adjusted to 100 parts by mass. Went.
  • Test 7 was conducted in the same manner except that the calcium acetate monohydrate used in the treatment liquid in Test 6 was changed to magnesium chloride.
  • Test 8 was conducted in the same manner except that the calcium acetate monohydrate used in the treatment liquid in Test 6 was changed to malonic acid.
  • Tests 9 and 10 In tests 6 and 8, tests 9 and 10 were carried out in the same manner except that the sorbitan fatty acid ester used in the treatment liquid was omitted.
  • Tests 11-13 Except that the addition amount of the sorbitan fatty acid ester used in the treatment liquid in Test 6 was changed to 0.14 parts by mass in the same manner as in Test 11, and the addition amount of the sorbitan fatty acid ester was similarly changed to 2.87 parts by mass. Test 12 was conducted in the same manner, and Test 13 was conducted in the same manner except that the addition amount of sorbitan fatty acid ester was changed to 7.17% by mass.
  • Tests 14-16 Tests 14, 15 and 16 were carried out in the same manner except that the sorbitan fatty acid esters used in the treatment solutions in Tests 11, 12 and 13 were each changed to polyglycerol fatty acid esters (“Poem J-0081HV” manufactured by Riken Vitamin Co., Ltd.). Went.
  • Test 17 was conducted in the same manner except that the wire bar used in the treatment liquid coating process of Test 6 was changed and the wet film thickness was 19 ⁇ m.
  • Test 18 was conducted in the same manner except that the addition amount of polypropylene resin fine particles was changed to 7.9 parts by mass and the addition amount of cationic resin fine particles having a polyurethane structure was changed to 15.2 parts by mass in the preparation of the treatment liquid of Test 6. It was.
  • Test 19 In the treatment liquid preparation of Test 6, the addition amount of polypropylene resin fine particles was 4.7 parts by mass, the addition amount of cationic resin fine particles having a polyurethane structure was 9.1 parts by mass, and the addition amount of sorbitan fatty acid ester was 0.29 masses. Test 19 was conducted in the same manner except that the part was changed to the same part.
  • Tests 20-22 Tests 20, 21 and 22 were conducted in the same manner except that the sorbitan fatty acid esters used in the treatment liquids in Tests 17, 18 and 19 were removed.
  • Test 23 was conducted in the same manner except that the polypropylene resin fine particles used in the treatment liquid and the cationic resin fine particles having a polyurethane structure were not used in Test 6.
  • the recording medium of the present invention using the treatment liquid containing resin fine particles and any one of glycerin fatty acid ester, polyglycerin fatty acid ester or sorbitan fatty acid ester (abbreviated as ester compound in Table 1) is cracked against bending. It can be seen that the film has good crack resistance against high humidity storage after inkjet recording. In particular, in tests 6, 7, 8, and 11 to 19 using a treatment liquid further containing a pigment flocculant, it can be seen that bleeding can be suppressed in higher-speed inkjet recording.
  • a high-quality image can be formed by an inkjet method using water-based ink on a non-water-absorbing substrate such as a film.
  • a non-water-absorbing substrate such as a film.
  • the present invention is expected to contribute to the widespread use of the inkjet method in this field by expanding the compatible range of image formation using water-based ink by the inkjet method.

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  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention a pour objet de fournir un support d'enregistrement pour jet d'encre qui permet d'obtenir un enregistrement présentant une adhésion élevée d'une image peu endommagée par des fissures ou des fissures par pliage, sur un matériau de base n'absorbant pas l'eau. En outre, l'invention concerne un enregistrement dans lequel une couche d'enregistrement comprenant au moins des microparticules de résine est formée sur le matériau de base n'absorbant pas l'eau. Ladite couche d'enregistrement présente une épaisseur après séchage supérieure ou égale à 0,3μｍ et inférieure ou égale à 3,0μｍ, et comprend au moins un ester d'acide gras de glycérine, un ester d'acide gras de polyglycérine et un ester d'acide gras de sorbitane.
PCT/JP2017/035495 2016-10-06 2017-09-29 Support d'enregistrement, enregistrement, et procédé de formation d'image WO2018066474A1 (fr)

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JP2018122589A (ja) * 2017-02-01 2018-08-09 東洋インキＳｃホールディングス株式会社 前処理液、及び前記前処理液を含むインキセット
JP2018122588A (ja) * 2017-10-05 2018-08-09 東洋インキＳｃホールディングス株式会社 前処理液、及び前記前処理液を含むインキセット
JP6388243B1 (ja) * 2017-12-25 2018-09-12 東洋インキＳｃホールディングス株式会社 前処理液、及び前記前処理液を含むインキセット
WO2020218612A1 (fr) * 2019-04-26 2020-10-29 富士フイルム株式会社 Composition d'encre pour enregistrement par jet d'encre, jeu d'encres, et procédé d'enregistrement d'image

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JP2018122589A (ja) * 2017-02-01 2018-08-09 東洋インキＳｃホールディングス株式会社 前処理液、及び前記前処理液を含むインキセット
JP7030262B2 (ja) 2017-02-01 2022-03-07 東洋インキＳｃホールディングス株式会社 前処理液、及び前記前処理液を含むインキセット
JP2018122588A (ja) * 2017-10-05 2018-08-09 東洋インキＳｃホールディングス株式会社 前処理液、及び前記前処理液を含むインキセット
JP6388243B1 (ja) * 2017-12-25 2018-09-12 東洋インキＳｃホールディングス株式会社 前処理液、及び前記前処理液を含むインキセット
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WO2020218612A1 (fr) * 2019-04-26 2020-10-29 富士フイルム株式会社 Composition d'encre pour enregistrement par jet d'encre, jeu d'encres, et procédé d'enregistrement d'image

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