WO2019187704A1 - Pretreatment agent composition, method for producing pretreatment agent composition, recording medium, method for producing recording medium, and recording method - Google Patents

Pretreatment agent composition, method for producing pretreatment agent composition, recording medium, method for producing recording medium, and recording method Download PDF

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Publication number
WO2019187704A1
WO2019187704A1 PCT/JP2019/004743 JP2019004743W WO2019187704A1 WO 2019187704 A1 WO2019187704 A1 WO 2019187704A1 JP 2019004743 W JP2019004743 W JP 2019004743W WO 2019187704 A1 WO2019187704 A1 WO 2019187704A1
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Prior art keywords
pretreatment
pretreatment agent
substrate
ink
water
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PCT/JP2019/004743
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French (fr)
Japanese (ja)
Inventor
悠人 榎本
Original Assignee
株式会社Ｓｃｒｅｅｎホールディングス
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Publication of WO2019187704A1 publication Critical patent/WO2019187704A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • the present invention relates to a pretreatment composition, a recording method, a recording medium, and a manufacturing method of the recording medium. More specifically, the present invention can impart excellent ink fixing properties and bleeding resistance to a substrate with low ink absorbability, such as an aluminum substrate or a soft packaging material, and further better adhesion.
  • the present invention relates to a pretreatment agent composition, a recording method, a recording medium, and a recording medium manufacturing method capable of forming a pretreatment layer that can be used for surface printing.
  • Aluminum base materials and soft packaging materials are very often used for the purpose of packaging things that people use, such as pharmaceuticals and food. For this reason, manufacturers are working to make the ink used for printing on these products excellent in environmental sanitation without affecting the human body. As an example, attention is focused on printing by an ink jet method using a water-based ink containing no monomer.
  • a hydrophobic substrate since the surface of an aluminum substrate or a soft packaging film (hereinafter referred to as a hydrophobic substrate) is hydrophobic, unlike paper, the water-based ink has low absorbability. For this reason, it is difficult for the water-based ink to be fixed on the hydrophobic substrate, and bleeding and beading due to the water-based ink are generated. Therefore, an ink permeation layer or ink receiving layer called a primer layer (pretreatment layer) is provided on the hydrophobic substrate, thereby allowing the water-based ink to be fixed to the hydrophobic substrate.
  • a primer layer pretreatment layer
  • the ink permeation layer has an effect that the water-based ink does not remain on the surface of the hydrophobic substrate by allowing the water-based ink to permeate the ink permeation layer.
  • the ink receiving layer contains a cationic substance, a metal salt, or a water-soluble resin, and these have an effect of fixing the water-based ink.
  • the printing method on the substrate is roughly divided into back printing and surface printing.
  • reverse printing after printing on the back surface of a substrate, an adhesive or an anchor coat agent is applied, and a resin or a film is bonded by dry lamination or extrusion lamination. Therefore, the scratch resistance and water resistance on the printed surface are not required to be large.
  • surface printing requires direct printing on the surface of the substrate and does not perform lamination or the like, and therefore requires scratch resistance and water resistance on the printed surface. That is, when surface printing is performed, the pretreatment layer is also required to have scratch resistance and water resistance.
  • the resin material is preferably dissolved in a solvent from the viewpoint of scratch resistance and water resistance.
  • a solvent from the viewpoint of scratch resistance and water resistance.
  • an acidic solvent or a basic solvent in accordance with the properties of the resin material.
  • an acidic solvent or a basic solvent there is a problem that aggregation or sedimentation occurs when a metal salt or an acid that is a component responsible for fixing the pretreatment layer and the aqueous ink to the base material is blended. is there.
  • the present invention has been made in view of the above problems, and one object thereof is to satisfactorily fix the ink while suppressing the occurrence of bleeding and beading, exhibit good adhesion to the substrate, and
  • An object of the present invention is to provide a pretreatment composition capable of forming a pretreatment layer that can be used for surface printing and a method for producing the same.
  • Another object of the present invention is to provide a recording medium using the pretreatment composition as described above, a method for producing the same, and a recording method.
  • One embodiment of the present invention provides a pretreatment composition for performing pretreatment on at least one surface of a substrate.
  • This pretreatment agent composition includes at least one poorly water-soluble and / or water-insoluble resin, alcohols, and at least one polyvalent metal salt.
  • the content of the resin is 0.1% by mass to 30% by mass with respect to the total mass of the pretreatment agent composition.
  • the content of the polyvalent metal salt is 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition.
  • This pretreatment composition for example, in image formation on a substrate, fixes ink well while suppressing the occurrence of bleeding and beading, exhibits good adhesion to the substrate, and is printed on the surface. It is possible to form a pretreatment layer that can handle printing.
  • the method for producing a pretreatment composition includes a step of dissolving a at least one poorly water-soluble and / or water-insoluble resin in alcohols to produce a resin solution, A step of dissolving at least one polyvalent metal salt in a solvent to produce a polyvalent metal salt solution, and a step of mixing the resin solution and the polyvalent metal salt solution.
  • the ink is satisfactorily fixed while suppressing occurrence of bleeding and beading, good adhesion to the base material, and surface printing. It is possible to produce a pretreatment agent composition capable of forming a pretreatment layer that can cope with the above.
  • one Embodiment of this invention provides the recording medium containing a base material and the pre-processing layer provided on the at least one surface of the said base material.
  • at least a part of the pretreatment layer comprises a dry film of a pretreatment agent.
  • the pretreatment agent includes at least one poorly water-soluble and / or water-insoluble resin, alcohols, and at least one polyvalent metal salt, and the content of the resin is the pretreatment agent.
  • the content of the polyvalent metal salt is 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition. It consists of a pretreatment composition.
  • This recording medium has a pretreatment layer that fixes ink well while suppressing the occurrence of bleeding and beading during image formation, exhibits good adhesion to a substrate, and is compatible with surface printing. Can have.
  • a recording medium manufacturing method includes a base material and a pretreatment layer provided on at least one surface of the base material, and on the at least one surface of the base material. And a pretreatment agent forming step for applying a pretreatment agent, and a pretreatment layer forming step for drying the pretreatment agent applied in the pretreatment agent application step to form a pretreatment layer.
  • the pretreatment agent includes at least one poorly water-soluble and / or water-insoluble resin, alcohols, and at least one polyvalent metal salt, and the content of the resin is the pretreatment agent.
  • the content of the polyvalent metal salt is 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition. It consists of a pretreatment composition.
  • the recording method includes a pretreatment agent application step of applying a pretreatment agent on at least one surface of a substrate, and the pretreatment applied in the pretreatment agent application step.
  • the recording method includes a pretreatment agent application step for applying a pretreatment agent on at least one surface of a substrate, and the pretreatment agent applied in the pretreatment agent application step.
  • a pretreatment layer forming step for forming a pretreatment layer, a second ink application step for applying ink to the pretreatment layer formed by the pretreatment layer formation step, and the second ink application step And forming an image by drying the ink applied in step (b).
  • the pretreatment agent includes at least one poorly water-soluble and / or water-insoluble resin, alcohols, and at least one polyvalent metal salt, and the content of the resin is the pretreatment agent.
  • the content of the polyvalent metal salt is 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition. It consists of a pretreatment composition.
  • the ink is satisfactorily fixed while suppressing the occurrence of bleeding and beading, forming a pretreatment layer that exhibits good adhesion to the substrate and can be used for surface printing.
  • the image can then be recorded on the substrate.
  • the pretreatment composition of the present embodiment is used for pretreatment of a substrate before an image is printed (formed). That is, the pretreatment agent composition is used as a constituent material of a pretreatment layer formed on a substrate by pretreatment. Details of the substrate and the pretreatment layer will be described later.
  • An image is formed with water-based ink on the base material on which the pretreatment layer is formed.
  • the fixability of the water-based ink to the recording medium is improved.
  • “Fixability” means the fixing stability of an aqueous ink after an image is formed on a recording medium. When the fixing property is good, the occurrence of image beading, bleeding, color unevenness, and the like can be suppressed.
  • peel resistance means performance capable of suppressing peeling of a part or all of the pretreatment layer formed on the surface of the recording medium from the surface of the recording medium.
  • Abrasion resistance means performance capable of suppressing scratches on the pretreatment layer formed on the surface of the recording medium. Due to the high peel resistance and scratch resistance of the pretreatment layer in the recording medium, the peel resistance and scratch resistance to the recording medium are improved even in a printed image formed on the recording medium. Furthermore, when the pretreatment composition itself has water resistance, the pretreatment layer formed on the substrate is not affected by moisture. For this reason, it is possible to suppress the quality change of the printed image formed on the recording medium.
  • the pretreatment composition according to the present embodiment includes a poorly water-soluble and / or water-insoluble resin (hereinafter collectively referred to as “resin material”), an alcohol, and at least one polyvalent metal salt. At least.
  • a pretreatment agent composition in order to provide the wettability with respect to a base material to a pretreatment agent composition, contains a surface tension regulator as needed.
  • Resin material contributes to improvement in adhesion of the pretreatment composition or the pretreatment layer to the base material.
  • the resin material exists in a dissolved state in the pretreatment composition.
  • the pretreatment layer can be formed only by drying the film of the pretreatment agent composition, film formation is easy.
  • the film is formed by volatilization of the solvent, a high-strength film (pretreatment layer) can be formed.
  • the pretreatment agent comprising the pretreatment agent composition is ejected by the ink jet method, clogging of the nozzle can be prevented, so that the occurrence of ejection failure can be suppressed.
  • the “dissolved state” means a state of a solution in which the resin material is uniformly mixed with a solvent.
  • the water-insoluble resin and the water-insoluble resin are not particularly limited, but shellac resin, casein, vinyl acetate resin, acrylic resin, and rosin resin are preferable examples.
  • “Slightly water-soluble” means that 15 g or more is not dissolved (more preferably, 5 g or more is not dissolved) in 100 g of water at 25 ° C.
  • “Water-insoluble” means that 1 g or more is not dissolved in 100 g of water at 25 ° C.
  • shellac Commercial products can be used as shellac. Examples of such commercially available products include dry transparent white rack (Bleached DewaxedxShellac), NSC, rack glaze 50E (LACGLAZE), rack coat 50 (LACCOAT) (product) Names are all manufactured by Nippon Shellac Industrial Co., Ltd.
  • the resin materials exemplified above can be contained alone or in combination of two or more in the pretreatment composition as necessary.
  • the content of the resin material is in the range of 0.1% by mass to 30% by mass with respect to the total mass of the pretreatment agent composition, preferably 1% by mass to 20% by mass, more preferably 5% by mass to 10% by mass. It is the range of mass%.
  • other resin than the above resin material may be contained as long as it is within the range of the above resin material content.
  • the pretreatment composition of the present embodiment contains alcohols as the main solvent for the resin material.
  • alcohols lower alcohols are preferably used, primary alcohols are more preferably used, and ethanol or methanol is preferably used. Further, the content of the alcohol is not particularly limited as long as the resin material is completely dissolved.
  • the polyvalent metal salt contributes to the improvement of the fixability of the pretreatment composition or the pretreatment layer and the water-based ink.
  • the polyvalent metal salt means a divalent or higher polyvalent metal ion and an anion that binds to these polyvalent metal ions.
  • the polyvalent metal salt is a compound that is soluble in water, and exists in a dissolved state in the pretreatment agent composition.
  • the dissolved state means a state in which a polyvalent metal salt is uniformly mixed with a solvent such as water.
  • the polyvalent metal salt is at least one metal salt selected from the group consisting of magnesium salt, aluminum salt, calcium salt, titanium salt, manganese salt, iron salt, nickel salt, copper salt, zinc salt, tin salt and barium salt It is. These polyvalent metal salts may be either inorganic metal salts or organic metal salts. More specifically, the polyvalent metal salt is, for example, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, aluminum chloride, aluminum bromide, aluminum sulfate, aluminum nitrate, aluminum acetate, calcium chloride, calcium bromide.
  • the content of the polyvalent metal salt is in the range of 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition, preferably 0.1% by mass to 5.0% by mass, more preferably The range is from 0.1% by mass to 2.0% by mass.
  • water is contained as the main solvent for the polyvalent metal salt.
  • water it is preferable to use water from which ionic impurities have been removed.
  • pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water is preferable.
  • water sterilized by ultraviolet irradiation or addition of hydrogen peroxide or the like is preferable because generation of mold and bacteria can be prevented over a long period of time.
  • the water content is not particularly limited as long as the polyvalent metal is completely dissolved.
  • additives can be appropriately contained as necessary.
  • the additive include a surface tension adjuster (surfactant), a pH adjuster, a viscosity adjuster, a softener, a gloss imparting agent, waxes, a dispersant, a flow modifier, a stabilizer, an antistatic agent, Crosslinking agents, surface sizing agents, fluorescent brighteners, colorants, ultraviolet absorbers, antifoaming agents, water resistance agents, plasticizers, lubricants, preservatives, and fragrances can be mentioned.
  • the content of these additives is not particularly limited, and can be set as necessary. The content of the surface tension adjusting agent will be described later.
  • the addition of the surface tension adjusting agent can control the wettability of the pretreatment agent composition with respect to the substrate surface and aqueous ink.
  • the wettability with respect to the substrate surface can be increased, and the occurrence of coating unevenness can be prevented.
  • a printer component capable of making the surface tension of the pretreatment agent appropriate and contacting with a pretreatment agent such as a head nozzle surface;
  • the interfacial tension can be made appropriate. As a result, it is possible to improve the discharge failure of the nozzle due to the collapse of the meniscus.
  • the surface tension adjusting agent is not particularly limited, and examples thereof include nonionic surfactants, silicon surfactants, fluorine surfactants, acetylenic diol surfactants, and acrylic surfactants. These surface tension modifiers may be used alone or in combination of two or more.
  • the nonionic surfactant is not particularly limited.
  • polyoxyethylene secondary alcohol ether polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether , 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 alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, Le Kill amine oxide, acetylene glycol, acetylene alcohol, and the like.
  • the silicon-based surfactant is not particularly limited, and examples thereof include polyether-modified polysiloxane compounds. However, it is not preferable to use a silicon surfactant alone as the surface tension adjusting agent. This is because the adhesion of the pretreatment layer to the substrate is lowered and the pretreatment layer may be peeled off.
  • the fluorosurfactant is not particularly limited, and examples thereof include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate esters, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoro.
  • examples include alkylamine oxide compounds.
  • the acrylic surfactant is not particularly limited, and examples thereof include (meth) acrylic acid copolymers.
  • a (meth) acrylic acid copolymer means an acrylic acid copolymer and a methacrylic acid copolymer.
  • the content of the surface tension adjusting agent is not particularly limited, but is set in consideration of the wettability of the pretreatment agent composition with respect to the substrate.
  • the content of the surface tension adjusting agent is preferably set in consideration of the wettability of the water-based ink applied on the pretreatment layer with respect to the pretreatment layer.
  • the content of the surface tension adjusting agent is usually preferably in the range of 0.01% by mass to 3.0% by mass, and in the range of 0.05% by mass to 2% by mass with respect to the total mass of the pretreatment agent composition. More preferably, the range of 0.1% by mass to 1% by mass is particularly preferable.
  • the surface tension of the pretreatment composition at 25 ° C. is preferably in the range of 25 mN / m to 35 mN / m, more preferably in the range of 26 mN / m to 34 mN / m, and particularly preferably in the range of 27 mN / m to 32 mN / m. .
  • the surface tension is within this numerical range, for example, the wettability of the pretreatment composition with respect to a soft packaging material having a substrate surface tension of about 40 mN / m can be improved.
  • the pretreatment agent composed of the pretreatment agent composition is applied to the base material by the application method described later, the coating property of the pretreatment agent can be improved and uniformly applied.
  • the surface tension of the pretreatment agent composition can be obtained, for example, by measuring using a surface tension meter (trade name: DY-500, manufactured by Kyowa Interface Science Co., Ltd.) at a measurement temperature of 25 ° C. (Method for producing pretreatment agent composition)
  • the pretreatment agent composition is produced by the production method described below.
  • a resin material solution in which at least one resin material is dissolved in alcohols and a polyvalent metal salt solution in which at least one polyvalent metal salt is dissolved in water are prepared. It does not specifically limit as a preparation method of each solution, It can create by mixing each material and stirring the mixture. Producing a pretreatment composition by adding the prepared resin material solution, polyvalent metal salt solution, surface tension modifier, and other additives as necessary, in any order, and stirring and mixing. Can do.
  • the temperature and stirring time of the mixture at the time of stirring and mixing are not particularly limited, and can be appropriately set as necessary.
  • the recording medium of the present embodiment includes at least a base material and a pretreatment layer provided on at least one surface of the base material.
  • the recording medium is used for image printing by an inkjet recording method, for example.
  • the substrate is not particularly limited, but the present embodiment is preferably applied to a hydrophobic substrate.
  • the hydrophobic substrate include conventionally known papers and soft packaging materials.
  • plastic films such as polyester resin, polypropylene resin, vinyl chloride resin, polyimide resin; metal, metal-deposited paper, glass, leather, synthetic rubber, natural rubber, etc .; lightweight coated paper, coated paper, art paper, cast paper And coated paper such as finely coated paper.
  • the substrate is not limited to a hydrophobic substrate, and the present embodiment can also be applied to a conventionally known substrate exhibiting water absorption.
  • the thickness of the base material is not particularly limited, and can be set as necessary.
  • the pretreatment layer is a layer obtained by drying the pretreatment agent comprising the pretreatment composition and forming a dry film on the substrate.
  • the pretreatment layer may be provided on the entire surface of the substrate and / or the back surface, or a part thereof.
  • Resin material is included in the pretreatment layer, and the resin material contributes to improved adhesion to the substrate. As a result, it is possible to form an image having excellent peel resistance and scratch resistance. Furthermore, in the present embodiment, since a poorly water-soluble or water-insoluble resin material is used, it is possible to form an image with excellent water resistance.
  • the pretreatment layer contains a polyvalent metal salt, and polyvalent metal ions derived from the polyvalent metal salt can cause aggregation or gelation of the pigment contained in the aqueous ink, for example.
  • the pretreatment layer of the present embodiment functions as a water-based ink receiving layer and aggregating layer.
  • the pretreatment layer can improve the fixability of the water-based ink and can prevent the occurrence of beading, bleeding, and color unevenness due to aggregation of adjacent water-based ink droplets (or adjacent dots). .
  • the dot diameter is excellent in stability and an image with good image quality can be formed.
  • the thickness of the pretreatment layer (after drying) is preferably within a range of 0.1 ⁇ m to 20 ⁇ m, and more preferably within a range of 1 ⁇ m to 5 ⁇ m. By setting the thickness to 0.1 ⁇ m or more, it is possible to maintain the fixability of the water-based ink. On the other hand, when the thickness is 20 ⁇ m or less, the drying time after application of the pretreatment agent can be shortened.
  • the thickness of a conventional ink receiving layer using silica particles or the like is about 30 ⁇ m.
  • the thickness of the pretreatment layer of the present embodiment is as described above, and can be made thinner than the conventional ink receiving layer. Specifically, it is possible to realize a thickness (for example, about 1 ⁇ m) comparable to a pretreatment layer used for an electrophotographic soft packaging film.
  • One or both surfaces of the base material may be subjected to corona discharge treatment or easy adhesion treatment as necessary. Furthermore, an anti-curl layer for preventing curling of the recording medium may be provided on the surface of the base material on which the pretreatment layer is not formed. The curling of the recording medium may be prevented by forming a pretreatment layer having the same thickness on both surfaces of the substrate.
  • the recording method on the recording medium according to the present embodiment includes not only printing an image using a water-based ink on the recording medium but also a pretreatment applied to the substrate before printing the image.
  • the pretreatment includes a pretreatment agent application step for applying a pretreatment agent composed of a pretreatment agent composition to the substrate surface, a pretreatment layer formation step for drying the applied pretreatment agent and forming a pretreatment layer. At least.
  • the pretreatment agent application step is performed by applying a pretreatment agent on the substrate.
  • the application of the pretreatment agent can be performed on the entire surface of at least one surface of the base material or an arbitrary partial region corresponding to the image printing region. It does not specifically limit as the provision method of a pre-processing agent, For example, well-known methods, such as the apply
  • the coating method is not particularly limited, and examples thereof include bar coating, gravure coating, gravure reverse coating, roll coating, wire bar coating, blade coating, knife coating, air knife coating, comma coating, slot die coating, dip coating, and the like. It is done.
  • a pretreatment agent composed of a pretreatment agent composition is ejected as droplets from a fine nozzle, and the droplets are attached to a substrate.
  • the discharge method is not particularly limited, and for example, a known method such as a continuous injection type (charge control type, spray type, etc.), an on-demand type (piezo type, thermal type, electrostatic suction type, etc.) is adopted. Can do.
  • the viscosity of the pretreatment agent is preferably 2 mPa ⁇ s to 7 mPa ⁇ s, more preferably 3 mPa ⁇ s to 5 mPa ⁇ s when discharging the inkjet nozzle in consideration of ejection stability from the inkjet nozzle. .
  • the viscosity of the pretreatment agent can be obtained, for example, by measuring under a measurement temperature of 25 ° C. using a viscometer (trade name: VISCOMATE MODEL VM-10A, manufactured by Seconic Corporation).
  • the supply (application) amount of the pretreatment agent to the substrate is appropriately set according to the thickness of the pretreatment layer to be formed.
  • the preferred range of 0.05cc / m 2 ⁇ 2.0cc / m 2 in terms of solid content more preferably in the range of 0.1cc / m 2 ⁇ 0.7cc / m 2, 0.2cc / m 2 A range of ⁇ 0.6 cc / m 2 is particularly preferred.
  • the pretreatment layer forming step is performed by drying the pretreatment agent applied to the substrate surface.
  • the drying of the pretreatment agent is not particularly limited as long as it accelerates the evaporation of the solvent contained in the pretreatment agent.
  • a method of spraying hot air on the pretreatment agent natural drying, a method of bringing the pretreatment agent into contact with a heating drum set to an appropriate temperature and the like, and the like can be mentioned.
  • hot air treatment such as forced air heating, radiation heating, conduction heating, high frequency drying, microwave drying, heating with a heater, and the like are possible.
  • the drying conditions can be appropriately changed and set according to the supply amount of the pretreatment agent and the like.
  • a recording medium having a pretreatment layer formed on at least one surface of the substrate is obtained.
  • the obtained recording medium may be subjected to a calendar process, a super calendar process, or the like as necessary in order to increase the smoothness or surface strength of the surface.
  • the printing of the image using the water-based ink is performed, for example, on the pretreatment agent applied to the substrate surface by the pretreatment agent application step or the pretreatment layer formed on the substrate surface by the pretreatment layer formation step. To be done.
  • the recording method of the present embodiment is a first method in which aqueous ink is applied to the pretreatment agent on the substrate immediately after the pretreatment agent application step and before the pretreatment layer formation step. It further includes an ink application step.
  • the pretreatment layer forming step not only the pretreatment agent but also the water-based ink applied on the pretreatment agent is simultaneously dried to thereby form an image.
  • the recording method of the present embodiment further includes a second ink application step for applying aqueous ink on the pretreatment layer, and a drying step for drying the aqueous ink applied on the pretreatment layer.
  • the method for applying the water-based ink to the pretreatment agent applied on the substrate or the pretreatment layer formed on the substrate is not particularly limited, and a known method can be adopted. More specifically, the above-described inkjet recording method and the like can be mentioned. The method for discharging the water-based ink is not particularly limited and is as described above. Therefore, the detailed description is abbreviate
  • the pretreatment agent on the substrate or the polyvalent metal ion derived from the polyvalent metal salt contained in the pretreatment layer is a solid component (more specifically, a pigment or the like) of the aqueous ink attached to the pretreatment layer.
  • This lowers the dispersion function of particles such as coloring materials and anionic resins, and causes aggregation.
  • a pigment or the like can be closely fixed on the recording medium, a high-quality image can be recorded. Aggregation of the solid component particles can proceed faster when the aqueous ink is applied to the pretreatment agent on the substrate than when the aqueous ink is applied to the pretreatment layer. This is because the solvent contained in the pretreatment agent is not evaporated before the pretreatment layer is formed, and therefore exists in the state of polyvalent metal ions.
  • An inkjet printing apparatus capable of printing in a one-pass method usually includes a plurality of (typically, the number of colors) line-type head units having a printing width larger than the width of the substrate, and these are the substrates. Are arranged in the transport direction. Printing in such a one-pass method using such a printing apparatus can be performed by discharging droplets from adjacent head units one after another in a short time.
  • the drying temperature can be appropriately set according to the solvent contained in the water-based ink, the type of the substrate, the drying time, and the like.
  • the drying time is not particularly limited, and can be appropriately set according to the solvent in the water-based ink, the type of the substrate, the printing speed, and the like.
  • the drying temperature and drying time are also considered in consideration of the drying of the solvent contained in the pretreatment agent. Is set.
  • the drying temperature means the surface temperature of the substrate.
  • the method of heating and drying the discharged water-based ink is not particularly limited as long as it promotes evaporation of the solvent in the water-based ink.
  • a method of spraying hot air on the discharged water-based ink a method of bringing the water-based ink into contact with a heating drum set to an appropriate temperature, and the like, can be used.
  • hot air treatment such as forced air heating, radiation heating, conduction heating, high frequency drying, microwave drying, heating with a heater, and the like are possible.
  • the dried water-based ink can be solidified by drying to form an ink layer.
  • the thickness (after drying) of the ink layer is not particularly limited, and can be set as necessary. Usually, it is set within the range of 0.5 ⁇ m to 10 ⁇ m.
  • the water-based ink preferably contains at least one pigment and a binder.
  • the pigment and the binder those usually used in the ink composition can be used without particular limitation. From the viewpoint of adhesion to the resin material contained in the pretreatment composition, those coated with a styrene-acrylic resin as a pigment are preferable.
  • the binder is preferably a styrene-acrylic emulsion.
  • the pretreatment composition of the present invention fixes the non-aqueous ink well and is good for a substrate. It is possible to form a pretreatment layer exhibiting excellent adhesion.
  • the manufacturing method of the recording medium of the present embodiment includes at least the above-described pretreatment agent application step and pretreatment layer formation step. As a result, it is possible to form an image by satisfactorily fixing the ink while suppressing the occurrence of ink bleeding and beading, and the print image has a peel resistance, scratch resistance and water resistance. A medium can be manufactured.
  • the details of the pretreatment agent applying step and the pretreatment layer forming step are as described above, and thus the description thereof is omitted.
  • the recording medium manufacturing method of the present embodiment may further include other steps as necessary.
  • a calendar process, a super calendar process, or the like may be performed as necessary.
  • Example 1 to 8 In each of Examples 1 to 8, shellac as a resin material (trade name; dry transparent white rack, manufactured by Nippon Shellac Industrial Co., Ltd.), ethanol as a solvent for the resin material (trade name; ethanol (99.5), Japanese Kogaku Pharmaceutical Co., Ltd.), calcium lactate as a polyvalent metal salt (trade name; DL-calcium lactate pentahydrate, manufactured by Wako Pure Chemical Industries, Ltd.), pure water as a solvent for the polyvalent metal salt, and A surface tension modifier (trade name: SY Glister MCA-750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was mixed and stirred according to the preparation method of the pretreatment composition described above so that the blending ratios shown in Table 1 were obtained.
  • a surface tension modifier (trade name: SY Glister MCA-750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was mixed and stirred according to the preparation method of the pretreatment composition described above so that the blending ratios
  • Example 1 the mixing ratio of calcium lactate as a polyvalent metal salt was constant, and the mixing ratio of shellac as a resin material was changed for each example.
  • the ethanol content is appropriately changed as shown in Table 1 in accordance with the blending ratio of the resin material.
  • Comparative Example 1 differs from Example 4 in that calcium lactate as a polyvalent metal salt was not added.
  • Example 5 to 8 and Comparative Example 2 the blending ratio of shellac as the resin material was made constant, and the blending ratio of calcium lactate as the polyvalent metal salt was changed. At this time, the mixing ratio of pure water and ethanol is appropriately changed as shown in Table 1 in accordance with the mixing ratio of the polyvalent metal salt.
  • Example 9 to 13 In each of Examples 9 to 13, shellac as a resin material (trade name; dry transparent white rack, manufactured by Nippon Shellac Industrial Co., Ltd.), ethanol as a solvent for the resin material (trade name; ethanol (99.5), Japanese Komatsu Pharmaceutical Co., Ltd.), calcium acetate as a polyvalent metal salt (trade name; calcium acetate monohydrate, manufactured by Wako Pure Chemical Industries, Ltd.), pure water as a solvent for polyvalent metal salt, and surface tension
  • the modifier (trade name: SY Glister MCA-750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was mixed and stirred according to the preparation method of the pretreatment composition described above so that the mixing ratio shown in Table 2 was obtained.
  • a pretreatment composition was prepared.
  • Comparative Examples 3 to 5 In Comparative Examples 3 to 5, pretreatment agent compositions according to Comparative Examples 3 to 5 were prepared using the same materials as in Examples 9 to 13 and at the blending ratios shown in Table 2.
  • Example 9 the mixing ratio of calcium acetate as the polyvalent metal salt was made constant, and the mixing ratio of shellac as the resin material was changed for each example.
  • the ethanol content is appropriately changed as shown in Table 2 in accordance with the blending ratio of the resin material.
  • Comparative Example 3 differs from Example 12 in that calcium acetate as a polyvalent metal salt was not added.
  • Example 13 and Comparative Examples 4 to 5 the blending ratio of shellac as the resin material was made constant, and the blending ratio of calcium acetate as the polyvalent metal salt was changed. At this time, the mixing ratio of pure water and ethanol is appropriately changed as shown in Table 2 in accordance with the mixing ratio of the polyvalent metal salt.
  • pretreatment agent compositions according to Examples 1 to 13 and Comparative Examples 1 to 5 were produced. Subsequently, pretreatment and image printing were performed on the base material using each prepared pretreatment composition, and the pretreatment composition was evaluated. However, in Comparative Example 2, since the insoluble content of the polyvalent metal salt was generated, the pretreatment and image printing on the substrate could not be performed. In Comparative Example 4 and Comparative Example 5, since calcium acetate gelled with ethanol and lost fluidity, pretreatment and image printing on the substrate could not be performed.
  • a PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.) and an aluminum base material (trade name: UG-8495, sold by Captain Stag Co., Ltd.) were prepared as base materials.
  • One side of these base materials was pretreated using pretreatment agents comprising the pretreatment agent compositions of Examples 1 to 13, Comparative Examples 1 and 3, respectively.
  • the pretreatment was performed by first applying a pretreatment agent on a PET film and an aluminum substrate using a bar coater (trade name; Bar Coater No. 3, manufactured by ASONE Co., Ltd.). The coating amount was 0.6 cc / m 2 in terms of solid content.
  • the pretreatment agent applied on the PET film was heat-dried under the conditions of a heating temperature of 70 ° C. and a heating time of 1 min to form a pretreatment layer.
  • the pretreatment agent applied on the aluminum substrate was heat-dried under the conditions of a heating temperature of 70 ° C. and a heating time of 1 min to form a pretreatment layer.
  • recording media according to Examples 1 to 13 and Comparative Examples 1 and 3 were produced.
  • Image printing> printing was performed on the recording media according to Examples 1 to 13, Comparative Example 1 and Comparative Example 3 by an ink jet method using an aqueous ink composed of an aqueous ink composition.
  • An ink jet printer (trade name: PX-105, manufactured by Seiko Epson Corporation) was used for printing.
  • the pressure-sensitive adhesive tape (trade name: Cellotape (registered trademark) No. 1 was used for the pretreatment layer of the recording medium according to each example and comparative example. 405, manufactured by Nichiban Co., Ltd.) for evaluation. Specifically, the tape peelability was visually evaluated by confirming the peeling of the pretreatment layer when the adhesive tape was peeled off and the transfer state to the tape after the application. The results are shown in Tables 1 and 2.
  • ⁇ No pretreatment layer attached to adhesive tape
  • Pretreatment layer attached to adhesive tape As shown in Tables 1 and 2, recording media according to Examples 1 to 13, Comparative Example 1 and Comparative Example 3 In any of these, good tape peel resistance is shown. Therefore, it was confirmed that the pretreatment layer formed using the pretreatment agent composition exhibits good adhesion to the PET film and the aluminum substrate. (Scratch resistance of pretreatment layer) Regarding the scratch resistance of the pretreatment layer according to each Example and Comparative Example, the pretreatment layer of the recording medium according to each Example and Comparative Example is rubbed twice with a nail, and the peeling state of the pretreatment layer is confirmed. The scratch resistance was visually evaluated. The results are shown in Tables 1 and 2.
  • Pretreatment layer is not peeled
  • Pretreatment layer is peeled off
  • good water resistance is obtained in any of the recording media according to Examples 1 to 13, Comparative Example 1 and Comparative Example 3. Showing sex. Therefore, it was confirmed that the pretreatment layer formed using the pretreatment composition exhibits good adhesion to the PET film and the aluminum substrate even in an atmosphere containing a lot of moisture.
  • the ink fixability after printing an image with a water-based ink composed of a water-based ink composition on the recording media according to each of Examples and Comparative Examples was evaluated based on the following evaluation criteria. The results are shown in Tables 1 and 2.
  • ⁇ No occurrence of beading, bleeding and color unevenness in printed image
  • ⁇ Generation of beading, bleeding and color unevenness in printed image
  • Tables 1 and 2 on the recording media according to Examples 1 to 13 In any printed image, no beading, bleeding or color unevenness was observed in the printed image, and it was confirmed that the ink fixing property was good.
  • the printed images printed on the recording media according to Comparative Example 1 and Comparative Example 3 since the polyvalent metal salt was not added, occurrence of beading, bleeding and color unevenness was confirmed in the printed image. .

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Abstract

Provided are a pretreatment agent composition for performing pretreatment on at least one surface of a base material, and a method for producing the pretreatment agent composition. The pretreatment composition at least contains at least one type of sparingly water-soluble and/or water-insoluble resin, an alcohol, and at least one type of polyvalent metal salt. The resin content is 0.1-30 % by mass relative to the total mass of the pretreatment agent composition, and the polyvalent metal salt content is 0.1-10% by mass relative to the total mass of the pretreatment agent composition. Also provided are a recording medium in which the pretreatment composition is used as a pretreatment agent, a method for producing the recording medium, and an image recording method.

Description

前処理剤組成物、前処理剤組成物の製造方法、記録媒体、記録媒体の製造方法および記録方法Pretreatment composition, method for producing pretreatment composition, recording medium, method for producing recording medium, and recording method
　この出願は、２０１８年３月２８日提出の日本国特許出願２０１８－０６２５５５号に基づく優先権を主張しており、この出願の全内容はここに引用により組み込まれるものとする。 This application claims priority based on Japanese Patent Application No. 2018-062555 filed on Mar. 28, 2018, the entire contents of which are incorporated herein by reference.
　本発明は、前処理剤組成物、記録方法、記録媒体および記録媒体の製造方法に関する。本発明は、より詳細には、アルミ基材や軟包装材等、インクの吸収性が小さい基材に対し、優れたインク定着性と耐滲み性を付与することができ、更に良好な密着性を示し、表刷り印刷に対応できる前処理層の形成が可能な前処理剤組成物、記録方法、記録媒体および記録媒体の製造方法に関する。 The present invention relates to a pretreatment composition, a recording method, a recording medium, and a manufacturing method of the recording medium. More specifically, the present invention can impart excellent ink fixing properties and bleeding resistance to a substrate with low ink absorbability, such as an aluminum substrate or a soft packaging material, and further better adhesion. The present invention relates to a pretreatment agent composition, a recording method, a recording medium, and a recording medium manufacturing method capable of forming a pretreatment layer that can be used for surface printing.
　アルミ基材や軟包装用フィルム（軟包装材）に対する印刷技術の主流は、これまでのところ、グラビア印刷やフレキソ印刷である。 The mainstream of printing technology for aluminum substrates and soft packaging films (soft packaging materials) has been gravure printing and flexographic printing so far.
　一方、近年、デジタル印刷市場の拡大に伴い、ＵＶ（Ultra Violet）インクを用いるＵＶインクジェット印刷による印刷方法が提案されている。しかし、ＵＶインクに含有されるモノマーが未反応の状態で印刷物に残るおそれがあり、この未反応モノマーが人体に悪影響を及ぼすといった問題がある。 On the other hand, in recent years, with the expansion of the digital printing market, a printing method using UV inkjet printing using UV (Ultra Violet) ink has been proposed. However, there is a possibility that the monomer contained in the UV ink may remain in the printed matter in an unreacted state, and there is a problem that this unreacted monomer adversely affects the human body.
　アルミ基材や軟包装材は、医薬品や食品など、人が口にする物を包装する目的で使用することが非常に多い。そのため、それらへの印刷に用いられるインクにおいても、人体に影響のない環境衛生に優れた製品となるように、各メーカーが取り組んでいる。その一例として、モノマーを含まない水性インクを用いたインクジェット方式による印刷に注目が集まっている。 Aluminum base materials and soft packaging materials are very often used for the purpose of packaging things that people use, such as pharmaceuticals and food. For this reason, manufacturers are working to make the ink used for printing on these products excellent in environmental sanitation without affecting the human body. As an example, attention is focused on printing by an ink jet method using a water-based ink containing no monomer.
　しかし、アルミ基材や軟包装用フィルム（以下、疎水性基材）は、表面が疎水性であるため、紙とは異なり、水性インクの吸収性が小さい。そのため、水性インクが疎水性基材上に定着するのは困難であり、それに起因した滲みやビーディングが発生する。そこで、疎水性基材上にプライマー層（前処理層）と呼ばれるインク浸透層又はインク受容層を設け、これにより、水性インクが疎水性基材に定着することを可能にしている。インク浸透層は水性インクを当該インク浸透層に浸透させることで、疎水性基材の表面に水性インクが残存しない効果を有する。インク受容層は、カチオン性物質、金属塩、又は水溶性樹脂を含むことにより、これらが水性インクを定着させる効果を有する。 However, since the surface of an aluminum substrate or a soft packaging film (hereinafter referred to as a hydrophobic substrate) is hydrophobic, unlike paper, the water-based ink has low absorbability. For this reason, it is difficult for the water-based ink to be fixed on the hydrophobic substrate, and bleeding and beading due to the water-based ink are generated. Therefore, an ink permeation layer or ink receiving layer called a primer layer (pretreatment layer) is provided on the hydrophobic substrate, thereby allowing the water-based ink to be fixed to the hydrophobic substrate. The ink permeation layer has an effect that the water-based ink does not remain on the surface of the hydrophobic substrate by allowing the water-based ink to permeate the ink permeation layer. The ink receiving layer contains a cationic substance, a metal salt, or a water-soluble resin, and these have an effect of fixing the water-based ink.
　基材への印刷方法は、裏刷り印刷および表刷り印刷に大別される。裏刷り印刷においては、基材の裏面への印刷の後、接着剤又はアンカーコート剤を塗布し、ドライラミネート加工又は押出ラミネート加工により、樹脂又はフィルムなどの接着を行なう。そのため、印刷面への耐擦過性や耐水性は大きくは要求されない。しかし、表刷り印刷は、基材の表面に直接印刷し、ラミネート加工等を行わないため、印刷面の耐擦過性および耐水性が要求される。すなわち、表刷り印刷を行う場合、前処理層にも耐擦過性および耐水性が要求される。 The printing method on the substrate is roughly divided into back printing and surface printing. In reverse printing, after printing on the back surface of a substrate, an adhesive or an anchor coat agent is applied, and a resin or a film is bonded by dry lamination or extrusion lamination. Therefore, the scratch resistance and water resistance on the printed surface are not required to be large. However, surface printing requires direct printing on the surface of the substrate and does not perform lamination or the like, and therefore requires scratch resistance and water resistance on the printed surface. That is, when surface printing is performed, the pretreatment layer is also required to have scratch resistance and water resistance.
特開２０１６－１７５２９９号公報JP 2016-175299 A
　前処理層に耐擦過性および耐水性の両方を持たせるために、難水溶性又は非水溶性の樹脂材料を用いて、前処理層と基材との密着性を強化することが考えられる。しかしながら、難水溶性又は非水溶性の樹脂材料は、溶媒としての水に溶けない。そこで、樹脂材料をエマルジョン状態にして用いることが提案されている（例えば、特許文献１参照）。 In order to give both the scratch resistance and water resistance to the pretreatment layer, it is conceivable to enhance the adhesion between the pretreatment layer and the substrate by using a poorly water-soluble or water-insoluble resin material. However, poorly water-soluble or water-insoluble resin materials are not soluble in water as a solvent. Thus, it has been proposed to use the resin material in an emulsion state (see, for example, Patent Document 1).
　しかし、耐擦過性および耐水性の観点から、樹脂材料は溶媒に対して溶解していることが好ましい。樹脂材料を溶解させるために、樹脂材料の性質に合わせて酸性溶媒や塩基性溶媒を用いることが考えられる。しかしながら、酸性溶媒や塩基性溶媒を用いると、前処理層および水性インクの基材への定着性を担う成分である金属塩や酸類等を配合した際、凝集や沈降が発生するといった問題点がある。 However, the resin material is preferably dissolved in a solvent from the viewpoint of scratch resistance and water resistance. In order to dissolve the resin material, it is conceivable to use an acidic solvent or a basic solvent in accordance with the properties of the resin material. However, when an acidic solvent or a basic solvent is used, there is a problem that aggregation or sedimentation occurs when a metal salt or an acid that is a component responsible for fixing the pretreatment layer and the aqueous ink to the base material is blended. is there.
　本発明は前記問題点に鑑みなされたものであり、その一つの目的は、滲みやビーディングの発生を抑制しつつインクを良好に定着させ、基材に対して良好な密着性を示し、かつ、表刷り印刷に対応できる前処理層を形成することが可能な前処理剤組成物およびその製造方法を提供することである。また、この発明の他の一つの目的は、前述のような前処理剤組成物を用いた記録媒体およびその製造方法、ならびに記録方法を提供することである。 The present invention has been made in view of the above problems, and one object thereof is to satisfactorily fix the ink while suppressing the occurrence of bleeding and beading, exhibit good adhesion to the substrate, and An object of the present invention is to provide a pretreatment composition capable of forming a pretreatment layer that can be used for surface printing and a method for producing the same. Another object of the present invention is to provide a recording medium using the pretreatment composition as described above, a method for producing the same, and a recording method.
　本発明の一実施形態は、基材の少なくとも一方の面に対し、前処理を行うための前処理剤組成物を提供する。この前処理剤組成物は、少なくとも一種の難水溶性および／又は非水溶性の樹脂と、アルコール類と、少なくとも１種の多価金属塩と、を少なくとも含む。そして、前記樹脂の含有量が、前処理剤組成物の全質量に対し０．１質量％～３０質量％である。さらに、前記多価金属塩の含有量が、前処理剤組成物の全質量に対し０．１質量％～１０質量％である。 One embodiment of the present invention provides a pretreatment composition for performing pretreatment on at least one surface of a substrate. This pretreatment agent composition includes at least one poorly water-soluble and / or water-insoluble resin, alcohols, and at least one polyvalent metal salt. The content of the resin is 0.1% by mass to 30% by mass with respect to the total mass of the pretreatment agent composition. Furthermore, the content of the polyvalent metal salt is 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition.
　この前処理剤組成物は、例えば、基材に対する画像形成において、滲みやビーディングの発生を抑制しつつインクを良好に定着させ、基材に対して良好な密着性を示し、かつ、表刷り印刷に対応できる前処理層を形成することが可能である。 This pretreatment composition, for example, in image formation on a substrate, fixes ink well while suppressing the occurrence of bleeding and beading, exhibits good adhesion to the substrate, and is printed on the surface. It is possible to form a pretreatment layer that can handle printing.
　また、本発明の一実施形態に係る前処理剤組成物の製造方法は、少なくとも一種の難水溶性および／又は非水溶性の樹脂をアルコール類に溶解させて樹脂溶解液を作製する工程と、少なくとも一種の多価金属塩を溶媒に対して溶解させて多価金属塩溶解液を作製する工程と、前記樹脂溶解液と前記多価金属塩溶解液とを混合する工程と、を含む。 Moreover, the method for producing a pretreatment composition according to an embodiment of the present invention includes a step of dissolving a at least one poorly water-soluble and / or water-insoluble resin in alcohols to produce a resin solution, A step of dissolving at least one polyvalent metal salt in a solvent to produce a polyvalent metal salt solution, and a step of mixing the resin solution and the polyvalent metal salt solution.
　この製造方法によれば、例えば、基材に対する画像形成において、滲みやビーディングの発生を抑制しつつインクを良好に定着させ、基材に対して良好な密着性を示し、かつ、表刷り印刷に対応できる前処理層を形成することが可能な前処理剤組成物を製造できる。
また、本発明の一実施形態は、基材と、前記基材の少なくとも一方の面上に設けられた前処理層とを含む記録媒体を提供する。この記録媒体は、前記前処理層の少なくとも一部は前処理剤の乾燥皮膜からなる。前記前処理剤は、少なくとも一種の難水溶性および／又は非水溶性の樹脂と、アルコール類と、少なくとも１種の多価金属塩と、を少なくとも含み、前記樹脂の含有量が、前処理剤組成物の全質量に対し０．１質量％～３０質量％であり、前記多価金属塩の含有量が、前処理剤組成物の全質量に対し０．１質量％～１０質量％である前処理剤組成物からなる。 According to this manufacturing method, for example, in image formation on a base material, the ink is satisfactorily fixed while suppressing occurrence of bleeding and beading, good adhesion to the base material, and surface printing. It is possible to produce a pretreatment agent composition capable of forming a pretreatment layer that can cope with the above.
Moreover, one Embodiment of this invention provides the recording medium containing a base material and the pre-processing layer provided on the at least one surface of the said base material. In this recording medium, at least a part of the pretreatment layer comprises a dry film of a pretreatment agent. The pretreatment agent includes at least one poorly water-soluble and / or water-insoluble resin, alcohols, and at least one polyvalent metal salt, and the content of the resin is the pretreatment agent. The content of the polyvalent metal salt is 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition. It consists of a pretreatment composition.
　この記録媒体は、画像形成時の滲みやビーディングの発生を抑制しつつインクを良好に定着させ、基材に対して良好な密着性を示し、かつ、表刷り印刷に対応できる前処理層を有することができる。 This recording medium has a pretreatment layer that fixes ink well while suppressing the occurrence of bleeding and beading during image formation, exhibits good adhesion to a substrate, and is compatible with surface printing. Can have.
　また、本発明の一実施形態に係る記録媒体の製造方法は、基材と、前記基材の少なくとも一方の面上に設けられた前処理層とを含み、前記基材の少なくとも一方の面上に、前処理剤を付与する前処理剤付与工程と、前記前処理剤付与工程において付与された前記前処理剤を乾燥させて、前処理層を形成する前処理層形成工程と、を含む。前記前処理剤は、少なくとも一種の難水溶性および／又は非水溶性の樹脂と、アルコール類と、少なくとも１種の多価金属塩と、を少なくとも含み、前記樹脂の含有量が、前処理剤組成物の全質量に対し０．１質量％～３０質量％であり、前記多価金属塩の含有量が、前処理剤組成物の全質量に対し０．１質量％～１０質量％である前処理剤組成物からなる。 In addition, a recording medium manufacturing method according to an embodiment of the present invention includes a base material and a pretreatment layer provided on at least one surface of the base material, and on the at least one surface of the base material. And a pretreatment agent forming step for applying a pretreatment agent, and a pretreatment layer forming step for drying the pretreatment agent applied in the pretreatment agent application step to form a pretreatment layer. The pretreatment agent includes at least one poorly water-soluble and / or water-insoluble resin, alcohols, and at least one polyvalent metal salt, and the content of the resin is the pretreatment agent. The content of the polyvalent metal salt is 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition. It consists of a pretreatment composition.
　この方法によれば、画像形成時の滲みやビーディングの発生を抑制しつつインクを良好に定着させ、基材に対して良好な密着性を示し、かつ、表刷り印刷に対応できる前処理層を有する記録媒体を製造できる。
また、本発明の一実施形態に係る記録方法は、基材の少なくとも一方の面上に、前処理剤を付与する前処理剤付与工程と、前記前処理剤付与工程において付与された前記前処理剤上にインクを付与する第１インク付与工程と、前記第１インク付与工程後に、前記前処理剤と前記インクを乾燥させて前記画像を形成する画像形成工程とを含む。 According to this method, a pretreatment layer that can fix ink well while suppressing the occurrence of bleeding and beading during image formation, exhibits good adhesion to a substrate, and is compatible with surface printing. Can be produced.
Moreover, the recording method according to an embodiment of the present invention includes a pretreatment agent application step of applying a pretreatment agent on at least one surface of a substrate, and the pretreatment applied in the pretreatment agent application step. A first ink applying step of applying ink onto the agent, and an image forming step of forming the image by drying the pretreatment agent and the ink after the first ink applying step.
　本発明の他の実施形態に係る記録方法は、基材の少なくとも一方の面上に、前処理剤を付与する前処理剤付与工程と、前記前処理剤付与工程において付与された前記前処理剤を乾燥させて、前処理層を形成する前処理層形成工程と、前記前処理層形成工程により形成された前記前処理層にインクを付与する第２インク付与工程と、前記第２インク付与工程において付与された前記インクを乾燥させて前記画像を形成する画像形成工程と、を含む。 The recording method according to another embodiment of the present invention includes a pretreatment agent application step for applying a pretreatment agent on at least one surface of a substrate, and the pretreatment agent applied in the pretreatment agent application step. A pretreatment layer forming step for forming a pretreatment layer, a second ink application step for applying ink to the pretreatment layer formed by the pretreatment layer formation step, and the second ink application step And forming an image by drying the ink applied in step (b).
　前記前処理剤は、少なくとも一種の難水溶性および／又は非水溶性の樹脂と、アルコール類と、少なくとも１種の多価金属塩と、を少なくとも含み、前記樹脂の含有量が、前処理剤組成物の全質量に対し０．１質量％～３０質量％であり、前記多価金属塩の含有量が、前処理剤組成物の全質量に対し０．１質量％～１０質量％である前処理剤組成物からなる。 The pretreatment agent includes at least one poorly water-soluble and / or water-insoluble resin, alcohols, and at least one polyvalent metal salt, and the content of the resin is the pretreatment agent. The content of the polyvalent metal salt is 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition. It consists of a pretreatment composition.
　これらの記録方法によれば、滲みやビーディングの発生を抑制しつつインクを良好に定着させ、基材に対して良好な密着性を示し、かつ、表刷り印刷に対応できる前処理層を形成しながら、画像を基材上に記録できる。 According to these recording methods, the ink is satisfactorily fixed while suppressing the occurrence of bleeding and beading, forming a pretreatment layer that exhibits good adhesion to the substrate and can be used for surface printing. The image can then be recorded on the substrate.
（前処理剤組成物）
　先ず、本実施の形態の前処理剤組成物について、以下に説明する。 (Pretreatment composition)
First, the pretreatment composition of the present embodiment will be described below.
　本実施の形態の前処理剤組成物は、画像が印刷（形成）される前の基材に対して、前処理を行うために用いられる。即ち、前処理剤組成物は、前処理により基材上に形成される前処理層の構成材料として用いられ。基材および前処理層の詳細については、後述する。 The pretreatment composition of the present embodiment is used for pretreatment of a substrate before an image is printed (formed). That is, the pretreatment agent composition is used as a constituent material of a pretreatment layer formed on a substrate by pretreatment. Details of the substrate and the pretreatment layer will be described later.
　前処理層が形成された基材に対して、水性インクによって画像が形成される。基材に前処理を施して前処理層を形成することにより、記録媒体に対する水性インクの定着性が向上する。「定着性」とは、記録媒体に画像形成した後の水性インクの定着安定性を意味する。定着性が良好であると、画像のビーディング(beading)、滲み(bleeding)、色ムラ等の発生を抑制することができる。 An image is formed with water-based ink on the base material on which the pretreatment layer is formed. By performing the pretreatment on the substrate to form the pretreatment layer, the fixability of the water-based ink to the recording medium is improved. “Fixability” means the fixing stability of an aqueous ink after an image is formed on a recording medium. When the fixing property is good, the occurrence of image beading, bleeding, color unevenness, and the like can be suppressed.
　また、前処理層の基材に対する密着性が高いほど、記録媒体における前処理層の耐剥離性および耐擦過性が向上する。「耐剥離性」とは、記録媒体の表面に形成された前処理層の一部又は全部が、当該記録媒体表面から剥離するのを抑制し得る性能を意味する。「耐擦過性」とは、記録媒体の表面に形成された前処理層に傷が付くのを抑制し得る性能を意味する。記録媒体における前処理層の耐剥離性および耐擦過性が高いことにより、当該記録媒体上に形成された印刷画像においても記録媒体に対する耐剥離性および耐擦過性が向上する。さらに、前処理剤組成物そのものが耐水性を有する場合、基材に形成された前処理層が水分による影響を受けない。そのため、記録媒体上に形成された印刷画像が変質するのを抑制することが可能となる。 Also, the higher the adhesion of the pretreatment layer to the substrate, the better the peel resistance and scratch resistance of the pretreatment layer in the recording medium. “Peeling resistance” means performance capable of suppressing peeling of a part or all of the pretreatment layer formed on the surface of the recording medium from the surface of the recording medium. “Abrasion resistance” means performance capable of suppressing scratches on the pretreatment layer formed on the surface of the recording medium. Due to the high peel resistance and scratch resistance of the pretreatment layer in the recording medium, the peel resistance and scratch resistance to the recording medium are improved even in a printed image formed on the recording medium. Furthermore, when the pretreatment composition itself has water resistance, the pretreatment layer formed on the substrate is not affected by moisture. For this reason, it is possible to suppress the quality change of the printed image formed on the recording medium.
　本実施の形態の前処理剤組成物は、難水溶性および／又は非水溶性の樹脂（以下、総称する場合は「樹脂材料」という）と、アルコール類と、少なくとも１種の多価金属塩を少なくとも含有する。また、本実施の形態においては、基材に対する濡れ性を前処理剤組成物に付与するために、前処理剤組成物は、必要に応じて表面張力調整剤を含有する。 The pretreatment composition according to the present embodiment includes a poorly water-soluble and / or water-insoluble resin (hereinafter collectively referred to as “resin material”), an alcohol, and at least one polyvalent metal salt. At least. Moreover, in this Embodiment, in order to provide the wettability with respect to a base material to a pretreatment agent composition, a pretreatment agent composition contains a surface tension regulator as needed.
　樹脂材料は、基材に対する前処理剤組成物又は前処理層の密着性の向上に寄与する。樹脂材料は、前処理剤組成物中では溶解した状態で存在する。これにより、例えば、前処理剤組成物の膜を乾燥させるだけで前処理層を形成できるので、造膜が容易である。また、溶媒が揮発することで膜化するため、強度の高い膜（前処理層）を形成することができる。さらに、インクジェット方式で前処理剤組成物からなる前処理剤を吐出させる際には、ノズルの目詰まりを防止できるので、吐出不良の発生を抑制することができる。「溶解した状態」とは、樹脂材料が溶媒と均一に混合した溶液の状態を意味する。 Resin material contributes to improvement in adhesion of the pretreatment composition or the pretreatment layer to the base material. The resin material exists in a dissolved state in the pretreatment composition. Thereby, for example, since the pretreatment layer can be formed only by drying the film of the pretreatment agent composition, film formation is easy. In addition, since the film is formed by volatilization of the solvent, a high-strength film (pretreatment layer) can be formed. Further, when the pretreatment agent comprising the pretreatment agent composition is ejected by the ink jet method, clogging of the nozzle can be prevented, so that the occurrence of ejection failure can be suppressed. The “dissolved state” means a state of a solution in which the resin material is uniformly mixed with a solvent.
　難水溶性の樹脂および非水溶性の樹脂としては、特に限定されないが、セラック樹脂、カゼイン、酢酸ビニル樹脂、アクリル樹脂およびロジン樹脂が好ましい例である。「難水溶性」とは、２５℃の水１００ｇに１５ｇ以上溶解しない（より好ましくは５ｇ以上溶解しない）ことをいう。「非水溶性」とは、２５℃の水１００ｇに１ｇ以上溶解しないことをいう。 The water-insoluble resin and the water-insoluble resin are not particularly limited, but shellac resin, casein, vinyl acetate resin, acrylic resin, and rosin resin are preferable examples. “Slightly water-soluble” means that 15 g or more is not dissolved (more preferably, 5 g or more is not dissolved) in 100 g of water at 25 ° C. “Water-insoluble” means that 1 g or more is not dissolved in 100 g of water at 25 ° C.
　セラックとしては市販品を用いることが可能であり、そのような市販品としては、例えば、乾燥透明白ラック(Bleached Dewaxed Shellac)、ＮＳＣ、ラックグレーズ５０Ｅ(LACGLAZE)、ラックコート５０(LACCOAT)（商品名。何れも日本シェラック工業株式会社製）等が挙げられる。 Commercial products can be used as shellac. Examples of such commercially available products include dry transparent white rack (Bleached DewaxedxShellac), NSC, rack glaze 50E (LACGLAZE), rack coat 50 (LACCOAT) (product) Names are all manufactured by Nippon Shellac Industrial Co., Ltd.
　以上に例示した樹脂材料は、適宜必要に応じて、単独で又は二種以上を前処理剤組成物中に含有させることができる。 The resin materials exemplified above can be contained alone or in combination of two or more in the pretreatment composition as necessary.
　樹脂材料の含有量は、前処理剤組成物の全質量に対し、０．１質量％～３０質量％の範囲であり、好ましくは１質量％～２０質量％、より好ましくは５質量％～１０質量％の範囲である。樹脂材料の含有量を０．１質量％以上にすることにより、前処理剤組成物を用いて形成された前処理層における水性インクの定着性を良好にすることができる。その一方、樹脂材料の含有量を３０質量％以下にすることにより、樹脂材料が溶媒に対して溶解した状態を維持することができる。 The content of the resin material is in the range of 0.1% by mass to 30% by mass with respect to the total mass of the pretreatment agent composition, preferably 1% by mass to 20% by mass, more preferably 5% by mass to 10% by mass. It is the range of mass%. By setting the content of the resin material to 0.1% by mass or more, the fixability of the water-based ink in the pretreatment layer formed using the pretreatment agent composition can be improved. On the other hand, by setting the content of the resin material to 30% by mass or less, the state in which the resin material is dissolved in the solvent can be maintained.
　本実施の形態の前処理剤組成物においては、上記の樹脂材料の含有量の範囲内であれば、上記の樹脂材料以外のその他の樹脂を含有させてもよい。 In the pretreatment agent composition of the present embodiment, other resin than the above resin material may be contained as long as it is within the range of the above resin material content.
　本実施の形態の前処理剤組成物は、樹脂材料の主溶媒として、アルコール類を含有する。アルコール類としては、低級アルコールを用いるのが好ましく、第１級アルコールを用いるのがより好ましく、エタノール又はメタノールを用いるのが好適である。また、アルコール類の含有量は、樹脂材料が完全に溶解される量であれば、特に限定されない。 The pretreatment composition of the present embodiment contains alcohols as the main solvent for the resin material. As alcohols, lower alcohols are preferably used, primary alcohols are more preferably used, and ethanol or methanol is preferably used. Further, the content of the alcohol is not particularly limited as long as the resin material is completely dissolved.
　多価金属塩は、前処理剤組成物又は前処理層と水性インクの定着性の向上に寄与する。本明細書における多価金属塩とは、二価以上の多価金属イオンとこれらの多価金属イオンに結合する陰イオンとから構成されるものを意味する。多価金属塩は、水に可溶な化合物であり、前処理剤組成物中では溶解した状態で存在する。溶解した状態とは、多価金属塩が水等の溶媒と均一に混合した溶液の状態を意味する。 The polyvalent metal salt contributes to the improvement of the fixability of the pretreatment composition or the pretreatment layer and the water-based ink. In the present specification, the polyvalent metal salt means a divalent or higher polyvalent metal ion and an anion that binds to these polyvalent metal ions. The polyvalent metal salt is a compound that is soluble in water, and exists in a dissolved state in the pretreatment agent composition. The dissolved state means a state in which a polyvalent metal salt is uniformly mixed with a solvent such as water.
　多価金属塩は、マグネシウム塩、アルミニウム塩、カルシウム塩、チタン塩、マンガン塩、鉄塩、ニッケル塩、銅塩、亜鉛塩、スズ塩およびバリウム塩からなる群より選ばれる少なくとも１種の金属塩である。これらの多価金属塩は、無機金属塩又は有機金属塩の何れであってもよい。多価金属塩は、より具体的には、例えば、塩化マグネシウム、臭化マグネシウム、ヨウ化マグネシウム、硫酸マグネシウム、塩化アルミニウム、臭化アルミニウム、硫酸アルミニウム、硝酸アルミニウム、酢酸アルミニウム、塩化カルシウム、臭化カルシウム、ヨウ化カルシウム、亜硝酸カルシウム、硝酸カルシウム、リン酸二水素カルシウム、チオシアン酸カルシウム、乳酸カルシウム、酢酸カルシウム、フマル酸カルシウム、クエン酸カルシウム、塩化チタン、硫酸マンガン、硝酸マンガン、リン酸二水素マンガン、酢酸マンガン、サリチル酸マンガン、安息香酸マンガン、乳酸マンガン、塩化鉄、臭化鉄、ヨウ化鉄、硫酸鉄、硝酸鉄、シュウ酸鉄、乳酸鉄、フマル酸鉄、クエン酸鉄、塩化ニッケル、臭化ニッケル、硫酸ニッケル、硝酸ニッケル、酢酸ニッケル、塩化銅、臭化銅、硫酸銅、硝酸銅、酢酸銅、塩化亜鉛、臭化亜鉛、硫酸亜鉛、硝酸亜鉛、チオシアン酸亜鉛、酢酸亜鉛、硫酸スズ、塩化バリウム、臭化バリウム、ヨウ化バリウム、酸化バリウム、硝酸バリウム、チオシアン酸バリウム等である。これらの多価金属塩は、適宜必要に応じて、単独で又は二種以上を混合して用いることができる。 The polyvalent metal salt is at least one metal salt selected from the group consisting of magnesium salt, aluminum salt, calcium salt, titanium salt, manganese salt, iron salt, nickel salt, copper salt, zinc salt, tin salt and barium salt It is. These polyvalent metal salts may be either inorganic metal salts or organic metal salts. More specifically, the polyvalent metal salt is, for example, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, aluminum chloride, aluminum bromide, aluminum sulfate, aluminum nitrate, aluminum acetate, calcium chloride, calcium bromide. , Calcium iodide, calcium nitrite, calcium nitrate, calcium dihydrogen phosphate, calcium thiocyanate, calcium lactate, calcium acetate, calcium fumarate, calcium citrate, titanium chloride, manganese sulfate, manganese nitrate, manganese dihydrogen phosphate , Manganese acetate, manganese salicylate, manganese benzoate, manganese lactate, iron chloride, iron bromide, iron iodide, iron sulfate, iron nitrate, iron oxalate, iron lactate, iron fumarate, iron citrate, nickel chloride, odor Nickel bromide, nickel sulfate, nitric acid Nickel, nickel acetate, copper chloride, copper bromide, copper sulfate, copper nitrate, copper acetate, zinc chloride, zinc bromide, zinc sulfate, zinc nitrate, zinc thiocyanate, zinc acetate, tin sulfate, barium chloride, barium bromide Barium iodide, barium oxide, barium nitrate, barium thiocyanate and the like. These polyvalent metal salts can be used alone or in admixture of two or more as required.
　多価金属塩の含有量は、前処理剤組成物の全質量に対し０．１質量％～１０質量％の範囲であり、好ましくは０．１質量％～５．０質量％、より好ましくは０．１質量％～２．０質量％の範囲である。多価金属塩の含有量を０．１質量％以上にすることにより、水性インクの定着性の向上が可能になる。その一方、多価金属塩の含有量を１０質量％以下にすることにより、多価金属塩の不溶分が前処理剤組成物中に発生するのを抑制することができる。 The content of the polyvalent metal salt is in the range of 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition, preferably 0.1% by mass to 5.0% by mass, more preferably The range is from 0.1% by mass to 2.0% by mass. By making the content of the polyvalent metal salt 0.1% by mass or more, the fixing property of the water-based ink can be improved. On the other hand, by setting the content of the polyvalent metal salt to 10% by mass or less, it is possible to suppress the insoluble matter of the polyvalent metal salt from being generated in the pretreatment agent composition.
　本実施の形態の前処理剤組成物においては、多価金属塩の主溶媒として水を含有する。水としては、イオン性不純物を除去した水を用いるのが好ましく、具体的には、イオン交換水、限外ろ過水、逆浸透水、蒸留水等の純水、又は超純水等が好ましい。特に、紫外線照射又は過酸化水素添加等により滅菌処理した水は、長期間に亘ってカビやバクテリアの発生を防止することができるので好適である。また、水の含有量は、多価金属が完全に溶解される量であれば、特に限定されない。 In the pretreatment agent composition of the present embodiment, water is contained as the main solvent for the polyvalent metal salt. As the water, it is preferable to use water from which ionic impurities have been removed. Specifically, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water is preferable. In particular, water sterilized by ultraviolet irradiation or addition of hydrogen peroxide or the like is preferable because generation of mold and bacteria can be prevented over a long period of time. The water content is not particularly limited as long as the polyvalent metal is completely dissolved.
　本実施の形態の前処理剤組成物においては、適宜必要に応じて、他の添加剤を含有させることができる。添加剤としては、例えば、表面張力調整剤（界面活性剤）、ｐＨ調節剤、粘度調節剤、柔軟剤、光沢付与剤、ワックス類、分散剤、流動変性剤、安定化剤、帯電防止剤、架橋剤、表面サイズ剤、蛍光増白剤、着色剤、紫外線吸収剤、消泡剤、耐水化剤、可塑剤、滑剤、防腐剤および香料等が挙げられる。表面張力調整剤を除き、これらの添加剤の含有量は特に限定されず、適宜必要に応じて設定することができる。表面張力調整剤の含有量については後述する。 In the pretreatment agent composition of the present embodiment, other additives can be appropriately contained as necessary. Examples of the additive include a surface tension adjuster (surfactant), a pH adjuster, a viscosity adjuster, a softener, a gloss imparting agent, waxes, a dispersant, a flow modifier, a stabilizer, an antistatic agent, Crosslinking agents, surface sizing agents, fluorescent brighteners, colorants, ultraviolet absorbers, antifoaming agents, water resistance agents, plasticizers, lubricants, preservatives, and fragrances can be mentioned. Except for the surface tension adjusting agent, the content of these additives is not particularly limited, and can be set as necessary. The content of the surface tension adjusting agent will be described later.
　これらの添加剤のうち、表面張力調整剤の添加は、基材表面および水性インクに対する前処理剤組成物の濡れ性を制御することができる。前処理剤組成物の表面張力を小さくすることで、基材表面に対する濡れ性を大きくすることができ、塗布ムラの発生を防止することができる。前処理剤組成物からなる前処理剤をインクジェット方式により基材上に付与する場合には、前処理剤の表面張力を適正にでき、かつヘッドノズル面等の前処理剤と接触するプリンター部品との界面張力を適正にすることができる。その結果、メニスカスの崩れによるノズルの吐出不良の改善を図ることができる。 Among these additives, the addition of the surface tension adjusting agent can control the wettability of the pretreatment agent composition with respect to the substrate surface and aqueous ink. By reducing the surface tension of the pretreatment composition, the wettability with respect to the substrate surface can be increased, and the occurrence of coating unevenness can be prevented. When applying a pretreatment agent comprising a pretreatment agent composition onto a substrate by an ink jet method, a printer component capable of making the surface tension of the pretreatment agent appropriate and contacting with a pretreatment agent such as a head nozzle surface; The interfacial tension can be made appropriate. As a result, it is possible to improve the discharge failure of the nozzle due to the collapse of the meniscus.
　表面張力調整剤としては特に限定されず、例えば、非イオン性界面活性剤、シリコン系界面活性剤、フッ素系界面活性剤、アセチレンジオール系界面活性剤、アクリル系界面活性剤等が挙げられる。これらの表面張力調整剤は、一種単独で、又は二種以上を混合して用いてもよい。 The surface tension adjusting agent is not particularly limited, and examples thereof include nonionic surfactants, silicon surfactants, fluorine surfactants, acetylenic diol surfactants, and acrylic surfactants. These surface tension modifiers may be used alone or in combination of two or more.
　非イオン性界面活性剤としては特に限定されず、例えば、ポリオキシエチレン２級アルコールエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンステロールエーテル、ポリオキシエチレンラノリン誘導体、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレンヒマシ油、硬化ヒマシ油、ポリオキシエチレンソルビトール脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、脂肪酸モノグリセリド、ポリ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、ショ糖脂肪酸エステル、脂肪酸アルカノールアミド、ポリオキシエチレン脂肪酸アミド、ポリオキシエチレンアルキルアミン、アルキルアミンオキサイド、アセチレングリコール、アセチレンアルコール等が挙げられる。 The nonionic surfactant is not particularly limited. For example, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether , 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 alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, Le Kill amine oxide, acetylene glycol, acetylene alcohol, and the like.
　シリコン系界面活性剤としては特に限定されず、例えば、ポリエーテル変性ポリシロキサン化合物等が挙げられる。但し、表面張力調整剤としてシリコン系界面活性剤を単独で用いるのは好ましくない。前処理層の基材に対する密着性が低下し、前処理層が剥離する場合があるからである。 The silicon-based surfactant is not particularly limited, and examples thereof include polyether-modified polysiloxane compounds. However, it is not preferable to use a silicon surfactant alone as the surface tension adjusting agent. This is because the adhesion of the pretreatment layer to the substrate is lowered and the pretreatment layer may be peeled off.
　フッ素系界面活性剤としては特に限定されず、例えば、パーフルオロアルキルスルホン酸化合物、パーフルオロアルキルカルボン酸化合物、パーフルオロアルキルリン酸エステル、パーフルオロアルキルエチレンオキサイド付加物、パーフルオロアルキルベタイン、パーフルオロアルキルアミンオキサイド化合物等が挙げられる。 The fluorosurfactant is not particularly limited, and examples thereof include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate esters, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoro. Examples include alkylamine oxide compounds.
　アクリル系界面活性剤としては特に限定されず、例えば、（メタ）アクリル酸系共重合体等が挙げられる。（メタ）アクリル酸共重合体とは、アクリル酸共重合体およびメタクリル酸共重合体を意味する。 The acrylic surfactant is not particularly limited, and examples thereof include (meth) acrylic acid copolymers. A (meth) acrylic acid copolymer means an acrylic acid copolymer and a methacrylic acid copolymer.
　表面張力調整剤の含有量は特に限定されないが、基材に対する前処理剤組成物の濡れ性を考慮して設定される。また、表面張力調整剤の含有量は、前処理層上に付与される水性インクの当該前処理層に対する濡れ性も考慮して設定されるのが好ましい。表面張力調整剤の含有量は、通常は、前処理剤組成物の全質量に対し０．０１質量％～３．０質量％の範囲が好ましく、０．０５質量％～２質量％の範囲がより好ましく、０．１質量％～１質量％の範囲が特に好ましい。 The content of the surface tension adjusting agent is not particularly limited, but is set in consideration of the wettability of the pretreatment agent composition with respect to the substrate. The content of the surface tension adjusting agent is preferably set in consideration of the wettability of the water-based ink applied on the pretreatment layer with respect to the pretreatment layer. The content of the surface tension adjusting agent is usually preferably in the range of 0.01% by mass to 3.0% by mass, and in the range of 0.05% by mass to 2% by mass with respect to the total mass of the pretreatment agent composition. More preferably, the range of 0.1% by mass to 1% by mass is particularly preferable.
　前処理剤組成物の２５℃における表面張力は、２５ｍＮ／ｍ～３５ｍＮ／ｍの範囲が好ましく、２６ｍＮ／ｍ～３４ｍＮ／ｍの範囲がより好ましく、２７ｍＮ／ｍ～３２ｍＮ／ｍの範囲が特に好ましい。表面張力がこの数値範囲内であると、例えば、基材の表面張力が約４０ｍＮ／ｍ程度の軟包装材に対する前処理剤組成物の濡れ性を良好にできる。その結果、例えば、前処理剤組成物からなる前処理剤の基材への付与を、後述の塗布方法で行う場合には、当該前処理剤の塗布性が向上し、均一に塗布することができる。また、インクジェット法により前処理を行う際にも、前処理剤組成物の吐出安定性の確保等が図れる。更に、前処理剤組成物を用いて基材上に前処理層を形成し、記録媒体を作製した場合に、当該記録媒体にカールが発生するのを効果的に抑制することもできる。前処理剤組成物の表面張力は、例えば、表面張力計（商品名；ＤＹ－５００、協和界面科学株式会社製）を用いて、測定温度２５℃の条件下で測定することにより得られる。
（前処理剤組成物の製造方法）
　前処理剤組成物は以下に記載の製造方法で製造される。 The surface tension of the pretreatment composition at 25 ° C. is preferably in the range of 25 mN / m to 35 mN / m, more preferably in the range of 26 mN / m to 34 mN / m, and particularly preferably in the range of 27 mN / m to 32 mN / m. . When the surface tension is within this numerical range, for example, the wettability of the pretreatment composition with respect to a soft packaging material having a substrate surface tension of about 40 mN / m can be improved. As a result, for example, when the pretreatment agent composed of the pretreatment agent composition is applied to the base material by the application method described later, the coating property of the pretreatment agent can be improved and uniformly applied. it can. In addition, when performing the pretreatment by the ink jet method, it is possible to ensure the discharge stability of the pretreatment agent composition. Furthermore, when a pretreatment layer is formed on a substrate using a pretreatment agent composition to produce a recording medium, the occurrence of curling on the recording medium can be effectively suppressed. The surface tension of the pretreatment agent composition can be obtained, for example, by measuring using a surface tension meter (trade name: DY-500, manufactured by Kyowa Interface Science Co., Ltd.) at a measurement temperature of 25 ° C.
(Method for producing pretreatment agent composition)
The pretreatment agent composition is produced by the production method described below.
　まず、アルコール類に対して少なくとも一種の樹脂材料を溶解させた樹脂材料溶解液と、水に対して少なくとも一種の多価金属塩を溶解させた多価金属塩溶解液とを作成する。各溶解液の作成方法としては特に限定されず、各材料を混合し、その混合物を撹拌することによって作成することができる。作成した樹脂材料溶解液、多価金属塩溶解液、必要に応じて表面張力調整剤、およびその他の添加剤を任意の順番で加え、撹拌および混合することで前処理剤組成物を製造することができる。撹拌および混合に際しての混合物の温度および撹拌時間は、特に限定されず、適宜必要に応じて設定することができる。 First, a resin material solution in which at least one resin material is dissolved in alcohols and a polyvalent metal salt solution in which at least one polyvalent metal salt is dissolved in water are prepared. It does not specifically limit as a preparation method of each solution, It can create by mixing each material and stirring the mixture. Producing a pretreatment composition by adding the prepared resin material solution, polyvalent metal salt solution, surface tension modifier, and other additives as necessary, in any order, and stirring and mixing. Can do. The temperature and stirring time of the mixture at the time of stirring and mixing are not particularly limited, and can be appropriately set as necessary.
　混合後に粗大粒子やダストの除去を目的として混合物の濾過を行ってもよい。濾過に用いるフィルターの開孔径は、特に限定されず、適宜設定することができる。濾過は、複数種のフィルターを用いて行ってもよい。
（記録媒体）
　本実施の形態の記録媒体は、基材と、当該基材の少なくとも一方の面に設けられた前処理層とを少なくとも有する。記録媒体は、例えば、インクジェット記録方法による画像印刷等に用いられる。 After mixing, the mixture may be filtered for the purpose of removing coarse particles and dust. The aperture diameter of the filter used for filtration is not particularly limited, and can be set as appropriate. Filtration may be performed using a plurality of types of filters.
(recoding media)
The recording medium of the present embodiment includes at least a base material and a pretreatment layer provided on at least one surface of the base material. The recording medium is used for image printing by an inkjet recording method, for example.
　基材としては、特に限定されないが、本実施の形態は疎水性の基材に適用されるのが好適である。疎水性基材としては、従来公知の紙類や軟包装材等が挙げられる。例えば、ポリエステル系樹脂、ポリプロピレン系樹脂、塩化ビニル樹脂、ポリイミド樹脂等のプラスチックフィルム；金属、金属蒸着紙、ガラス、皮革、合成ゴム、天然ゴム等；軽量コート紙、コート紙、アート紙、キャスト紙、微塗工紙等の塗工紙等が挙げられる。 The substrate is not particularly limited, but the present embodiment is preferably applied to a hydrophobic substrate. Examples of the hydrophobic substrate include conventionally known papers and soft packaging materials. For example, plastic films such as polyester resin, polypropylene resin, vinyl chloride resin, polyimide resin; metal, metal-deposited paper, glass, leather, synthetic rubber, natural rubber, etc .; lightweight coated paper, coated paper, art paper, cast paper And coated paper such as finely coated paper.
　基材としては、疎水性基材に限定されず、従来公知の吸水性を示す基材にも、本実施の形態を適用可能である。 The substrate is not limited to a hydrophobic substrate, and the present embodiment can also be applied to a conventionally known substrate exhibiting water absorption.
　基材の厚さは、特に限定されず、適宜必要に応じて設定することができる。 The thickness of the base material is not particularly limited, and can be set as necessary.
　前処理層は、前処理剤組成物からなる前処理剤が乾燥し、基材上で乾燥皮膜化した層である。前処理層は、基材の表面および／又は裏面の全面、又はその一部に設けられていてもよい。 The pretreatment layer is a layer obtained by drying the pretreatment agent comprising the pretreatment composition and forming a dry film on the substrate. The pretreatment layer may be provided on the entire surface of the substrate and / or the back surface, or a part thereof.
　前処理層には樹脂材料が含まれており、樹脂材料は基材に対する密着性の向上に寄与する。その結果、耐剥離性および耐擦過性に優れた画像形成が可能になる。さらに、本実施の形態では難水溶性又は非水溶性の樹脂材料を用いるため、耐水性に優れた画像形成も可能になる。 前 Resin material is included in the pretreatment layer, and the resin material contributes to improved adhesion to the substrate. As a result, it is possible to form an image having excellent peel resistance and scratch resistance. Furthermore, in the present embodiment, since a poorly water-soluble or water-insoluble resin material is used, it is possible to form an image with excellent water resistance.
　前処理層には多価金属塩が含まれており、多価金属塩に由来する多価金属イオンは、例えば、水性インクに含まれる顔料の凝集やゲル化を生じさせ得る。その結果、本実施の形態の前処理層は、水性インクの受容層および凝集層としての機能を発揮する。これにより、前処理層は、水性インクの定着性を向上させ、隣接する水性インクの液滴同士（あるいは隣接するドット同士）の凝集によるビーディング、滲み、色ムラの発生を防止することができる。その結果、ドット径の安定性に優れ、良好な画質の画像を形成することができる。 The pretreatment layer contains a polyvalent metal salt, and polyvalent metal ions derived from the polyvalent metal salt can cause aggregation or gelation of the pigment contained in the aqueous ink, for example. As a result, the pretreatment layer of the present embodiment functions as a water-based ink receiving layer and aggregating layer. As a result, the pretreatment layer can improve the fixability of the water-based ink and can prevent the occurrence of beading, bleeding, and color unevenness due to aggregation of adjacent water-based ink droplets (or adjacent dots). . As a result, the dot diameter is excellent in stability and an image with good image quality can be formed.
　前処理層の（乾燥後の）厚さは０．１μｍ～２０μｍの範囲内が好ましく、１μｍ～５μｍの範囲内がより好ましい。厚さを０．１μｍ以上にすることにより、水性インクの定着性の維持が図られる。その一方、厚さを２０μｍ以下にすることにより、前処理剤の付与後の乾燥時間の短縮化が可能になる。 The thickness of the pretreatment layer (after drying) is preferably within a range of 0.1 μm to 20 μm, and more preferably within a range of 1 μm to 5 μm. By setting the thickness to 0.1 μm or more, it is possible to maintain the fixability of the water-based ink. On the other hand, when the thickness is 20 μm or less, the drying time after application of the pretreatment agent can be shortened.
　シリカ粒子等を用いた従来のインク受容層の厚さは３０μｍ程度である。一方、本実施の形態の前処理層の厚さは前述の通りであり、従来のインク受容層よりも厚さを薄くすることができる。具体的には、電子写真方式の軟包装用フィルムに用いられる前処理層と同等程度の厚さ（例えば、１μｍ程度）を実現することができる。 The thickness of a conventional ink receiving layer using silica particles or the like is about 30 μm. On the other hand, the thickness of the pretreatment layer of the present embodiment is as described above, and can be made thinner than the conventional ink receiving layer. Specifically, it is possible to realize a thickness (for example, about 1 μm) comparable to a pretreatment layer used for an electrophotographic soft packaging film.
　基材の一方又は両方の面に、必要に応じて、コロナ放電処理や易接着処理を施してもよい。更に、前処理層を形成していない基材の面に、記録媒体のカールを防止するためのカール防止層を設けてもよい。基材の両面に、同程度の厚さの前処理層を形成することによっても、記録媒体のカールの発生を防止してもよい。
（記録媒体への記録方法）
　本実施の形態の記録媒体への記録方法は、記録媒体上に水性インクを用いて画像を印刷するだけでなく、当該画像の印刷前に基材に施される前処理も含む。 One or both surfaces of the base material may be subjected to corona discharge treatment or easy adhesion treatment as necessary. Furthermore, an anti-curl layer for preventing curling of the recording medium may be provided on the surface of the base material on which the pretreatment layer is not formed. The curling of the recording medium may be prevented by forming a pretreatment layer having the same thickness on both surfaces of the substrate.
(Recording method to recording medium)
The recording method on the recording medium according to the present embodiment includes not only printing an image using a water-based ink on the recording medium but also a pretreatment applied to the substrate before printing the image.
　前処理は、基材表面に前処理剤組成物からなる前処理剤を付与する前処理剤付与工程と、付与された前処理剤を乾燥させ、前処理層を形成する前処理層形成工程とを少なくとも含む。 The pretreatment includes a pretreatment agent application step for applying a pretreatment agent composed of a pretreatment agent composition to the substrate surface, a pretreatment layer formation step for drying the applied pretreatment agent and forming a pretreatment layer. At least.
　前処理剤付与工程は、基材上に前処理剤を付与することにより行われる。前処理剤の付与は、基材の少なくとも一方の面の全面、又は画像の印刷領域に対応した任意の一部の領域に行うことができる。前処理剤の付与方法としては、特に限定されず、例えば、塗布法、インクジェット法、浸漬法（ディップコート）等の公知の方法が挙げられる。 The pretreatment agent application step is performed by applying a pretreatment agent on the substrate. The application of the pretreatment agent can be performed on the entire surface of at least one surface of the base material or an arbitrary partial region corresponding to the image printing region. It does not specifically limit as the provision method of a pre-processing agent, For example, well-known methods, such as the apply | coating method, the inkjet method, and the immersion method (dip coating), are mentioned.
　塗布方法としては、特に限定されず、例えば、バーコート、グラビアコート、グラビアリバースコート、ロールコート、ワイヤーバーコート、ブレードコート、ナイフコート、エアーナイフコート、コンマコート、スロットダイコート、ディップコート等が挙げられる。 The coating method is not particularly limited, and examples thereof include bar coating, gravure coating, gravure reverse coating, roll coating, wire bar coating, blade coating, knife coating, air knife coating, comma coating, slot die coating, dip coating, and the like. It is done.
　インクジェット法は、前処理剤組成物からなる前処理剤を微細なノズルより液滴として吐出し、その液滴を基材に付着させる。吐出方法としては、特に限定されず、例えば、連続噴射型（荷電制御型、スプレー型等）、オンデマンド型（ピエゾ方式、サーマル方式、静電吸引方式等）等の公知の方法を採用することができる。 In the inkjet method, a pretreatment agent composed of a pretreatment agent composition is ejected as droplets from a fine nozzle, and the droplets are attached to a substrate. The discharge method is not particularly limited, and for example, a known method such as a continuous injection type (charge control type, spray type, etc.), an on-demand type (piezo type, thermal type, electrostatic suction type, etc.) is adopted. Can do.
　インクジェット法を用いる場合、前処理剤の粘度は、インクジェットノズルからの吐出安定性を考慮して、インクジェットノズル吐出時において２ｍＰａ・ｓ～７ｍＰａ・ｓが好ましく、３ｍＰａ・ｓ～５ｍＰａ・ｓがより好ましい。前処理剤の粘度を前述の範囲内にすることにより、インクジェットノズルでの目詰まりの発生を抑制して良好な吐出安定性の維持が図れ、飛翔性の低下を抑制することができる。前処理剤の粘度は、例えば、粘度計（商品名：ＶＩＳＣＯＭＡＴＥ　ＭＯＤＥＬ　ＶＭ－１０Ａ、株式会社セコニック製）を用いて、測定温度２５℃の条件下で測定することにより得られる。 When the inkjet method is used, the viscosity of the pretreatment agent is preferably 2 mPa · s to 7 mPa · s, more preferably 3 mPa · s to 5 mPa · s when discharging the inkjet nozzle in consideration of ejection stability from the inkjet nozzle. . By setting the viscosity of the pretreatment agent within the above-described range, it is possible to suppress the occurrence of clogging at the ink jet nozzle, maintain good ejection stability, and suppress the decrease in flying property. The viscosity of the pretreatment agent can be obtained, for example, by measuring under a measurement temperature of 25 ° C. using a viscometer (trade name: VISCOMATE MODEL VM-10A, manufactured by Seconic Corporation).
　前処理剤の基材への供給（塗布）量は、形成したい前処理層の厚さに応じて適宜設定される。通常は、固形分換算で０．０５ｃｃ／ｍ２～２．０ｃｃ／ｍ２の範囲が好ましく、０．１ｃｃ／ｍ２～０．７ｃｃ／ｍ２の範囲がより好ましく、０．２ｃｃ／ｍ２～０．６ｃｃ／ｍ２の範囲が特に好ましい。供給量を０．０５ｃｃ／ｍ２以上にすることにより、記録媒体に水性インクの十分な定着性と密着性を付与することができ、画質が良好な印刷画像を得ることができる。その一方、供給量を２．０ｃｃ／ｍ２以下にすることにより、前処理層の厚さが厚くなり過ぎるのを抑制し、後加工を容易に行うことができる。 The supply (application) amount of the pretreatment agent to the substrate is appropriately set according to the thickness of the pretreatment layer to be formed. Typically, the preferred range of 0.05cc / m 2 ~ 2.0cc / m 2 in terms of solid content, more preferably in the range of 0.1cc / m 2 ~ 0.7cc / m 2, 0.2cc / m 2 A range of ˜0.6 cc / m 2 is particularly preferred. By setting the supply amount to 0.05 cc / m 2 or more, sufficient fixability and adhesion of water-based ink can be imparted to the recording medium, and a printed image with good image quality can be obtained. On the other hand, by setting the supply amount to 2.0 cc / m 2 or less, it is possible to suppress the pretreatment layer from becoming too thick and to easily perform post-processing.
　前処理層形成工程は、基材表面に付与された前処理剤を乾燥させることにより行われる。前処理剤の乾燥は、前処理剤に含まれる溶媒の蒸発を促進させるものであれば特に限定されない。例えば、前処理剤に熱風を吹き付ける方法や自然乾燥、適宜の温度に設定された加熱ドラム等に当該前処理剤を接触させて乾燥させる方法等が挙げられる。具体的には、強制空気加熱等の温風処理、輻射加熱、伝導加熱、高周波乾燥、マイクロ波乾燥、ヒーターによる加熱等が可能である。乾燥条件は、前処理剤の供給量等に応じて、適宜変更して設定することができる。前処理剤の乾燥により、基材の少なくとも一方の面上に前処理層が形成された記録媒体が得られる。乾燥後、得られた記録媒体に対し、その表面の平滑度又は表面強度を高めるために、必要に応じて、カレンダー処理、スーパーカレンダー処理等を行ってもよい。 The pretreatment layer forming step is performed by drying the pretreatment agent applied to the substrate surface. The drying of the pretreatment agent is not particularly limited as long as it accelerates the evaporation of the solvent contained in the pretreatment agent. For example, a method of spraying hot air on the pretreatment agent, natural drying, a method of bringing the pretreatment agent into contact with a heating drum set to an appropriate temperature and the like, and the like can be mentioned. Specifically, hot air treatment such as forced air heating, radiation heating, conduction heating, high frequency drying, microwave drying, heating with a heater, and the like are possible. The drying conditions can be appropriately changed and set according to the supply amount of the pretreatment agent and the like. By drying the pretreatment agent, a recording medium having a pretreatment layer formed on at least one surface of the substrate is obtained. After drying, the obtained recording medium may be subjected to a calendar process, a super calendar process, or the like as necessary in order to increase the smoothness or surface strength of the surface.
　水性インクを用いた画像の印刷は、例えば、前処理剤付与工程によって基材表面に付与された前処理剤に対して、あるいは、前処理層形成工程によって基材表面に形成された前処理層に対して行われる。 The printing of the image using the water-based ink is performed, for example, on the pretreatment agent applied to the substrate surface by the pretreatment agent application step or the pretreatment layer formed on the substrate surface by the pretreatment layer formation step. To be done.
　前者の場合、本実施の形態の記録方法は、前処理剤付与工程の直後であって、前処理層形成工程の前に、基材上の前処理剤に対して水性インクを付与する第１インク付与工程を更に含む。この場合、前処理層形成工程は、前処理剤だけでなく、当該前処理剤上に付与された水性インクも同時に乾燥させ、これにより画像を形成する。 In the former case, the recording method of the present embodiment is a first method in which aqueous ink is applied to the pretreatment agent on the substrate immediately after the pretreatment agent application step and before the pretreatment layer formation step. It further includes an ink application step. In this case, in the pretreatment layer forming step, not only the pretreatment agent but also the water-based ink applied on the pretreatment agent is simultaneously dried to thereby form an image.
　後者の場合、本実施の形態の記録方法は、前処理層上に水性インクを付与する第２インク付与工程と、前処理層上に付与された水性インクを乾燥させる乾燥工程とを更に含む。 In the latter case, the recording method of the present embodiment further includes a second ink application step for applying aqueous ink on the pretreatment layer, and a drying step for drying the aqueous ink applied on the pretreatment layer.
　基材上に付与された前処理剤、又は当該基材上に形成された前処理層に対する水性インクの付与方法は特に限定されず、公知の方法を採用することができる。より具体的には、前述のインクジェット記録方法等が挙げられる。水性インクの吐出方法についても特に限定されず、前述の通りである。従って、その詳細な説明は省略する。 The method for applying the water-based ink to the pretreatment agent applied on the substrate or the pretreatment layer formed on the substrate is not particularly limited, and a known method can be adopted. More specifically, the above-described inkjet recording method and the like can be mentioned. The method for discharging the water-based ink is not particularly limited and is as described above. Therefore, the detailed description is abbreviate | omitted.
　基材上の前処理剤、又は前処理層に含まれる多価金属塩由来の多価金属イオンは、当該前処理層等に付着した水性インクの固体成分（より具体的には、顔料等の色材やアニオン性の樹脂等）の粒子の分散機能を低下させ、凝集を引き起こす。その結果、水性インクの液滴同士の混合による滲みや色ムラの発生を低減することができる。また、記録媒体上に顔料等を密に固着させることができるので、高画質の画像を記録することができる。固体成分の粒子の凝集は、前処理層に水性インクを付与するよりも、基材上の前処理剤に水性インクを付与する場合の方が、速く進行させることができる。前処理層の形成前には、前処理剤に含まれる溶媒が蒸発していないので、多価金属イオンの状態で存在するためである。 The pretreatment agent on the substrate or the polyvalent metal ion derived from the polyvalent metal salt contained in the pretreatment layer is a solid component (more specifically, a pigment or the like) of the aqueous ink attached to the pretreatment layer. This lowers the dispersion function of particles such as coloring materials and anionic resins, and causes aggregation. As a result, it is possible to reduce the occurrence of bleeding and color unevenness due to mixing of water-based ink droplets. Further, since a pigment or the like can be closely fixed on the recording medium, a high-quality image can be recorded. Aggregation of the solid component particles can proceed faster when the aqueous ink is applied to the pretreatment agent on the substrate than when the aqueous ink is applied to the pretreatment layer. This is because the solvent contained in the pretreatment agent is not evaporated before the pretreatment layer is formed, and therefore exists in the state of polyvalent metal ions.
　基材上の前処理剤に対する水性インクの付与には、インクジェットヘッドの１回の走査で基材に印刷する、いわゆる１パス（シングルパス）方式での印刷を用いることが好適である。１パス方式での印刷が可能なインクジェット印刷装置は、通常、基材幅以上の印刷幅をもつライン状のヘッドユニットを、複数個（通常は色の数の分）だけ備え、それらを基材の搬送方向に並べた構造を有している。この様な印刷装置を用いた１パス方式での印刷は、短時間で、隣接するヘッドユニットから液滴を相次いで吐出して印刷することができる。従って、このようなインクジェット印刷装置を用いれば、一つのヘッドユニットから基材上に前処理剤を吐出した直後に、当該前処理剤上に次のヘッドユニットから水性インクの液滴を吐出することができる。それにより、前処理剤を用いた前処理と、水性インクを用いた画像印刷とを１パス方式にて高速で実行することができる。 For applying the water-based ink to the pretreatment agent on the substrate, it is preferable to use so-called one-pass (single-pass) printing, in which printing is performed on the substrate by one scan of the inkjet head. An inkjet printing apparatus capable of printing in a one-pass method usually includes a plurality of (typically, the number of colors) line-type head units having a printing width larger than the width of the substrate, and these are the substrates. Are arranged in the transport direction. Printing in such a one-pass method using such a printing apparatus can be performed by discharging droplets from adjacent head units one after another in a short time. Therefore, using such an ink jet printing apparatus, immediately after discharging a pretreatment agent on a substrate from one head unit, a droplet of aqueous ink is discharged from the next head unit onto the pretreatment agent. Can do. Thereby, pre-processing using a pre-processing agent and image printing using water-based ink can be executed at high speed by a one-pass method.
　前処理剤上、又は前処理層上に水性インクの液滴を吐出して付着させた後は、吐出された水性インクを加熱乾燥することにより印刷画像を定着する。乾燥温度は、水性インクに含まれる溶媒や基材の種類、乾燥時間等に応じて適宜設定することができる。乾燥時間についても特に限定されず、水性インク中の溶媒や基材の種類、印刷速度等に応じて適宜設定することができる。吐出された水性インクの加熱乾燥を、基材上に付与された前処理剤の加熱乾燥と共に行う場合は、当該前処理剤に含まれる溶媒等の乾燥も考慮して、乾燥温度および乾燥時間が設定される。乾燥温度とは基材の表面温度を意味する。 After the water-based ink droplets are ejected and adhered onto the pretreatment agent or the pretreatment layer, the printed image is fixed by heating and drying the ejected aqueous ink. The drying temperature can be appropriately set according to the solvent contained in the water-based ink, the type of the substrate, the drying time, and the like. The drying time is not particularly limited, and can be appropriately set according to the solvent in the water-based ink, the type of the substrate, the printing speed, and the like. When performing heat drying of the discharged water-based ink together with heat drying of the pretreatment agent applied on the substrate, the drying temperature and drying time are also considered in consideration of the drying of the solvent contained in the pretreatment agent. Is set. The drying temperature means the surface temperature of the substrate.
　吐出された水性インクの加熱乾燥の方法は、水性インク中の溶媒の蒸発を促進させるものであれば特に限定されない。例えば、吐出された水性インクに熱風を吹き付ける方法や、適宜の温度に設定された加熱ドラム等に当該水性インクを接触させて乾燥させる方法等が挙げられる。具体的には、強制空気加熱等の温風処理、輻射加熱、伝導加熱、高周波乾燥、マイクロ波乾燥、ヒーターによる加熱等が可能である。 The method of heating and drying the discharged water-based ink is not particularly limited as long as it promotes evaporation of the solvent in the water-based ink. For example, a method of spraying hot air on the discharged water-based ink, a method of bringing the water-based ink into contact with a heating drum set to an appropriate temperature, and the like, can be used. Specifically, hot air treatment such as forced air heating, radiation heating, conduction heating, high frequency drying, microwave drying, heating with a heater, and the like are possible.
　吐出された水性インクの乾燥によりこれを固化し、インク層を形成することができる。インク層の（乾燥後の）厚さは特に限定されず、適宜必要に応じて設定することができる。通常は、０．５μｍ～１０μｍの範囲内で設定される。 The dried water-based ink can be solidified by drying to form an ink layer. The thickness (after drying) of the ink layer is not particularly limited, and can be set as necessary. Usually, it is set within the range of 0.5 μm to 10 μm.
　以上により、本実施の形態においては、滲みや色ムラが抑制され、良好なインク定着性を示す高画質の画像を記録媒体上に印刷することができる。 As described above, in this embodiment, bleeding and color unevenness are suppressed, and a high-quality image showing good ink fixing properties can be printed on a recording medium.
　水性インクとしては、少なくとも１種の顔料と、バインダーとを含むものが好ましい。顔料およびバインダーとしては、インク組成物に通常用いられているものを特に制限なく使用することができる。前処理剤組成物に含まれる樹脂材料との密着性の観点からは、顔料としてスチレン－アクリル系樹脂で被覆されたものが好ましい。この場合、バインダーとしてはスチレン－アクリル系エマルジョンが好ましい。 The water-based ink preferably contains at least one pigment and a binder. As the pigment and the binder, those usually used in the ink composition can be used without particular limitation. From the viewpoint of adhesion to the resin material contained in the pretreatment composition, those coated with a styrene-acrylic resin as a pigment are preferable. In this case, the binder is preferably a styrene-acrylic emulsion.
　本実施の形態においては、水性インクを例にして本発明の一例を説明したが、本発明はこれに限定されるものではない。溶剤系又は油性の非水性インク（但し、ＵＶインクを除く。）に対しても、本発明の前処理剤組成物は、当該非水性インクを良好に定着させ、かつ、基材に対して良好な密着性を示す前処理層の形成を可能にする。
（記録媒体の製造方法）
　本実施の形態の記録媒体の製造方法は、前述の前処理剤付与工程と、前処理層形成工程とを少なくとも含むものである。これにより、インクの滲みやビーディングの発生を抑制しつつ、インクを良好に定着して画像を形成することが可能で、かつ、印刷画像の耐剥離性、耐擦過性および耐水性を有する記録媒体を製造することができる。前処理剤付与工程および前処理層形成工程の詳細については、前述の通りであるので、その説明は省略する。 In the present embodiment, an example of the present invention has been described using water-based ink as an example, but the present invention is not limited to this. Even for solvent-based or oil-based non-aqueous inks (excluding UV inks), the pretreatment composition of the present invention fixes the non-aqueous ink well and is good for a substrate. It is possible to form a pretreatment layer exhibiting excellent adhesion.
(Recording medium manufacturing method)
The manufacturing method of the recording medium of the present embodiment includes at least the above-described pretreatment agent application step and pretreatment layer formation step. As a result, it is possible to form an image by satisfactorily fixing the ink while suppressing the occurrence of ink bleeding and beading, and the print image has a peel resistance, scratch resistance and water resistance. A medium can be manufactured. The details of the pretreatment agent applying step and the pretreatment layer forming step are as described above, and thus the description thereof is omitted.
　また、本実施の形態の記録媒体の製造方法は、更に、必要に応じて他の工程を有していてもよい。例えば、表面の平滑度又は表面強度を高めるために、必要に応じてカレンダー処理、スーパーカレンダー処理等を行ってもよい。カレンダー処理等を行う際の処理条件については特に限定されず、適宜必要に応じて設定することができる。 Further, the recording medium manufacturing method of the present embodiment may further include other steps as necessary. For example, in order to increase the smoothness or surface strength of the surface, a calendar process, a super calendar process, or the like may be performed as necessary. There are no particular limitations on the processing conditions when performing calendar processing or the like, and it can be set as necessary.
　以下に、この発明の好適な実施例を例示的に詳しく説明する。但し、下記の実施例に記載されている材料や含有量等は、特に限定的な記載がない限りは、この発明の範囲をそれらに限定するものではない。
（実施例１～８）
　各実施例１～８においては、樹脂材料としてのセラック(商品名；乾燥透明白ラック、日本シェラック工業株式会社製)、樹脂材料の溶媒としてのエタノール(商品名；エタノール（９９．５）、和光純薬工業株式会社製)、多価金属塩としての乳酸カルシウム（商品名；ＤＬ－乳酸カルシウム五水和物、和光純薬工業株式会社製）、多価金属塩の溶媒としての純水、および表面張力調整剤（商品名；ＳＹグリスターＭＣＡ－７５０、阪本薬品工業株株式会社製）を、それぞれ表１に示す配合割合となる様に前述した前処理剤組成物の製造方法に従って混合および撹拌し、それぞれの前処理剤組成物を作製した。
（比較例１～２）
　比較例１および比較例２においては、実施例１～８と同じ材料を用いて、表１に示す配合割合にて、比較例１および比較例２に係る前処理剤組成物を作製した。 Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, materials, contents, and the like described in the following examples do not limit the scope of the present invention unless otherwise specified.
(Examples 1 to 8)
In each of Examples 1 to 8, shellac as a resin material (trade name; dry transparent white rack, manufactured by Nippon Shellac Industrial Co., Ltd.), ethanol as a solvent for the resin material (trade name; ethanol (99.5), Japanese Kogaku Pharmaceutical Co., Ltd.), calcium lactate as a polyvalent metal salt (trade name; DL-calcium lactate pentahydrate, manufactured by Wako Pure Chemical Industries, Ltd.), pure water as a solvent for the polyvalent metal salt, and A surface tension modifier (trade name: SY Glister MCA-750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was mixed and stirred according to the preparation method of the pretreatment composition described above so that the blending ratios shown in Table 1 were obtained. Each pretreatment agent composition was prepared.
(Comparative Examples 1 and 2)
In Comparative Example 1 and Comparative Example 2, pretreatment agent compositions according to Comparative Example 1 and Comparative Example 2 were prepared using the same materials as in Examples 1 to 8 at the blending ratios shown in Table 1.
　実施例１～４では、多価金属塩としての乳酸カルシウムの配合割合を一定とし、樹脂材料としてのセラックの配合割合を実施例毎に変更した。樹脂材料の配合割合に合わせてエタノールの含有量も表１に示すように適宜変更している。比較例１では、実施例４と比較すると、多価金属塩としての乳酸カルシウムを添加しなかった点が異なる。 In Examples 1 to 4, the mixing ratio of calcium lactate as a polyvalent metal salt was constant, and the mixing ratio of shellac as a resin material was changed for each example. The ethanol content is appropriately changed as shown in Table 1 in accordance with the blending ratio of the resin material. Comparative Example 1 differs from Example 4 in that calcium lactate as a polyvalent metal salt was not added.
　実施例５～８および比較例２では、樹脂材料としてのセラックの配合割合を一定とし、多価金属塩としての乳酸カルシウムの配合割合を変更した。このとき、多価金属塩の配合割合に合わせて純水およびエタノールの配合割合も表１に示すように適宜変更している。
（実施例９～１３）
　各実施例９～１３においては、樹脂材料としてのセラック(商品名；乾燥透明白ラック、日本シェラック工業株式会社製)、樹脂材料の溶媒としてのエタノール(商品名；エタノール（９９．５）、和光純薬工業株式会社製)、多価金属塩としての酢酸カルシウム（商品名；酢酸カルシウム一水和物、和光純薬工業株式会社製）、多価金属塩の溶媒としての純水、および表面張力調整剤（商品名；ＳＹグリスターＭＣＡ－７５０、阪本薬品工業株式会社製）を、それぞれ表２に示す配合割合となる様に前述した前処理剤組成物の製造方法に従って混合および撹拌し、それぞれの前処理剤組成物を作製した。
（比較例３～５）
　比較例３～５においては、実施例９～１３と同じ材料を用いて、表２に示す配合割合にて、比較例３～５に係る前処理剤組成物を作製した。 In Examples 5 to 8 and Comparative Example 2, the blending ratio of shellac as the resin material was made constant, and the blending ratio of calcium lactate as the polyvalent metal salt was changed. At this time, the mixing ratio of pure water and ethanol is appropriately changed as shown in Table 1 in accordance with the mixing ratio of the polyvalent metal salt.
(Examples 9 to 13)
In each of Examples 9 to 13, shellac as a resin material (trade name; dry transparent white rack, manufactured by Nippon Shellac Industrial Co., Ltd.), ethanol as a solvent for the resin material (trade name; ethanol (99.5), Japanese Komatsu Pharmaceutical Co., Ltd.), calcium acetate as a polyvalent metal salt (trade name; calcium acetate monohydrate, manufactured by Wako Pure Chemical Industries, Ltd.), pure water as a solvent for polyvalent metal salt, and surface tension The modifier (trade name: SY Glister MCA-750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was mixed and stirred according to the preparation method of the pretreatment composition described above so that the mixing ratio shown in Table 2 was obtained. A pretreatment composition was prepared.
(Comparative Examples 3 to 5)
In Comparative Examples 3 to 5, pretreatment agent compositions according to Comparative Examples 3 to 5 were prepared using the same materials as in Examples 9 to 13 and at the blending ratios shown in Table 2.
　実施例９～１２では、多価金属塩としての酢酸カルシウムの配合割合を一定とし、樹脂材料としてのセラックの配合割合を実施例毎に変更した。樹脂材料の配合割合に合わせてエタノールの含有量も表２に示すように適宜変更している。比較例３では、実施例１２と比較すると、多価金属塩としての酢酸カルシウムを添加しなかった点が異なる。 In Examples 9 to 12, the mixing ratio of calcium acetate as the polyvalent metal salt was made constant, and the mixing ratio of shellac as the resin material was changed for each example. The ethanol content is appropriately changed as shown in Table 2 in accordance with the blending ratio of the resin material. Comparative Example 3 differs from Example 12 in that calcium acetate as a polyvalent metal salt was not added.
　実施例１３および比較例４～５では、樹脂材料としてのセラックの配合割合を一定とし、多価金属塩としての酢酸カルシウムの配合割合を変更した。このとき、多価金属塩の配合割合に合わせて純水およびエタノールの配合割合も表２に示すように適宜変更している。 In Example 13 and Comparative Examples 4 to 5, the blending ratio of shellac as the resin material was made constant, and the blending ratio of calcium acetate as the polyvalent metal salt was changed. At this time, the mixing ratio of pure water and ethanol is appropriately changed as shown in Table 2 in accordance with the mixing ratio of the polyvalent metal salt.
　こうして実施例１～１３および比較例１～５に係る前処理剤組成物を作製した。続いて、作製した各前処理剤組成物を用いて基材に対して前処理および画像印刷を施し、前処理剤組成物の評価を行った。ただし、比較例２においては、多価金属塩の不溶分が発生したため、基材に対する前処理および画像印刷は実施できなかった。比較例４および比較例５においては、酢酸カルシウムがエタノールによってゲル化して流動性を失ったため、基材に対する前処理および画像印刷は実施できなかった。
＜前処理層の形成＞
　まず、基材としてＰＥＴフィルム（商品名：Ｅ５１００、東洋紡株式会社製）およびアルミ基材（商品名：ＵＧ－８４９５、キャプテンスタッグ株式会社販売）を準備した。これらの基材の一方の面に、各実施例１～１３、比較例１および比較例３の前処理剤組成物からなる前処理剤を用いてそれぞれ前処理を施した。前処理は、先ずバーコーター（商品名；バーコーターＮｏ.３、アズワン株式会社製）を用いて、ＰＥＴフィルム上およびアルミ基材上に前処理剤を塗布して行った。塗布量は固形分換算で０．６ｃｃ／ｍ２とした。次いで、ＰＥＴフィルム上に塗布した前処理剤は、加熱温度７０℃、加熱時間１ｍｉｎの条件下で加熱乾燥し、前処理層を形成した。また、アルミ基材上に塗布した前処理剤は、加熱温度７０℃、加熱時間１ｍｉｎの条件下で加熱乾燥し、前処理層を形成した。これにより、各実施例１～１３および比較例１および３に係る記録媒体を作製した。
＜画像印刷＞
　次に、水性インク組成物からなる水性インクを用いて、各実施例１～１３、比較例１および比較例３に係る記録媒体に対しインクジェット方式により印刷を行った。印刷には、インクジェットプリンター（商品名：ＰＸ－１０５ 、セイコーエプソン株式会社製）を用いた。 Thus, pretreatment agent compositions according to Examples 1 to 13 and Comparative Examples 1 to 5 were produced. Subsequently, pretreatment and image printing were performed on the base material using each prepared pretreatment composition, and the pretreatment composition was evaluated. However, in Comparative Example 2, since the insoluble content of the polyvalent metal salt was generated, the pretreatment and image printing on the substrate could not be performed. In Comparative Example 4 and Comparative Example 5, since calcium acetate gelled with ethanol and lost fluidity, pretreatment and image printing on the substrate could not be performed.
<Formation of pretreatment layer>
First, a PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.) and an aluminum base material (trade name: UG-8495, sold by Captain Stag Co., Ltd.) were prepared as base materials. One side of these base materials was pretreated using pretreatment agents comprising the pretreatment agent compositions of Examples 1 to 13, Comparative Examples 1 and 3, respectively. The pretreatment was performed by first applying a pretreatment agent on a PET film and an aluminum substrate using a bar coater (trade name; Bar Coater No. 3, manufactured by ASONE Co., Ltd.). The coating amount was 0.6 cc / m 2 in terms of solid content. Next, the pretreatment agent applied on the PET film was heat-dried under the conditions of a heating temperature of 70 ° C. and a heating time of 1 min to form a pretreatment layer. Moreover, the pretreatment agent applied on the aluminum substrate was heat-dried under the conditions of a heating temperature of 70 ° C. and a heating time of 1 min to form a pretreatment layer. Thus, recording media according to Examples 1 to 13 and Comparative Examples 1 and 3 were produced.
<Image printing>
Next, printing was performed on the recording media according to Examples 1 to 13, Comparative Example 1 and Comparative Example 3 by an ink jet method using an aqueous ink composed of an aqueous ink composition. An ink jet printer (trade name: PX-105, manufactured by Seiko Epson Corporation) was used for printing.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（前処理層の耐テープ剥離性）　
　各実施例および比較例に係る前処理層の耐テープ剥離性については、各実施例および比較例に係る記録媒体の前処理層に対して、粘着テープ（商品名：セロテープ（登録商標）Ｎｏ．４０５、ニチバン株式会社製）を貼り付けて評価した。具体的には、貼り付け後に、粘着テープを剥がしたときの前処理層の剥がれやテープへの移り状態を確認することにより、テープ剥離性を目視で評価した。結果を表１、表２に示す。 (Tape peel resistance of pretreatment layer)
Regarding the tape peel resistance of the pretreatment layer according to each example and comparative example, the pressure-sensitive adhesive tape (trade name: Cellotape (registered trademark) No. 1 was used for the pretreatment layer of the recording medium according to each example and comparative example. 405, manufactured by Nichiban Co., Ltd.) for evaluation. Specifically, the tape peelability was visually evaluated by confirming the peeling of the pretreatment layer when the adhesive tape was peeled off and the transfer state to the tape after the application. The results are shown in Tables 1 and 2.
　○：粘着テープへの前処理層の付着なし
　×：粘着テープへの前処理層の付着あり
　表１および表２に示す通り、実施例１～１３、比較例１および比較例３に係る記録媒体の何れにおいても、良好な耐テープ剥離性を示している。従って、当該前処理剤組成物を用いて形成された前処理層は、ＰＥＴフィルムおよびアルミ基材に対し、良好な密着性を示すことが確認された。
（前処理層の耐擦過性）
　各実施例および比較例に係る前処理層の耐擦過性については、各実施例および比較例に係る記録媒体の前処理層を爪で２回擦り、前処理層の剥がれ状態を確認することにより、耐擦過性を目視で評価した。結果を表１、表２に示す。 ○: No pretreatment layer attached to adhesive tape ×: Pretreatment layer attached to adhesive tape As shown in Tables 1 and 2, recording media according to Examples 1 to 13, Comparative Example 1 and Comparative Example 3 In any of these, good tape peel resistance is shown. Therefore, it was confirmed that the pretreatment layer formed using the pretreatment agent composition exhibits good adhesion to the PET film and the aluminum substrate.
(Scratch resistance of pretreatment layer)
Regarding the scratch resistance of the pretreatment layer according to each Example and Comparative Example, the pretreatment layer of the recording medium according to each Example and Comparative Example is rubbed twice with a nail, and the peeling state of the pretreatment layer is confirmed. The scratch resistance was visually evaluated. The results are shown in Tables 1 and 2.
　○：前処理層の剥がれなし
　×：前処理層の剥がれあり
　表１および表２に示す通り、実施例１～１３、比較例１および比較例３に係る記録媒体の何れにおいても、良好な耐擦過性を示している。従って、当該前処理剤組成物を用いて形成された前処理層は、ＰＥＴフィルムおよびアルミ基材に対し、良好な密着性を示すことが確認された。
（前処理層の耐水性）
　各実施例および比較例に係る前処理層の耐水性については、各実施例および比較例に係る記録媒体の前処理層に対して、濡らしたガーゼでワイプを行って評価した。具体的には、ワイプ後の前処理層の剥がれ状態を確認することにより、耐水性を目視で評価した。結果を表１、表２に示す。 ○: No peeling of the pretreatment layer ×: Peeling of the pretreatment layer As shown in Tables 1 and 2, the recording media according to Examples 1 to 13, Comparative Example 1 and Comparative Example 3 had good resistance to peeling. It shows fretting properties. Therefore, it was confirmed that the pretreatment layer formed using the pretreatment agent composition exhibits good adhesion to the PET film and the aluminum substrate.
(Water resistance of pretreatment layer)
The water resistance of the pretreatment layers according to the examples and comparative examples was evaluated by wiping the pretreatment layers of the recording media according to the examples and comparative examples with wet gauze. Specifically, the water resistance was visually evaluated by confirming the peeling state of the pretreatment layer after wiping. The results are shown in Tables 1 and 2.
　○：前処理層の剥がれなし
　×：前処理層の剥がれあり
　表１および表２に示す通り、実施例１～１３、比較例１および比較例３に係る記録媒体の何れにおいても、良好な耐水性を示している。従って、当該前処理剤組成物を用いて形成された前処理層はＰＥＴフィルムおよびアルミ基材に対し、水分を多く含む雰囲気下においても良好な密着性を示すことが確認された。
（前処理層に対する水性インクの定着性）
　各実施例および比較例に係る記録媒体に、水性インク組成物からなる水性インクで画像を印刷した後のインク定着性については、次の評価基準に基づき評価を行った。結果を表１、表２に示す。 ○: Pretreatment layer is not peeled ×: Pretreatment layer is peeled off As shown in Tables 1 and 2, good water resistance is obtained in any of the recording media according to Examples 1 to 13, Comparative Example 1 and Comparative Example 3. Showing sex. Therefore, it was confirmed that the pretreatment layer formed using the pretreatment composition exhibits good adhesion to the PET film and the aluminum substrate even in an atmosphere containing a lot of moisture.
(Fixability of water-based ink to the pretreatment layer)
The ink fixability after printing an image with a water-based ink composed of a water-based ink composition on the recording media according to each of Examples and Comparative Examples was evaluated based on the following evaluation criteria. The results are shown in Tables 1 and 2.
　○：印刷画像にビーディング、滲みおよび色ムラの発生なし
　×：印刷画像にビーディング、滲みおよび色ムラの発生あり
　表１および表２に示す通り、実施例１～１３に係る記録媒体上に印刷された印刷画像においては、何れも印刷画像にビーディング、滲みおよび色ムラの発生が観察されず、インク定着性が良好であることが確認された。その一方、比較例１および比較例３に係る記録媒体上に印刷された印刷画像においては、多価金属塩を添加しなかったため、印刷画像にビーディング、滲みおよび色ムラの発生が確認された。 ○: No occurrence of beading, bleeding and color unevenness in printed image ×: Generation of beading, bleeding and color unevenness in printed image As shown in Tables 1 and 2, on the recording media according to Examples 1 to 13 In any printed image, no beading, bleeding or color unevenness was observed in the printed image, and it was confirmed that the ink fixing property was good. On the other hand, in the printed images printed on the recording media according to Comparative Example 1 and Comparative Example 3, since the polyvalent metal salt was not added, occurrence of beading, bleeding and color unevenness was confirmed in the printed image. .

Claims (20)

  1. 　基材の少なくとも一方の面に対し、前処理を行うための前処理剤組成物であって、
    　少なくとも一種の難水溶性および／又は非水溶性の樹脂と、アルコール類と、少なくとも１種の多価金属塩と、を少なくとも含み、
    　前記樹脂の含有量が、前処理剤組成物の全質量に対し０．１質量％～３０質量％であり、
    　前記多価金属塩の含有量が、前処理剤組成物の全質量に対し０．１質量％～１０質量％である、前処理剤組成物。     A pretreatment agent composition for performing pretreatment on at least one surface of a substrate,
    Including at least one poorly water-soluble and / or water-insoluble resin, an alcohol, and at least one polyvalent metal salt,
    The content of the resin is 0.1% by mass to 30% by mass with respect to the total mass of the pretreatment agent composition,
    The pretreatment agent composition, wherein the content of the polyvalent metal salt is 0.1% by mass to 10% by mass with respect to the total mass of the pretreatment agent composition.
  2. 　前記多価金属塩が、マグネシウム塩、アルミニウム塩、カルシウム塩、チタン塩、マンガン塩、鉄塩、ニッケル塩、銅塩、亜鉛塩、スズ塩およびバリウム塩からなる群より選ばれる少なくとも１種である、請求項１に記載の前処理剤組成物。 The polyvalent metal salt is at least one selected from the group consisting of magnesium salt, aluminum salt, calcium salt, titanium salt, manganese salt, iron salt, nickel salt, copper salt, zinc salt, tin salt and barium salt. The pretreatment agent composition according to claim 1.
  3. 　前記カルシウム塩が、乳酸カルシウムおよび酢酸カルシウムの少なくとも一方を含む、請求項２に記載の前処理剤組成物。 The pretreatment composition according to claim 2, wherein the calcium salt contains at least one of calcium lactate and calcium acetate.
  4. 　前記乳酸カルシウムの含有量が、前処理剤組成物の全質量に対し５質量％未満である、請求項３に記載の前処理剤組成物。 The pretreatment composition according to claim 3, wherein the content of the calcium lactate is less than 5 mass% with respect to the total mass of the pretreatment composition.
  5. 　前記酢酸カルシウムの含有量が、前処理剤組成物の全質量に対し２質量％未満である、請求項３に記載の前処理剤組成物。 The pretreatment agent composition according to claim 3, wherein the content of the calcium acetate is less than 2% by mass relative to the total mass of the pretreatment agent composition.
  6. 　前記樹脂が、セラック樹脂、酢酸ビニル樹脂、アクリル樹脂、およびロジン樹脂の少なくとも何れかを含む、請求項１～５の何れか１項に記載の前処理剤組成物。 The pretreatment composition according to any one of claims 1 to 5, wherein the resin contains at least one of shellac resin, vinyl acetate resin, acrylic resin, and rosin resin.
  7. 　前記アルコール類が、第１級アルコールである、請求項１～６の何れか１項に記載の前処理剤組成物。 The pretreatment composition according to any one of claims 1 to 6, wherein the alcohol is a primary alcohol.
  8. 　前記第１級アルコールが、メタノールおよびエタノールの少なくとも一方を含む、請求項７に記載の前処理剤組成物。 The pretreatment composition according to claim 7, wherein the primary alcohol contains at least one of methanol and ethanol.
  9. 　前記基材が、疎水性の基材である、請求項１～８のいずれか１項に記載の前処理剤組成物。 The pretreatment composition according to any one of claims 1 to 8, wherein the substrate is a hydrophobic substrate.
  10. 　基材の少なくとも一方の面に対し、前処理を行うための前処理剤組成物の製造方法であって、
    　少なくとも一種の難水溶性および／又は非水溶性の樹脂をアルコール類に溶解させて樹脂溶解液を作製する工程と、
    　少なくとも一種の多価金属塩を溶媒に対して溶解させて多価金属塩溶解液を作製する工程と、
    　前記樹脂溶解液と前記多価金属塩溶解液とを混合する工程と、を含む前処理剤組成物の製造方法。     A method for producing a pretreatment composition for performing pretreatment on at least one surface of a substrate,
    A step of preparing a resin solution by dissolving at least one kind of poorly water-soluble and / or water-insoluble resin in alcohols;
    Dissolving at least one polyvalent metal salt in a solvent to produce a polyvalent metal salt solution;
    The process of mixing the said resin solution and the said polyvalent metal salt solution, The manufacturing method of the pretreatment agent composition.
  11. 　前記溶媒が、水である、請求項１０に記載の前処理剤組成物の製造方法。 The method for producing a pretreatment agent composition according to claim 10, wherein the solvent is water.
  12. 　基材と、前記基材の少なくとも一方の面上に設けられた前処理層とを含む記録媒体であって、
    　前記前処理層の少なくとも一部は前処理剤の乾燥皮膜からなり、
    　前記前処理剤は、請求項１～９の何れか１項に記載の前処理剤組成物からなるものである、記録媒体。     A recording medium comprising a substrate and a pretreatment layer provided on at least one surface of the substrate,
    At least a part of the pretreatment layer comprises a dry film of a pretreatment agent,
    A recording medium comprising the pretreatment agent composition according to any one of claims 1 to 9, wherein the pretreatment agent is a pretreatment agent composition.
  13. 　前記基材が、疎水性の基材である、請求項１２に記載の記録媒体。 The recording medium according to claim 12, wherein the substrate is a hydrophobic substrate.
  14. 　基材と、前記基材の少なくとも一方の面上に設けられた前処理層とを含む記録媒体の製造方法であって、
    　前記基材の少なくとも一方の面上に、請求項１～９の何れか１項に記載の前処理剤組成物からなる前処理剤を付与する前処理剤付与工程と、
    　前記前処理剤付与工程において付与された前記前処理剤を乾燥させて、前処理層を形成する前処理層形成工程と、
    を含む記録媒体の製造方法。     A method for producing a recording medium comprising a substrate and a pretreatment layer provided on at least one surface of the substrate,
    A pretreatment agent application step of applying a pretreatment agent comprising the pretreatment agent composition according to any one of claims 1 to 9 on at least one surface of the substrate;
    A pretreatment layer forming step of drying the pretreatment agent applied in the pretreatment agent application step to form a pretreatment layer;
    A method for manufacturing a recording medium including:
  15. 　前記基材として、疎水性の基材を用いる、請求項１４に記載の記録媒体の製造方法。 The method for manufacturing a recording medium according to claim 14, wherein a hydrophobic base material is used as the base material.
  16. 　基材に画像を形成する記録方法であって、
    　基材の少なくとも一方の面上に、請求項１～９の何れか１項に記載の前処理剤組成物からなる前処理剤を付与する前処理剤付与工程と、
    　前記前処理剤付与工程において付与された前記前処理剤上にインクを付与する第１インク付与工程と、
    　前記第１インク付与工程後に、前記前処理剤および前記インクを乾燥させて前記画像を形成する画像形成工程と、
    を含む記録方法。     A recording method for forming an image on a substrate,
    A pretreatment agent application step of applying a pretreatment agent comprising the pretreatment agent composition according to any one of claims 1 to 9 on at least one surface of the substrate;
    A first ink application step of applying ink onto the pretreatment agent applied in the pretreatment agent application step;
    An image forming step of forming the image by drying the pretreatment agent and the ink after the first ink application step;
    Recording method.
  17. 　基材に画像を形成する記録方法であって、
    　基材の少なくとも一方の面上に、請求項１～９の何れか１項に記載の前処理剤組成物からなる前処理剤を付与する前処理剤付与工程と、
    　前記前処理剤付与工程において付与された前記前処理剤を乾燥させて、前処理層を形成する前処理層形成工程と、
    　前記前処理層形成工程により形成された前記前処理層にインクを付与する第２インク付与工程と、
    　前記第２インク付与工程において付与された前記インクを乾燥させて前記画像を形成する画像形成工程と、
    を含む記録方法。     A recording method for forming an image on a substrate,
    A pretreatment agent application step of applying a pretreatment agent comprising the pretreatment agent composition according to any one of claims 1 to 9 on at least one surface of the substrate;
    A pretreatment layer forming step of drying the pretreatment agent applied in the pretreatment agent application step to form a pretreatment layer;
    A second ink application step for applying ink to the pretreatment layer formed by the pretreatment layer formation step;
    An image forming step of forming the image by drying the ink applied in the second ink application step;
    Recording method.
  18. 　前記基材が、疎水性の基材である、請求項１６又は請求項１７に記載の記録方法。 The recording method according to claim 16 or 17, wherein the substrate is a hydrophobic substrate.
  19. 　前記前処理剤付与工程、前記第１インク付与工程又は前記第２インク付与工程の少なくとも何れかの工程を、インクジェット記録方式により行う請求項１６～１８の何れか１項に記載の記録方法。 The recording method according to any one of claims 16 to 18, wherein at least one of the pretreatment agent application step, the first ink application step, and the second ink application step is performed by an ink jet recording method.
  20. 　前記インクとして水性インクを用いる、請求項１７～１９の何れか１項に記載の記録方法。 The recording method according to any one of claims 17 to 19, wherein a water-based ink is used as the ink.
PCT/JP2019/004743 2018-03-28 2019-02-08 Pretreatment agent composition, method for producing pretreatment agent composition, recording medium, method for producing recording medium, and recording method WO2019187704A1 (en)

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JP2009286117A (en) * 2008-05-28 2009-12-10 Toshiba Corp Inkjet recording method, and pretreatment liquid for inkjet recording
JP2015074692A (en) * 2013-10-08 2015-04-20 セイコーエプソン株式会社 Reaction liquid and recording method
WO2016136914A1 (en) * 2015-02-27 2016-09-01 富士フイルム株式会社 Ink set and image forming method
JP2017013350A (en) * 2015-06-30 2017-01-19 セイコーエプソン株式会社 Recording method and ink set

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JPS60110753A (en) * 1983-11-21 1985-06-17 Koutou Kk Shellac composition
JP2002219866A (en) * 2001-01-29 2002-08-06 Toyo Ink Mfg Co Ltd Coating agent for forming ink receiving layer and recording material using the coating agent
JP2009286117A (en) * 2008-05-28 2009-12-10 Toshiba Corp Inkjet recording method, and pretreatment liquid for inkjet recording
JP2015074692A (en) * 2013-10-08 2015-04-20 セイコーエプソン株式会社 Reaction liquid and recording method
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