JP6474933B1 - ANCHOR COAT COMPOSITION FOR ACTIVE ENERGY RAY CURABLE INKJET INK, ACTIVE ENERGY RAY CURABLE INKJET INK SET, ACTIVE ENERGY RAY CURABLE INKJET INK PRINTED MATERIAL, AND METHOD FOR PRODUCING ACTIVE ENERGY RAY CURABLE INKJET INK PRINTED - Google Patents

Abstract

Active energy ray curable type capable of forming an anchor coat layer that adheres to both a plastic film and an active energy ray curable inkjet ink, does not block anchor coat layer surfaces, and does not repel active energy ray curable inkjet ink. An anchor coat composition for inkjet ink is provided.
SOLUTION: A thermoplastic resin, silica, a silane coupling agent, and a solvent are contained, and the silane coupling agent is contained in an amount of 0.1 to 20% by mass, and a mercapto-based silane. It is at least one selected from a coupling agent, an epoxy-based silane coupling agent, and an amino-based silane coupling agent, and the silica is contained in the composition in an amount of 0.01 to 30% by mass. An active energy ray-curable anchor coat composition for inkjet inks.
[Selection figure] None

Description

  The present invention relates to an anchor coating composition for an active energy ray-curable inkjet ink.

  Conventionally, a film material in which an anchor coat layer is provided on a film substrate and a printing layer or a protective layer is provided on the anchor coat layer has been proposed.

  Patent Document 1 discloses a surface-treated plastic film in which a surface coating layer is formed on at least one surface of a plastic film, each having a bleeding index for water-based and alcohol-based inks on the surface coating layer side of the surface-treated plastic film. A surface-treated plastic film of 1.0 to 1.2, and an ink jet recording body in which an ink receiving layer is provided on the surface coating layer of the plastic film are described, and particularly high-quality image printing is possible. Inkjet recording media have been proposed.

  Patent Document 2 describes an ink for forming an ink-jet ink receiving layer containing a hydrophobic binder resin, an organic solvent compatible with the binder resin, and hydrophilic porous fine particles, and is excellent in printing ink suitability. Thus, an ink receiving layer can be easily formed at a required predetermined position of a sheet base material (sometimes referred to as a card base material), and the ink receiving layer formed using this ink is (1) absorption of ink. Fast fixing and good, no dripping of ink after printing, (2) high printing density and excellent color development, and (3) ink droplet diffusion and dot diameter In addition to having properties such as not to be larger than necessary, it has been proposed to have excellent blocking resistance, crack resistance, water resistance and weather resistance.

  Patent Document 3 discloses a precoat agent used for forming a precoat layer that receives an ink for forming an image by an inkjet method, and includes water, a cationic resin having a polyurethane structure, and two or more identical functional groups. A pre-coating agent containing an organic acid having a crosslinking agent capable of reacting with the functional group is described, and a non-absorbent recording medium is formed on a formed coating film and thereafter, regardless of the material of the recording medium There has been proposed an image having high image durability and good image quality of the formed image.

  Patent Document 4 discloses a decorative sheet obtained by laminating a colored layer, a primer layer, and a surface protective layer in this order on a substrate made of a resin film, and the surface protective layer is an ionizing radiation curable resin composition. A decorative sheet is described in which the primer layer contains silica having a surface-treated silica, and simultaneously satisfies low-temperature impact resistance, hair dye resistance, alkali resistance, and bendability. Things have been proposed.

  Patent Document 5 discloses a polymer (A) in which the main chain contains an alkyl acrylate monomer unit and / or an alkyl methacrylate monomer unit and has at least one hydrolyzable silicon-containing group per molecule. And a primer composition containing a silane coupling agent (B) and a solvent (C) are described, which are excellent in adhesion to a glass substrate and glass weather resistance, and can be applied to various sealing materials. Proposed.

  Patent Document 1 discloses a polyurethane resin having polyvinyl alcohol and a blocked isocyanate group in Examples 9 to 13 of paragraph 0082, spherical silica particles, and water as an ink receiving layer that receives inkjet ink on a plastic film. The ink-receiving layer solution contained is used to obtain an ink jet recording material, but it is a water-based ink-receiving layer solution, and there is no description or suggestion about the application of the active energy ray-curable ink-jet ink on the ink-receiving layer. In addition, the ink-jet ink may not be accepted, and ink repelling may occur. Further, the ink-receiving layer is not evaluated for blocking resistance, and may be inferior.

  Patent Document 2 contains a binder resin having hydrophobicity, an organic solvent, and hydrophilic porous fine particles as an ink for forming an inkjet ink receiving layer on a substrate. As an inkjet ink, it is only described that an anionic ink is suitable, there is no description about the application of the active energy ray-curable inkjet ink, and there is a possibility that the inkjet ink may not be accepted. There is a risk of repelling. Further, the receiving layer is not evaluated for blocking resistance, and may be inferior.

  Patent Document 3 includes water, a cationic resin having a polyurethane structure, an organic acid having two or more identical functional groups, and a crosslinking agent capable of reacting with the functional group as a precoat agent. The ink-jet ink received on the layer is described as an anionic ink, there is no description or suggestion about the application of the active energy ray-curable ink-jet ink, the ink-jet ink may not be accepted, and the ink repelling May occur.

  Patent Document 4 contains a binder and surface-treated silica as a primer layer, and a surface protective layer made of an ionizing radiation curable resin composition is laminated on the primer layer. In order to protect the surface, a surface protective layer is provided, there is no description or suggestion about the application of the active energy ray-curable ink jet ink, the ink jet ink may not be accepted, and ink repelling may occur. There is. Further, the primer layer has not been evaluated for blocking resistance and may be inferior.

  Patent Document 5 includes an acrylic polymer having a hydrolyzable silicon-containing group, a silane coupling agent, and a solvent as a primer layer. The primer layer is applied to a glass substrate, and further sealed. When a material (sealing material that fills joints of building structures) is applied, it adheres to both the glass substrate and the sealing material, and has excellent weather resistance, and is used as a plastic film substrate There is no description or suggestion of what can be done, nor is there any description of the ability to accept ink on the primer layer.

  Therefore, the active energy ray curable ink jet that can form an anchor coat layer that adheres to both the plastic film and the active energy ray curable ink jet ink, does not block the anchor coat layer surfaces, and does not repel the active energy ray curable ink jet ink. An ink anchor coat composition has been desired.

JP 2001-212912 A JP 2004-223762 A WO2017 / 013894 JP2012-30524A JP 2005-281519 A

  Therefore, the present invention provides an active energy capable of forming an anchor coat layer that adheres to both the plastic film and the active energy ray-curable inkjet ink, does not block the anchor coat layer surfaces, and does not repel the active energy ray-curable inkjet ink. An object of the present invention is to provide an anchor coat composition for a linear curable inkjet ink.

  As a result of intensive studies, the present inventor made an anchor coating composition for an active energy ray-curable inkjet ink containing a thermoplastic resin, silica, a specific silane coupling agent, and a solvent. The inventors have found that the object can be achieved and have completed the present invention.

That is, the present invention
(1) An anchor coating composition for an active energy ray-curable inkjet ink containing a thermoplastic resin, silica, a silane coupling agent, and an organic solvent ,
The thermoplastic resin is either one of the following (A) or (B),
The silane coupling agent is contained in the composition in an amount of 0.1 to 20% by mass, and at least selected from mercapto silane coupling agents, epoxy silane coupling agents, and amino silane coupling agents. One kind,
An anchor coat composition for gravure printing, wherein the silica is contained in an amount of 0.01 to 30% by mass in the composition,
(A) Polyurethane resin and vinyl chloride-vinyl acetate copolymer having a mass ratio of 2: 8 to 8: 2 (B) Polyurethane resin and acrylic resin having a mass ratio of 6: 4 to 0:10 Resin (2) The active energy ray-curable inkjet ink anchor coat composition according to (1) , which is substantially free of water,
(3) A laminate comprising an active energy ray-curable inkjet ink anchor coat layer directly on at least one of the plastic film layers,
The active energy ray-curable inkjet ink anchor coat layer comprises the active energy ray-curable inkjet ink anchor coat composition according to (1) or (2),
(4) The laminate according to (3), wherein the active energy ray-curable inkjet ink anchor coat layer further comprises an isocyanate compound,
(5) Using the laminate according to (3) or (4), on the anchor coat layer of the laminate,
An active energy ray curable inkjet ink print comprising an active energy ray curable inkjet ink layer comprising an active energy ray curable inkjet ink composition;
(6) An active energy ray curable inkjet ink anchor coat layer comprising the active energy ray curable inkjet ink anchor coat composition according to (1) or (2) is directly formed on at least one of the plastic films. Process,
Forming an active energy ray-curable inkjet ink layer comprising the active energy ray-curable inkjet ink composition on the active energy ray-curable inkjet ink anchor coat layer;
Including
A method of producing an active energy ray-curable inkjet ink print, wherein the step of directly forming the anchor coat layer for the active energy ray-curable inkjet ink is performed by a gravure printing method;
(7) The active energy ray-curable composition according to (6), further comprising an isocyanate compound in the composition used in the step of directly forming the anchor coat layer for the active energy ray-curable inkjet ink. Type inkjet ink printed matter manufacturing method,
It is about.

  According to the present invention, the active energy capable of forming an anchor coat layer that adheres to both the plastic film and the active energy ray-curable inkjet ink, does not block the anchor coat layer surfaces, and does not repel the active energy ray-curable inkjet ink. An anchor coat composition for a linear curable inkjet ink can be provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. The present embodiment is merely one form for carrying out the present invention, and the present invention is not limited by the present embodiment, and various modifications and embodiments are possible without departing from the gist of the present invention. Is possible.

  The anchor coating composition for an active energy ray-curable inkjet ink of the present invention (hereinafter also simply referred to as “anchor coating agent”) contains a thermoplastic resin, silica, a silane coupling agent, and a solvent. The silane coupling agent is contained in the composition in an amount of 0.1 to 20% by mass, and at least selected from mercapto silane coupling agents, epoxy silane coupling agents, and amino silane coupling agents. It is 1 type and it is preferable that the said silica contains 0.01-30 mass% in solid content in a composition.

  The thermoplastic resin is a silk screen printing method, gravure printing method, flexographic printing method, roller coater method, brush coating method, spray method, knife jet coater method, ink jet printing method, pad printing method, gravure offset printing method, die coater. Any resin may be used as long as it is applicable to a known printing method such as a method, a bar coater method, a spin coater method, a comma coater method, an impregnation coater method, a dispenser method, and a metal mask method. Especially, it is more preferable that it is resin applicable to a gravure printing method and a flexographic printing method, and it is still more preferable that it is resin applicable to a gravure printing method.

  Specific examples of the thermoplastic resin include shellacs, rosin-modified maleic resin, rosin-modified phenol resin, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, and vinyl halide resin. (For example, vinyl chloride resin, fluorine-containing vinyl resin, etc.), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polystyrene resin, acrylic resin, acrylic styrene copolymer, polyacrylic ester, polyester resin , Polyvinylidene chloride resin, ketone resin, ethylene vinyl acetate resin, polyurethane resin, polyamide resin, nitrocellulose resin, chlorinated polyethylene resin, chlorinated polypropylene resin, chlorinated ethylene-vinyl acetate resin, rosin resin, styrene Maleic acid resins, alkyd resins, and ethylene - vinyl alcohol resins. Of these, polyurethane resins, acrylic resins, nitrocellulose resins, polyamide resins, chlorinated polypropylene resins, vinyl chloride-vinyl acetate copolymers, and the like are more preferable. Furthermore, at least one selected from a polyurethane resin and a vinyl chloride-vinyl acetate copolymer, or a polyurethane resin and an acrylic resin is more preferable. At least one selected from these is preferable, and two or more may be used in combination.

  The thermoplastic resin is preferably 1 to 70% by mass in solid content in the anchor coating agent, more preferably 2 to 65% by mass, and further preferably 3 to 60% by mass. When the amount is less than 1% by mass, sufficient adhesion cannot be obtained. When the amount is more than 70% by mass, the solid content is too high, the viscosity becomes high, and the coating is difficult.

  In the case of the polyurethane resin and the vinyl chloride-vinyl acetate copolymer, the mass ratio is preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3, and 4: 6. More preferably, it is ˜6: 4.

  In the case of the polyurethane resin and the acrylic resin, the mass ratio is preferably 6: 4 to 0:10, more preferably 3: 7 to 0:10, and 2: 8 to 0:10. More preferably it is.

  The silane coupling agent is preferably at least one selected from mercapto silane coupling agents, epoxy silane coupling agents, and amino silane coupling agents. By being these silane coupling agents, it reacts effectively with a thermoplastic resin. Among these, a mercapto silane coupling agent is more preferable. Examples of mercapto silane coupling agents include KBM-802, KBM-803, X41-1805, and X41-1810 (all manufactured by Shin-Etsu Chemical Co., Ltd.). , KBM-303, KBM-402, KBM-403, KBE-402, KBE-403 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and amino silane coupling agents include KBM-602, KBM. -603, KBM-903, KBE-9103P, KBM-573, KBM-575 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  The silane coupling agent is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, and 0.4 to 5% by mass in the anchor coating agent. Is more preferable. When the amount is less than 0.1% by mass, the adhesion with the active energy ray-curable inkjet ink composition is inferior, and when it is more than 20% by mass, the blocking resistance is inferior.

  As the silica, either untreated or treated silica is preferably used. The treated silica is preferably used for any of hydrophobic treatment, hydrophilic treatment, inorganic treatment, and organic treatment. For example, Acemat Series, Aerosil Series, Sipper Nut Series (Evonik Japan Co., Ltd.), Silicia Series, Silo Hovic Series, Syrosphere Series (Fuji Silysia Chemical Co., Ltd.)), Toxeal Series, Fine Seal series (made by Oriental Silica Co., Ltd.), nip seal series, nip gel series (made by Tosoh Silica Co., Ltd.), High Plessica series (made by Ube Eximo Co., Ltd.), HPS series (made by Toagosei Co., Ltd.), etc. Can be mentioned.

  The silica is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and more preferably 0.2 to 10% by mass in solid content in the anchor coating agent. Is more preferable. When it is less than 0.01% by mass, the blocking resistance is inferior, and when it is more than 30% by mass, the adhesion is inferior, and the gloss and transparency are lowered.

  The solvent is preferably various organic solvents for imparting appropriate fluidity during printing and adjusting the viscosity, and preferably dissolves or disperses the thermoplastic resin in the solvent.

  Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, methanol, ethanol, isopropyl alcohol, normal propyl alcohol, and 1-butanol. Alcohol solvents such as 2-butanol, isobutanol and tert-butanol, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, ester solvents such as tert-butyl acetate, acetone , Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether Ter, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and other glycol ether solvents and esterified products thereof. For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Seteto and the like. At least one selected from these is preferable, and two or more may be used in combination.

  It is preferable that the said solvent is 1-90 mass% in an anchor coating agent, It is more preferable that it is 5-80 mass%, It is further more preferable that it is 10-70 mass%. If the amount is less than 1% by mass, sufficient printability cannot be obtained. If the amount is more than 90% by mass, the solid content decreases and the adhesion to the plastic film is lowered.

  For anchor coating agents, coloring materials, inorganic fillers, organic fillers, antifoaming agents, leveling agents, etc., for the purpose of improving the required physical properties such as design, usage, hue, and the stability of the coating agent and printability. Antiblocking agent, wax, pigment dispersant, antistatic agent, slip agent, plasticizer, tackifier, antioxidant, surfactant, ultraviolet absorber, surface adjuster, pH adjuster, charge imparting agent, bactericidal agent Further, it can contain a deodorant, a wetting agent, an anti-skinning agent, a metal chelating agent and the like. Any known and commonly used ones can be selected as long as the printability and the properties of the anchor coating agent are not impaired.

  The color material can contain a pigment, a dye, or a mixture thereof. Examples of the pigment include titanium oxide, petal, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, pearl, aluminum, carbon black and other inorganic pigments, phthalocyanine-based, insoluble azo-based, condensed azo Organic pigments such as organic, dioxazine, anthraquinone, quinacridone, perylene, perinone, and thioindigo, and various other fluorescent pigments, metal powder pigments, extender pigments, and the like. At least one selected from these is preferable, and two or more may be used in combination. The dye is preferably one that dissolves or disperses in a solvent, preferably at least one selected from these, and two or more may be used in combination. Among these, it is preferable to use a pigment from the viewpoint of durability. Since it can contain a coloring material, it is very useful in terms of color variation and design.

  The anchor coating agent is preferably provided on the plastic film so as to be an anchor coating layer for an active energy ray-curable inkjet ink having a thickness of 0.01 to 10 μm (hereinafter also simply referred to as “anchor coating layer”). . When the film thickness is smaller than 0.01 μm, the active energy ray-curable inkjet ink receiving effect is hardly exhibited, and when the film thickness is larger than 10 μm, it is difficult to provide an anchor coat layer and blocking occurs.

  The laminate of the present invention comprises a plastic film layer and an active energy ray-curable inkjet ink anchor coat layer, and the active energy ray-curable inkjet ink anchor coat layer comprises the active energy ray-curable inkjet ink. It preferably comprises an ink anchor coat composition.

  Any plastic film layer may be used as long as it is used for a packaging material, and a plastic film or sheet is preferable. Especially, what is used for a flexible packaging bag is more preferable. For example, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene, polypropylene and ethylene-vinyl acetate, polystyrene films, alcohol-based films such as ethylene-vinyl alcohol and polyvinyl alcohol, polyamide films Or transparent polyamide film with a barrier layer placed between them, polycarbonate film, polyacrylonitrile film, polyimide film, cellophane, moisture-proof cellophane, PET film or polyamide film with a deposition layer such as alumina or silica or transparent Vapor-deposited polyamide film, PET film or polyamide film, polyethylene film, Aluminum deposition film in which aluminum is vapor-deposited, such as polypropylene films, polyvinylidene chloride resins, polyvinyl alcohol resins, various coating films and coated polyacrylic acid resins, and co-extruded film was co-extruded with further different resins. These may be either stretched or unstretched, and may be used alone or in combination of two or more. Appropriate ones can be selected in consideration of mechanical strength and dimensional stability. Further, in order to improve the adhesion on the surface on which the anchor coat layer is formed, a corona treatment, a low temperature plasma treatment, a flame treatment, a solvent treatment, a coating treatment, or the like can be applied, or a pre-treated one can be selected.

  The laminate of the present invention preferably further comprises an isocyanate compound in the active energy ray-curable inkjet ink anchor coat layer.

  The isocyanate compound is not particularly limited as long as it can react with the thermoplastic resin and be cured, but a polyvalent isocyanate compound is more preferable. Examples thereof include aromatic diisocyanate compounds such as tolylene diisocyanate and 4,4-diphenylmethane diisocyanate, aliphatic diisocyanate compounds such as xylylene diisocyanate and hexamethylene diisocyanate, polymers thereof and derivatives thereof.

  More preferably, the anchor coat layer further comprises a solvent. The solvent is preferably various organic solvents for imparting appropriate fluidity during printing and adjusting the viscosity, and is preferably one that dissolves or disperses the thermoplastic resin in the solvent.

  The anchor coat layer is preferably laminated directly on at least one of the plastic film layers, and includes a silk screen printing method, a gravure printing method, a flexographic printing method, a roller coater method, a brush coating method, a spray method, a knife jet coater method, It is formed by a known printing method such as an inkjet printing method, a pad printing method, a gravure offset printing method, a die coater method, a bar coater method, a spin coater method, a comma coater method, an impregnation coater method, a dispenser method, and a metal mask method. The formed anchor coat layer is stable. Therefore, the laminate in which the anchor coat layer is laminated on the plastic film layer can be stored without blocking even if it is normally wound.

  The active energy ray-curable inkjet ink print of the present invention uses the laminate, and an active energy ray-curable inkjet ink layer comprising the active energy ray-curable inkjet ink composition on the anchor coat layer of the laminate. It is preferable to provide.

  As described above, even if the laminate is wound and stored, blocking does not occur. Therefore, while the laminate is rewound, active energy ray curing is separately performed on the anchor coat layer of the laminate by an inkjet printing method. Since a type inkjet ink layer can be formed, the versatility is very high.

  The active energy ray-curable inkjet ink composition is a composition containing a photopolymerizable monomer, a photopolymerizable oligomer and the like, and may contain a stabilizer, a filler, a colorant (dye, pigment) and the like as additives. Good. In addition, when the active energy ray-curable ink-jet ink composition is polymerized with ultraviolet rays, in general, a photopolymerization initiator, a photosensitizer, and the like are required to smoothly carry out the polymerization. It is not required if you want to

  The photopolymerizable monomer or photopolymerizable oligomer is preferably a compound having a (meth) acryl group (hereinafter also referred to as (meth) acrylate), and even if it is a monofunctional (meth) acrylate, ) Acrylate may be used. Moreover, urethane (meth) acrylate and polyester (meth) acrylate may be used.

  For example, as monofunctional (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecane monomethylol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl Polyfunctional (meth) acrylates such as (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (Meth) acrylate, butylene di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (meth) acrylate di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) ) Bifunctional (meth) acrylates such as acrylate, 1,12-dodecanediol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tricyclodecane dimethylol dicaprolactonate di (meth) acrylate, Trimethylol Trifunctional (meth) acrylates such as propane tri (meth) acrylate, glycerin tri (meth) acrylate, glycerin propoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol Tetra (meth) acrylate, pentaerythritol tetracaprolactonate tetra (meth) acrylate, diglycerin tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa ( (Meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Tetrafunctional or more polyfunctional, such as pentaerythritol polyalkylene oxide hepta (meth) acrylate (meth) acrylate.

  Moreover, the (meth) acrylate of the polyol which has a C1-C18 alkyl group may be sufficient. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meta) ) Monofunctional (meth) acrylates such as acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, pentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalyl hydroxypivalate di (meth) acrylate Todi (meth) acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di (meth) acrylate, hexanediol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tricyclodecane dimethylol dicaprolactonate Di (meth) acrylate, bisphenol A tetrapropylene oxide adduct di (meth) acrylate, bisphenol A polyalkylene oxide adduct di (meth) acrylate, bisphenol F tetrapropylene oxide adduct di (meth) acrylate, bisphenol F polyalkylene oxide Adduct di (meth) acrylate, bisphenol S tetraethylene oxide adduct di (meth) acrylate, bisphenol S polyalkylene oxide Adduct di (meth) acrylate, water-added bisphenol A tetrapropylene oxide adduct di (meth) acrylate, water-added bisphenol A polyalkylene oxide adduct di (meth) acrylate, water-added bisphenol F tetrapropylene oxide adduct di (meth) ) Acrylate, water-added bisphenol F polyalkylene oxide adduct di (meth) acrylate, water-added bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate, dihydroxybenzene (catechol, resorcin, hydroquinone, etc.) polyalkylene Oxide di (meth) acrylate, alkyldihydroxybenzene polyalkylene oxide di (meth) acrylate, bisphenol A tetraethylene oxide adduct di Bifunctional (meth) acrylates such as caprolactonate di (meth) acrylate, bisphenol F tetraethylene oxide adduct dicaprolactonate di (meth) acrylate, glycerin poly (2-20) alkylene (C2-C20) oxide Adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolpropane poly (2-20) alkylene (C2-C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, Propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolethane poly (2-20) alkylene (C2-C20) oxide adduct (as alkylene oxide) For example, trifunctional (meth) acrylates such as ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, pentaerythritol poly (2-20) alkylene (C2-C20) oxide adduct (alkylene oxide, for example, ethylene Oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, diglycerin poly (2-20) alkylene (C2-C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) Acrylate, diglycerin poly (2-20) alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide) adduct tetra (Meth) acrylate, ditrimethylolpropane poly (2-20) alkylene (C2-C20) oxide adduct (as alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethylolpropane poly (2- 20) Alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate, tetra (meth) acrylate, ditrimethylolethane poly (2-20) alkylene (C2- C20) Oxide adduct (As alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylic A tetrafunctional or higher polyfunctional (meth) acrylate such as a rate may be mentioned.

  Moreover, epoxidized vegetable oil (meth) acrylate may be sufficient. Epoxidized vegetable oil (meth) acrylate is a compound obtained by polyaddition reaction of (meth) acrylic acid to an epoxy group of an epoxidized vegetable oil obtained by epoxidizing an unsaturated vegetable oil with a double bond of peracetic acid or perbenzoic acid. The unsaturated vegetable oil is a triglyceride in which at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond in the triglyceride of glycerin and a fatty acid, such as epoxidized soybean oil (meth) acrylate. Can be mentioned.

  The method for producing an active energy ray-curable inkjet ink print of the present invention includes an anchor for an active energy ray-curable inkjet ink comprising the anchor coating composition for an active energy ray-curable inkjet ink on at least one of a plastic film. A step of directly forming a coating layer, and a step of forming an active energy ray-curable inkjet ink layer comprising the active energy ray-curable inkjet ink composition on the anchor coat layer for the active energy ray-curable inkjet ink. It is preferable that it is included.

  The method for producing an active energy ray-curable inkjet ink printed material according to the present invention includes the step of directly forming the anchor coat layer for an active energy ray-curable inkjet ink comprising the active energy ray-curable inkjet ink anchor coat composition. In addition, it is preferable to further comprise an isocyanate compound.

  The step of directly forming the anchor coat layer for the active energy ray-curable ink jet ink includes a silk screen printing method, a gravure printing method, a flexographic printing method, a roller coater method, a brush coating method, a spray method, a knife jet coater method, and an inkjet. It is performed by at least one selected from a printing method, a pad printing method, a gravure offset printing method, a die coater method, a bar coater method, a spin coater method, a comma coater method, an impregnation coater method, a dispenser method, and a metal mask method. It is preferable. Among these, it is more preferable to perform by at least one selected from a gravure printing method and a flexographic printing method, and it is more preferable to perform by a gravure printing method.

  Further, the formed anchor coat layer is stable. This is because, for example, after forming an anchor coat layer on a plastic film by a gravure printing method, it can be stored without blocking even if it is normally wound up. Since the active energy ray-curable inkjet ink layer can be separately formed by an inkjet printing method, the versatility is very high. In addition, since the adhesion between the anchor coat layer and the active energy ray-curable inkjet ink layer is excellent, an anchor coat layer is formed on the entire surface, especially when an endless plate is used as a printing plate for gravure printing, and the active energy is formed thereon. Even when an ink-jet ink layer made of a line-curable ink-jet ink is formed, removal of the formed ink-jet ink layer is suppressed in a heat sealing process such as subsequent bag making.

  As described above, the anchor coat layer may be applied on the entire surface of the plastic film, or may be applied partially. Further, an active energy ray-curable inkjet ink layer may be formed on the anchor coat layer, and an overcoat layer may be further formed. The overcoat layer may be laminated with an overcoat film or the like through an adhesive layer, or may be laminated with a thermoplastic resin or the like by dry lamination, non-solvent lamination, extrusion lamination, or the like. Moreover, you may have a heat seal layer on the plastic film on the opposite side to an anchor coat layer.

  Any plastic film may be used as long as it is used for a packaging material, and it may be in the form of a sheet. Especially, what is used for a flexible packaging bag is more preferable. For example, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene, polypropylene and ethylene-vinyl acetate, polystyrene films, alcohol-based films such as ethylene-vinyl alcohol and polyvinyl alcohol, polyamide films Or transparent polyamide film with a barrier layer placed between them, polycarbonate film, polyacrylonitrile film, polyimide film, cellophane, moisture-proof cellophane, PET film or polyamide film with a deposition layer such as alumina or silica or transparent Vapor-deposited polyamide film, PET film or polyamide film, polyethylene film, Aluminum deposition film in which aluminum is vapor-deposited, such as polypropylene films, polyvinylidene chloride resins, polyvinyl alcohol resins, various coating films and coated polyacrylic acid resins, and co-extruded film was co-extruded with further different resins. These may be either stretched or unstretched, and may be used alone or in combination of two or more. Appropriate ones can be selected in consideration of mechanical strength and dimensional stability. Further, in order to improve the adhesion on the surface on which the anchor coat layer is formed, a corona treatment, a low temperature plasma treatment, a flame treatment, a solvent treatment, a coating treatment, or the like can be applied, or a pre-treated one can be selected.

  Although there will be no restriction | limiting in particular if the thickness of a plastic film is in the range which does not have trouble in printability, winding-up property, etc., 1-1000 micrometers is preferable and 3-100 micrometers is more preferable.

  The active energy ray curable inkjet ink print of the present invention is for packaging, food preservation, agriculture, civil engineering, fishery, interior / exterior for automobiles, for ships, for daily necessities, for interior / exterior of building materials, for residential equipment, medical / It can be used for medical equipment, medicine, household appliances, furniture, stationery and office supplies, sales promotion, commercial, electrical and electronics industries, clothing, and ornaments.

  The packaging bag is preferably formed using the active energy ray-curable inkjet ink print. Packing bag forms include two-side seals, three-side seals, four-side seals, pillow seals, standing pouches, envelope stickers, gussets, fusing seals, tubes, caramel packaging, overholds, fin seals, manju packaging, twists, rockets, etc. It can be preferably used as a form.

  In addition, as a label, it can be preferably used in the form of a label attached to a glass bottle, a metal can, a plastic bottle, another container, or a body-wound label.

  The anchor coating composition for an active energy ray-curable inkjet ink can be produced by a known method by uniformly dissolving or dispersing a thermoplastic resin, silica, a silane coupling agent, a solvent, a pigment, various additives, and the like. Dissolver or disperser is various agitators or dispersers such as dissolver, roll mill, ball mill, bead mill, sand mill, attritor, paint shaker, agitator, Henschel mixer, colloid mill, pearl mill, ultrasonic homogenizer, wet jet mill, kneader, homomixer, etc. You can use the machine. These devices may be used alone or in combination of two or more. In the case where bubbles or coarse particles are contained in the anchor coating agent, it is preferable to remove them using a known filter or centrifuge in order to lower the printability and the printed matter quality.

  The viscosity of the active energy ray-curable inkjet ink anchor coat composition is not particularly limited as long as it does not interfere with printing. The viscosity used in gravure printing or flexographic printing is preferably 10 to 1,000 mPa · s at 25 ° C. in consideration of production suitability and handling. In this case, it can be measured using a commercially available viscometer such as a Brookfield viscometer or a cone plate viscometer.

  The anchor coating composition for active energy ray-curable inkjet ink used in gravure printing and flexographic printing can be applied as it is, but Zaan Cup # 3 (Corporation) depending on the coating conditions and coating effect. Can be used after adjusting to a desired viscosity by diluting with a diluent solvent. The viscosity in this case is preferably 10 to 40 seconds at 25 ° C.

  The dilution solvent may be any one as long as it can be used after adjusting the viscosity of the anchor coat composition for an active energy ray-curable inkjet ink, and the above-described organic solvent is preferable, and a commercially available one can also be used. Examples of commercially available products include WA735, TA52, PU515, SL9155, CN104, AC372, PP575, and PA463 (all manufactured by Tokyo Ink Co., Ltd.).

  Moreover, the anchor coating composition for active energy ray-curable inkjet ink used in gravure printing or flexographic printing may contain an isocyanate compound, and a commercially available one can also be used. Examples of commercially available products include LG curing agent A and LG curing agent D (all of which are manufactured by Tokyo Ink Co., Ltd.).

  The mixing ratio (anchor coating agent / isocyanate / diluent solvent) of the active energy ray-curable ink jet ink anchor coat composition, the isocyanate compound, and the diluent solvent depends on the desired viscosity, coating conditions, and coating effect. The range is preferably 100/0 to 30/5 to 200, more preferably 100/3 to 20/10 to 150, and more preferably 100/5 to 15/10 to 100. Further preferred.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these. In addition, the part in an Example and a comparative example represents a mass part, and% represents the mass%.

[Preparation of an active energy ray curable anchor coat composition for inkjet ink]
Anchor coating agent 1 (Example 1)
40 parts of acrylic resin varnish (solid content 35%, Acryt 1LO-735T, manufactured by Taisei Fine Chemical Co., Ltd.), 0.4 part of silica (Acemat OK520, manufactured by Evonik Japan Co., Ltd.), mercapto silane coupling agent (X41-1805, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.8 parts, PU515 solvent (manufactured by Tokyo Ink Co., Ltd.) 60 parts, polyethylene wax (CERAFLOUR 925, manufactured by Big Chemie Japan Co., Ltd.) 1 part, BYK051N ( 0.1 parts of an antifoaming agent (Bic Chemie Japan Co., Ltd.) was charged, and kneaded with a paint shaker to prepare a mill base. Similarly, according to the mixing | blending of Table 1-Table 6, the anchor coating agent of Examples 2-32 and Comparative Examples 1-10 was produced.

The materials used are as follows.
TA24-537Q: Urethane resin varnish, solid content 30% (manufactured by Hitachi Chemical Co., Ltd.)
Kane Vinyl HM515: Vinyl chloride-vinyl acetate copolymer resin varnish (Kane Vinyl HM515 (manufactured by Kaneka Corporation) prepared with a mixed solvent of methylcyclohexanone / ethyl acetate = 50/50), solid content 30%
PVA PVA117: Polyvinyl alcohol, purity 94.0% or more (manufactured by Kuraray Co., Ltd.)
Elastron H-38: polyurethane resin having a block type isocyanate group, solid content 20% (Daiichi Kogyo Seiyaku Co., Ltd.)
Pergut S-20: Chlorinated rubber resin (manufactured by Sumika Bayer Urethane Co., Ltd.)
Super Clone C: Chlorinated polyolefin resin, solid content 55% (Nippon Paper Industries Co., Ltd.)
JER828: Epoxy resin (Mitsubishi Chemical Corporation)
Acemat OK412: Silica (Evonik Japan Co., Ltd.)
Silicia 770: Silica (Fuji Silysia Chemical Co., Ltd.)
Silo Hovic 200: Silica (Fuji Silysia Chemical Co., Ltd.)
Cyros Sphere C1504: Silica (Fuji Silysia Chemical Co., Ltd.)
NIPSIL E-200: Silica (manufactured by Tosoh Silica Co., Ltd.)
X41-1810: Mercapto silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-802: Mercapto silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-803: Mercapto silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-402: Epoxy silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-602: Amino-based silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-503: Methacrylic silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBE-1003: Vinyl-based silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-9007: Isocyanate-based silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBE-13: Methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

  About each anchor coating agent of Examples 1-32 and Comparative Examples 1-10, the anti-blocking property, the repelling of the inkjet ink of an anchor coating layer, and adhesiveness were evaluated. Tables 7 and 8 show the results.

<Blocking resistance>
Each of the anchor coating agents of Examples 1 to 32 and Comparative Examples 1 to 10, a curing agent (LG curing agent D, manufactured by Tokyo Ink Co., Ltd.), and a solvent (PU515, manufactured by Tokyo Ink Co., Ltd.), 100 It was mixed at a ratio of / 10/15. A test piece was applied to a stretched polypropylene film (OPP film, OP U-1, manufactured by Futamura Chemical Co., Ltd.) having a thickness of 40 μm using a simple coating experiment machine A-Bar OSP-10 (manufactured by Matsuo Sangyo Co., Ltd.). Was then aged at 50 ° C. for 24 hours.
The anchor coating agent-coated surfaces of the test pieces were combined and left at a pressure of 500 gf / cm ² at 50 ° C. dry or 40 ° C. and 90% RH for 24 hours. Thereafter, each of the test pieces was pinched with fingers and rapidly peeled off to confirm the degree of peeling resistance and the degree of ink removal.
The smaller the peel resistance or the less ink is removed, the better the blocking resistance.
The peeling resistance was evaluated in four stages: ：: peeling without any resistance, ◯: almost no resistance, Δ: somewhat resistant (practical withstandability), x: surfaces bonded to each other and not peeled.
About ink removal: ◎: No ink is removed, ○: Some ink is removed, △: Partially ink is removed (can be practically used), ×: More than half area The ink was taken out at 4 grades.

<Repel>
An active energy ray-curable inkjet ink composition (TIC-JET 1023R-ST 160M, manufactured by Tokyo Ink Co., Ltd.) is applied to the anchor coating agent-coated surface of the test piece prepared in the above <Blocking resistance> test. No. 5 (manufactured by Daiichi Rika Co., Ltd.) and using a UV-LED light source device (manufactured by Eye Graphics Co., Ltd.) at 110 W / cm, irradiation distance 20 cm, and conveyor speed 10 m / min. Irradiation was performed once to form an active energy ray-curable inkjet ink layer, and a test print was produced.
The surface state of the test printed material that had been irradiated with ultraviolet rays was visually observed to confirm the coated surface state.
The more uniform the coated surface state, the less the repelling and the better.
About repellency, the evaluation was made in three stages: ○: uniform and smooth coated surface, △: somewhat uneven, but no uncoated surface (no problem in practical use), x: uncoated portion .

<Adhesion>
In the above <repellency> test, an adhesion test was performed on a test printed material having an evaluation of Δ or higher (“−” is described for those not subjected to the adhesion test). A pressure-sensitive adhesive tape (18 mm width, manufactured by Nichiban Co., Ltd.) was attached to the surface of the ink-jet ink layer of the test print, and it was peeled off rapidly at an angle of 60 degrees, and the area of the peeled ink-jet ink layer was evaluated. The smaller the peeled area, the better the adhesion of the anchor coat layer. About peeling area, (circle): It does not peel at all, (triangle | delta): The peeling area is less than 10% (no problem in practical use), x: The peeling area is 10% or more, and evaluated in three steps.

  According to Table 7 and Table 8, the active energy ray-curable ink jet ink anchor coat compositions (anchor coat agents 1 to 32) of Examples 1 to 32 are excellent in blocking resistance, and the repelling of the ink jet ink is suppressed. In addition, since it is clear that the adhesion with the anchor coat layer is good, it is useful for improving the quality and stability of the image. The anchor coating compositions for active energy ray-curable inkjet inks of Comparative Examples 1 to 4 (anchor coating agents 33 to 36) are those that do not correspond to the silane coupling agent of the present invention, but are resistant to blocking. It is clear that both repelling and adhesion are inferior. Further, Comparative Example 5 having a high silica content was inferior in blocking resistance and inferior in repelling. Further, Comparative Example 6 having a high content of the silane coupling agent was inferior in blocking resistance and in repelling under severe conditions of high humidity. Comparative example 7 similar to cited reference 1, comparative example 8 similar to cited reference 2, comparative example 9 similar to cited reference 4, and comparative example 10 similar to cited reference 5 are all inferior in blocking resistance and repelling. It was.

Claims (7)

An active energy ray-curable inkjet ink anchor coat composition containing a thermoplastic resin, silica, a silane coupling agent, and an organic solvent ,
The thermoplastic resin is either one of the following (A) or (B),
The silane coupling agent is contained in the composition in an amount of 0.1 to 20% by mass, and at least selected from mercapto silane coupling agents, epoxy silane coupling agents, and amino silane coupling agents. One kind,
An anchor coating composition for an active energy ray-curable inkjet ink, wherein the silica is contained in an amount of 0.01 to 30% by mass in the composition.
(A) Polyurethane resin and vinyl chloride-vinyl acetate copolymer having a mass ratio of 2: 8 to 8: 2 (B) Polyurethane resin and acrylic resin having a mass ratio of 6: 4 to 0:10 resin   The active energy ray-curable inkjet ink anchor coat composition according to claim 1, wherein the active energy ray-curable inkjet ink anchor coat composition does not substantially contain water. A laminate comprising an active energy ray-curable ink jet ink anchor coat layer directly on at least one of the plastic film layers,
A laminate comprising the active energy ray-curable ink jet ink anchor coat layer comprising the active energy ray-curable ink jet ink anchor coat composition according to claim 1 or 2.   The laminate according to claim 3, further comprising an isocyanate compound in the active energy ray-curable inkjet ink anchor coat layer. Using the laminate according to claim 3 or 4, on the anchor coat layer of the laminate,
An active energy ray-curable inkjet ink print comprising an active energy ray-curable inkjet ink layer comprising an active energy ray-curable inkjet ink composition. Directly forming an active energy ray-curable inkjet ink anchor coat layer comprising the active energy ray-curable inkjet ink anchor coat composition according to claim 1 or 2 on at least one of the plastic film;
Forming an active energy ray-curable inkjet ink layer comprising the active energy ray-curable inkjet ink composition on the active energy ray-curable inkjet ink anchor coat layer;
Including
A method for producing an active energy ray-curable inkjet ink print, wherein the step of directly forming the anchor coat layer for the active energy ray-curable inkjet ink is performed by a gravure printing method. The active energy ray-curable inkjet ink according to claim 6, further comprising an isocyanate compound in the composition used in the step of directly forming the anchor coat layer for the active energy ray-curable inkjet ink. Manufacturing method of printed matter.