WO2023054473A1 - Composition adhésive non aqueuse, procédé d'impression, procédé destiné á la production de matière imprimée, jeu de compositions, dispositif et matière imprimée - Google Patents

Composition adhésive non aqueuse, procédé d'impression, procédé destiné á la production de matière imprimée, jeu de compositions, dispositif et matière imprimée Download PDF

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Publication number
WO2023054473A1
WO2023054473A1 PCT/JP2022/036178 JP2022036178W WO2023054473A1 WO 2023054473 A1 WO2023054473 A1 WO 2023054473A1 JP 2022036178 W JP2022036178 W JP 2022036178W WO 2023054473 A1 WO2023054473 A1 WO 2023054473A1
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WIPO (PCT)
Prior art keywords
adhesive composition
aqueous adhesive
resin
composition according
carbon atoms
Prior art date
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PCT/JP2022/036178
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English (en)
Japanese (ja)
Inventor
由佳 折笠
悟志 井手之上
圭士郎 吉森
保真 齋藤
公淳 宇高
充功 田村
Original Assignee
株式会社Ｄｎｐファインケミカル
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Priority to JP2023551600A priority Critical patent/JPWO2023054473A1/ja
Publication of WO2023054473A1 publication Critical patent/WO2023054473A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • 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

Definitions

  • the present invention relates to a non-aqueous adhesive composition, a recording method, a method for producing a recorded matter, a composition set, an apparatus, and a recorded matter.
  • non-aqueous ink compositions in which various coloring materials and resins are dissolved or dispersed in a mixed liquid with an organic solvent are widely used. Characters and images can be obtained by ejecting the ink composition from a nozzle of an inkjet method or the like onto a substrate such as paper directly or via another layer, and drying the non-aqueous ink composition.
  • Patent Document 1 discloses an ink jet recording method in which an acrylic resin solution-polymerized in a glycol ether dialkyl ether solvent using a radical polymerization initiator is contained in an oil-based ink composition having a glycol ether dialkyl ether as a main solvent. Disclosed is an oil-based ink composition for Patent Document 1 discloses that this composition can obtain good print drying property, scratch resistance and re-solubility by using solubilized acrylic resin, which has been difficult to dissolve in the past. It is stated that it is possible.
  • an image having a metallic tone is sometimes expressed on a substrate (recording medium) or a substrate such as a printed matter in which a colored layer is partially or entirely laminated on the surface.
  • Techniques for imparting such metallic luster include applying an ink composition using metal powder made from brass, aluminum fine particles, etc., foil stamping using metal foil, and thermal transfer using metal foil. etc. have been used.
  • Patent Literature 2 describes a metal thin film decorative sheet and its manufacturing method.
  • Patent Document 2 describes that by adjusting the projected area and thickness of the metal film, it is possible to obtain a sheet-like material decorated with a thin metal film that is excellent in appearance and texture and has high peel strength.
  • An object of the present invention is to provide a novel adhesive composition that can be discharged onto a substrate from a nozzle and that can fix solids such as powder and foil to the substrate.
  • the present inventors have made intensive studies to solve the above problems, and found that the above problems can be solved by a composition containing an organic solvent and a resin containing a resin A having a predetermined glass transition temperature. I found it and came to solve the present invention.
  • a non-aqueous adhesive composition discharged from a nozzle comprising an organic solvent and a resin, wherein the resin contains a resin A having a glass transition temperature of ⁇ 50° C. or more and 40° C. or less.
  • Water-based adhesive composition
  • the monomer (a) constituting the resin A contains at least one selected from the group consisting of methyl acrylate, cyclohexyl acrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate; A non-aqueous adhesive composition as described.
  • the content of the resin contained in the non-aqueous adhesive composition is 1% by mass or more and 30% by mass or less in the total amount of the non-aqueous adhesive composition (1) to (5).
  • Non-aqueous adhesive composition 1% by mass or more and 30% by mass or less in the total amount of the non-aqueous adhesive composition (1) to (5).
  • a recording method comprising ejecting the non-aqueous adhesive composition according to any one of (1) to (20) onto a substrate.
  • a method for producing a recorded matter comprising the step of ejecting the non-aqueous adhesive composition according to any one of (1) to (20) onto a substrate.
  • the ink composition which is the second composition, contains an organic solvent and a resin, and the resin contains a resin B having a glass transition temperature of more than 40° C. and not more than 120° C.
  • the resin contains a resin B having a glass transition temperature of more than 40° C. and not more than 120° C.
  • the present invention can provide an adhesive composition that can be discharged onto a substrate from a nozzle and that can fix solids such as powder and foil to the substrate.
  • Non-aqueous adhesive composition is a non-aqueous adhesive composition that is discharged from a nozzle and contains an organic solvent and a resin.
  • ejected from a nozzle means ejecting a predetermined amount of a composition (liquid) through a nozzle onto a substrate such as a substrate.
  • a discharge form such as
  • the non-aqueous adhesive composition is a composition containing an organic solvent as a liquid medium without intentionally containing water, and having adhesiveness at a predetermined temperature by volatilizing the solvent. It means a composition that has the function of fixing solid substances such as powders and foils to a substrate due to its stickiness.
  • the non-aqueous adhesive composition according to the present embodiment is a composition containing an organic solvent as a liquid medium without intentionally containing water, it can be suitably used particularly for a resin substrate. can.
  • the substrate that can be used for the non-aqueous adhesive composition according to the present embodiment may be a non-absorbent substrate or an absorbent substrate, and various substrates. can be used.
  • the phrase "does not intentionally contain water” means that water that is inevitably contained due to moisture in the atmosphere or additives is not taken into consideration.
  • the water content in the non-aqueous adhesive composition according to the present embodiment is preferably 5.0% by mass or less, more preferably 3.0% by mass, based on the total amount of the non-aqueous adhesive composition. , more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less.
  • the resin contained in this non-aqueous adhesive composition is characterized by containing a resin A having a glass transition temperature of -50°C or higher and 40°C or lower.
  • the non-aqueous adhesive composition becomes adhesive at a predetermined temperature, and the adhesiveness causes powder or It has the function of fixing a solid object such as a foil to the base material.
  • the non-aqueous adhesive composition can be stably applied to the subject (substrate).
  • the inkjet method and the dispenser method since it is possible to eject to a desired position on the surface of the object (base material), the powder, foil, etc. can be applied to the desired position on the surface of the object (base material).
  • the non-aqueous adhesive composition according to the present embodiment when the non-aqueous adhesive composition according to the present embodiment is ejected by an inkjet method, the inkjet ejection stability can be increased, and the non-aqueous adhesive composition can form a uniform coating film (adhesive layer ) can be formed. Therefore, it is preferable that the non-aqueous adhesive composition according to the present embodiment is ejected by an inkjet recording apparatus by an inkjet method and mounted on the inkjet recording apparatus.
  • the "glass transition temperature" of a resin means a calculated value obtained by the following FOX formula.
  • 1/Tg W1 / Tg1 + W2 / Tg2 +...+ Wn / Tgn
  • W 1 to W n represent the weight fraction of each monomer
  • Tg 1 to Tg n are the glass transition temperatures of homopolymers obtained by polymerizing each monomer alone (unit is absolute temperature Represents "K").
  • Tg value glass transition temperature
  • the non-aqueous adhesive composition according to this embodiment contains a resin.
  • the resin has flexibility at a predetermined temperature, thereby imparting the function of fixing solid objects such as powder and foil to the base material.
  • This resin is characterized by containing a resin A having a glass transition temperature of -50°C or higher and 40°C or lower.
  • the non-aqueous adhesive composition on the substrate becomes flexible at a predetermined temperature, thereby allowing the solid material to adhere to the substrate. It becomes possible to fix to the material. In addition, it is possible to improve the abrasion resistance and peeling resistance of the fixed solid matter.
  • the glass transition temperature of Resin A is preferably -45°C or higher, more preferably -40°C or higher, and even more preferably -35°C or higher.
  • the glass transition temperature of Resin A is preferably 35° C. or lower, more preferably 30° C. or lower, and even more preferably 25° C. or lower.
  • the content of resin A is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more of the total amount of resin contained in the non-aqueous adhesive composition. More preferred.
  • the type of resin A is not particularly limited, and examples include acrylic resins (including copolymers such as styrene-acrylic resins), polystyrene resins, polyester resins, vinyl chloride resins, and acetic acid.
  • Acrylic resins including copolymers such as styrene-acrylic resins
  • polystyrene resins polystyrene resins
  • polyester resins vinyl chloride resins
  • acetic acid vinyl resin, vinyl chloride vinyl acetate copolymer resin, polyethylene resin, polyurethane resin, rosin-modified resin, phenol resin, terpene resin, polyamide resin, vinyl toluene- ⁇ -methylstyrene copolymer, ethylene-vinyl acetate copolymers, cellulose acetate butyrate, cellulose acetate propionate, silicone (silicon) resins, acrylamide resins, epoxy resins, polyether resins, polycarbonate resins, or copolymer resins
  • the resin A preferably contains an acrylic resin, a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer resin, a cellulose resin, a polyester resin, or a polyurethane resin. It is preferable to contain an acrylic resin.
  • the acrylic resin means a resin containing the following monomer represented by formula (A) as a constituent monomer.
  • Rx and Ry are not particularly limited as long as they are substituent groups.
  • Rx is a hydrogen group or an optionally substituted, branched or cyclic hydrocarbon group
  • Ry is a hydrogen group or It is a hydrocarbon group that may be substituted, branched, or cyclic.
  • the acrylic resin is not particularly limited, it is preferable that a (meth)acrylic acid ester monomer is included in the constituent monomers.
  • a (meth)acrylic acid ester monomer a known compound can be used, and a monofunctional (meth)acrylic acid ester can be preferably used. Examples thereof include (meth)acrylic acid alkyl esters, (meth)acrylic acid aralkyl esters, (meth)acrylic acid alkoxyalkyl esters, and the like.
  • Monomers constituting the acrylic resin may include an acid group-containing monomer having an acid group, a hydroxyl group-containing monomer having a hydroxyl group, and an amino group-containing monomer having an amino group.
  • Acid group-containing monomers having an acid group include, for example, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, Ethylenically unsaturated monomers such as carboxyl group-containing aliphatic monomers such as monomethyl itaconate, monobutyl itaconate, vinyl benzoic acid, monohydroxyethyl oxalate (meth)acrylate, carboxyl group-terminated caprolactone-modified (meth)acrylate, etc.
  • Carboxyl group-containing monomers having saturated double bonds and carboxyl groups can be mentioned.
  • the hydroxyl-containing monomer containing a hydroxyl group is not particularly limited as long as it has an unsaturated double bond and a hydroxyl group. Examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) ) acrylate, 3-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, methyl ⁇ - (hydroxymethyl) (meth)acrylate, ethyl ⁇ -(hydroxymethyl) (meth)acrylate, n-butyl ⁇ -(hydroxymethyl) (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 4- Hydroxybutyl (meth)acrylate and the like can
  • the amino group-containing monomer is not particularly limited as long as it has an unsaturated double bond and an amino group.
  • examples include (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl ( meth)acrylamide, N,N-dimethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, methylenebis(meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, Acrylamide compounds such as N,N-dimethylaminopropyl acrylamide and diacetone acrylamide, nitrogen atom-containing (meth)acrylates such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and ethylene oxide addition (meth)acrylate of morpholine compounds, N-vin
  • the monomers constituting the acrylic resin other than the above (meth)acrylic acid ester monomers and the like, other monomers may be included as necessary.
  • Such other monomers are not particularly limited as long as they can be copolymerized with the (meth)acrylic acid ester monomer, and a monofunctional monomer having one ethylenically unsaturated double bond. or a polyfunctional monomer having 2 or more.
  • vinyl monomers such as vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, N-vinylcarbazole, vinylimidazole, vinyl ether, vinylketone, vinylpyrrolidone; ⁇ -, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives, vinyl toluene, aromatic vinyl monomers such as chlorostyrene; ethylene, propylene, isopropylene, etc. olefin monomers; butadiene, chloroprene, etc.
  • diene monomers such as acrylonitrile and methacrylonitrile can be used.
  • diacrylate compounds such as polyethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butylene glycol diacrylate; triacrylate compounds such as trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate.
  • dimethacrylate compounds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate and triethylene glycol dimethacrylate; trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethane trimethacrylate; and divinylbenzene.
  • the acrylic resin can be formed using these monomers, but the form of copolymerization of the monomers is not particularly limited, and may be, for example, a block copolymer, a random copolymer, a graft copolymer, or the like. be able to.
  • acrylic resins it is preferable to include the following monomer (a) as a constitution.
  • Ry represents a hydrogen group or an optionally branched hydrocarbon group having 1 to 12 carbon atoms.
  • Rx may be branched or cyclic. represents a hydrocarbon group having 1 to 18 carbon atoms, and when Ry is an optionally branched hydrocarbon group having 1 to 12 carbon atoms, Rx is an optionally branched hydrocarbon group having 2 to 18 carbon atoms represents a group.
  • the ratio of the monomer (a) constituting the resin A is not particularly limited as long as the glass transition temperature of the resin A is within a predetermined range, but it is preferably 50% by mass or more of the total amount of the monomers constituting the resin A. , more preferably 70% by mass or more, more preferably 90% by mass or more.
  • Rx is preferably a hydrocarbon group of 2 or more and 12 or less which may be branched or cyclic, and 4 or more which may be branched or cyclic.
  • a hydrocarbon group of 12 or less is more preferable, and a hydrocarbon group of 4 or more and 8 or less which may be branched or cyclic is more preferable.
  • Rx is an optionally branched hydrocarbon group having 4 to 12 carbon atoms. More preferably, it is a hydrocarbon group having 4 or more and 8 or less carbon atoms which may be branched.
  • Examples of monomer (a) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-pentyl acrylate, and 3-pentyl acrylate.
  • -pentyl acrylate lauryl acrylate, cyclohexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n-pentyl methacrylate, and n-hexyl methacrylate.
  • those containing at least one selected from the group consisting of methyl acrylate, cyclohexyl acrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate are particularly preferred.
  • the monomer other than the monomer (a) that constitutes the resin A is not particularly limited as long as it is another ethylenically polymerizable monomer that can be copolymerized with the monomer (a).
  • the above aromatic vinyl monomers such as ethylene, the above diene monomers such as butadiene, the above vinyl cyanide monomers such as acrylonitrile, diacrylate compounds such as polyethylene glycol diacrylate, trimethylolpropane triacrylate
  • diacrylate compounds such as polyethylene glycol diacrylate, trimethylolpropane triacrylate
  • trimethacrylate compounds such as trimethylolpropane trimethacrylate, divinylbenzene, vinylcyclohexane, tert-butyl-4-ethynyl
  • Acrylamide monomers such as cyclohexane, dimethylacrylamide, diethylacrylamide, hydroxyethylacrylamide, and isopropylacrylamide are included.
  • the resin A may be synthesized using the above monomers as raw materials, or a commercially available resin may be used.
  • the vinyl chloride resin may be either a homopolymer composed of a vinyl chloride monomer or a copolymer using two or more selected polymerizable monomers.
  • copolymers of vinyl chloride resins include vinyl chloride-vinyl acetate copolymer resins.
  • a vinyl chloride-vinyl acetate copolymer resin is a polymer of vinyl chloride monomer and vinyl acetate monomer.
  • Vinyl chloride-vinyl acetate copolymer resins include, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic acid copolymer, vinyl chloride/vinyl acetate/vinyl alcohol copolymer, vinyl chloride/vinyl acetate / hydroxyalkyl acrylate copolymers, etc., and mixtures thereof having a glass transition temperature of -50°C or higher and 40°C or lower.
  • a commercially available vinyl chloride resin may be used as the vinyl chloride resin.
  • a vinyl chloride-vinyl acetate copolymer resin can be obtained by polymerizing a vinyl chloride monomer and a vinyl acetate monomer.
  • a conventionally known polymerization method may be used as the polymerization method.
  • the polymerization method is preferably emulsion polymerization or suspension polymerization, more preferably suspension polymerization.
  • As the vinyl chloride-vinyl acetate copolymer resin a commercially available vinyl chloride-vinyl acetate copolymer resin may be used.
  • a cellulose-based resin is a resin with a cellulose skeleton that is obtained by biologically or chemically introducing functional groups using cellulose as a raw material.
  • cellulose-based resins include cellulose acetate butyrate resins, cellulose acetate propionate resins, cellulose acetate alkylate resins such as cellulose acetate propionate butyrate resins, cellulose acetate resins, nitrocellulose resins, and mixtures thereof. mentioned.
  • a commercially available cellulose resin may be used as the cellulose resin.
  • a polyester resin contains at least a structural unit obtained by polycondensation of an alcohol component and a carboxylic acid component.
  • the polyester-based resin may include a modified polyester-based resin.
  • a commercially available polyester-based resin may be used as the polyester-based resin.
  • a polyurethane resin contains at least a structural unit obtained by copolymerizing an alcohol component and an isocyanate component.
  • Polyurethane-based resins may include polyurethane-based resins modified with polyester, polyether, or caprolactone.
  • a commercially available polyurethane-based resin may be used as the polyurethane-based resin.
  • acrylic resins vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins may be used alone, or two or more of them may be used in combination.
  • the weight average molecular weight (relative molecular mass) of Resin A is not particularly limited, it is preferably 10,000 or more, more preferably 15,000 or more.
  • the weight average molecular weight (relative molecular mass) is preferably 60,000 or less, more preferably 50,000 or less.
  • Relative molecular weights of resins can be measured by conventional GPC (gel permeation chromatography).
  • the resin contained in the non-aqueous adhesive composition according to the present embodiment may contain a resin other than resin A.
  • resin A examples include acrylic resins (including copolymers such as styrene-acrylic resins), polystyrene resins, polyester resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride vinyl acetate copolymer resins, and polyethylene resins.
  • polyurethane resin polyurethane resin, rosin modified resin, phenol resin, terpene resin, polyamide resin, vinyl toluene- ⁇ -methylstyrene copolymer, ethylene-vinyl acetate copolymer, cellulose acetate butyrate, cellulose acetate propio resins, silicone (silicon)-based resins, acrylamide-based resins, epoxy-based resins, or copolymer resins or mixtures thereof, which do not satisfy the requirements for resin A.
  • Commercially available resins may be used as these resins.
  • the content of the resin contained in the non-aqueous adhesive composition is not particularly limited, but it is preferably contained in the range of 1.0% by mass or more in the total amount of the non-aqueous adhesive composition, and 3.0% by mass or more. more preferably in the range of 5.0% by mass or more, and even more preferably in the range of 7.0% by mass or more.
  • the fixability of the solid substance is improved.
  • the foil transferability can be improved.
  • the resin contained in the non-aqueous adhesive composition is preferably contained in the range of 30.0% by mass or less in the total amount of the non-aqueous adhesive composition, and more preferably in the range of 20.0% by mass or less. It is preferably contained in the range of 15.0% by mass or less, and more preferably contained. This improves the ejection stability of the non-aqueous adhesive composition from the nozzle.
  • the non-aqueous adhesive composition according to the present embodiment is used as an inkjet non-aqueous adhesive composition for inkjet ejection, it is necessary to effectively improve the ejection stability from the ink head nozzle. becomes possible.
  • the non-aqueous adhesive composition according to this embodiment contains an organic solvent.
  • the organic solvent is a liquid medium for the non-aqueous adhesive composition, and has the function of dissolving (or dispersing) each component such as the resin.
  • the fluidity of the non-aqueous adhesive composition is improved, and it becomes possible to eject it from a nozzle such as an inkjet or a dispenser.
  • organic solvent for example, those contained in conventional non-aqueous ink compositions for inkjet (sometimes referred to as non-aqueous or oily) can be used.
  • examples include those containing a glycol ether solvent represented by the following formula (2).
  • R a (—OR b ) n —OR c (2)
  • R a and R c are each independently hydrogen or an optionally branched alkyl group having 1 to 8 carbon atoms
  • R b is a branched alkyl group having 1 to 4 carbon atoms.
  • n represents an integer of 1 or more and 6 or less).
  • Glycol ether-based solvents include glycol ether monoalkyl represented by the following formula (3) and glycol ether dialkyl represented by the following formula (4).
  • R d (—OR e ) n —OH (3)
  • R d is an alkyl group having 1 to 8 carbon atoms and may be branched
  • R e represents an alkylene group having 1 to 4 carbon atoms and may be branched
  • n represents an integer of 1 or more and 6 or less.
  • R f (—OR g ) n —OR h (4)
  • R f and R h are each independently an optionally branched alkyl group having 1 to 8 carbon atoms
  • R g is an optionally branched alkyl group having 1 to 4 carbon atoms. represents a good alkylene group
  • n represents an integer of 1 or more and 6 or less.
  • acrylic resins are easily dissolved in glycol ether solvents, and by containing a predetermined amount of glycol ether solvents, the ejection stability of the non-aqueous adhesive composition from nozzles is improved.
  • the non-aqueous adhesive composition according to the present embodiment is used as an inkjet non-aqueous adhesive composition for inkjet ejection, it is necessary to effectively improve the ejection stability from the ink head nozzle. becomes possible.
  • glycol ether monoalkyl examples include ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl (or ethyl, propyl, isopropyl , n-butyl, isobutyl, t-butyl, 2-ethylhexyl ether, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tetraethylene glycol monomethyl ether, Propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-2-ethylhe
  • diethylene glycol monomethyl ether diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol Monomethyl Ether, Tetraethylene Glycol Monoethyl Ether, Tetraethylene Glycol Monopropyl Ether, Tetraethylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Monopropyl Ether, Propylene Glycol Monobutyl Ether, Dipropylene Glycol Monomethyl Ether , dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl Ether ,
  • Glycol ether dialkyl includes ethylene glycol dibutyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl.
  • diethylene glycol dimethyl ether diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol methyl-2-ethylhexyl ether, triethylene glycol Dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl-2-ethylhexyl ether , dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether
  • the preferred content of the glycol ether solvent represented by formula (2) is preferably 20% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass in the total amount of the non-aqueous adhesive composition. It is more preferable that it is above.
  • the preferred content of the glycol ether solvent represented by formula (2) is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass of the total amount of the non-aqueous adhesive composition. More preferably:
  • the preferred content of the glycol ether monoalkyl represented by formula (3) is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass of the total amount of the non-aqueous adhesive composition. It is more preferable that it is above.
  • the preferred content of the glycol ether monoalkyl represented by formula (3) is preferably 30% by mass or less, more preferably 20% by mass or less, and 10% by mass of the total amount of the non-aqueous adhesive composition. More preferably:
  • the preferred content of the glycol ether dialkyl represented by formula (4) is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass or more in the total amount of the non-aqueous adhesive composition. is more preferable.
  • the preferred content of the glycol ether dialkyl represented by formula (4) is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less in the total amount of the non-aqueous adhesive composition. is more preferable.
  • the solvent represented by the general formula (5), the solvent represented by the general formula (6), and the general formula (7) It is preferable to contain at least one or more selected from the group consisting of solvents represented by.
  • R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms
  • R 2 and R 3 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • R 2 and R 3 in formula (5) are preferably alkyl groups having 1 to 4 carbon atoms, more preferably alkyl groups having 2 to 4 carbon atoms.
  • R 4 is an alkylene group having 3 to 5 carbon atoms
  • R 5 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group.
  • Unsaturated hydrocarbon group means a hydrocarbon group containing at least one or more multiple bonds such as a vinyl group.
  • R 5 in formula (6) is preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, or an unsaturated hydrocarbon group, and is preferably hydrogen, an alkyl group having 1 to 2 carbon atoms, or an unsaturated hydrocarbon group.
  • a hydrogen group is preferred.
  • R6 is an alkylene group having 3 to 5 carbon atoms
  • R7 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • R 6 is preferably 3 or more and 4 or less, and more preferably 3.
  • R 7 is preferably hydrogen or an alkyl group having 1 carbon atom, more preferably hydrogen.
  • the non-aqueous adhesive composition according to the present embodiment When used as an inkjet non-aqueous adhesive composition for inkjet ejection, it contains these alkylamide solvents, cyclic amide solvents, and lactone solvents. By doing so, it is possible to effectively eliminate clogging in the nozzles of the ink jet head and effectively improve the ejection stability from the ink head nozzles.
  • the resin It has high permeability to the base material and dries quickly on the resin base material after ejection.
  • solvent represented by formula (5), solvent represented by formula (6), solvent represented by formula (7) the resin It has high permeability to the base material and dries quickly on the resin base material after ejection.
  • the non-aqueous adhesive composition according to the present embodiment is discharged onto a resin substrate and the metal foil is transferred (fixed) to the resin substrate by the non-aqueous adhesive composition, drying on the resin substrate Since the transfer speed is fast, it is possible to transfer the metal foil particularly cleanly, and the surface shape of the metal foil on the obtained recorded matter is good, and the fineness is also good. Fine fixing is possible.
  • the solvent represented by formula (5) include N,N-diethylformamide, N,N-diethylacetamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N- Examples include alkylamide solvents such as diethylpropanamide, N,N-dipropylpropanamide, N-ethylformamide and N-ethylacetamide.
  • alkylamide solvents such as diethylpropanamide, N,N-dipropylpropanamide, N-ethylformamide and N-ethylacetamide.
  • solvents represented by formula (6) include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2 -pyrrolidone, ⁇ -caprolactam, N-methyl- ⁇ -caprolactam, N-vinylcaprolactam, N-ethyl- ⁇ -caprolactam, N-propyl- ⁇ -caprolactam, N-butyl- ⁇ -caprolactam, N-acetylcaprolactam, etc.
  • a cyclic amide-based solvent can be mentioned. Among these, it is preferable to contain at least one selected from the group consisting of ⁇ -caprolactam, N-methylcaprolactam, and N-vinylcaprolactam.
  • solvents represented by formula (7) include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -heptanolactone, ⁇ -octanolactone, ⁇ -nonalactone, ⁇ - decalactone, ⁇ -undecalactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -heptanolactone, ⁇ -octanolactone, ⁇ -nonalactone, ⁇ -decalactone, ⁇ -undecalactone, ⁇ -caprolactone, etc.
  • a lactone solvent can be mentioned.
  • the content of the solvent represented by formula (5) is not particularly limited, but the lower limit of the content of the solvent represented by formula (5) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 5% by mass or more is more preferred, and 8% by mass or more is even more preferred.
  • the upper limit of the content of the solvent represented by formula (5) is preferably 90% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the non-aqueous adhesive composition. It is even more preferable to have
  • the content of the solvent represented by formula (6) is not particularly limited, but the lower limit of the content of the solvent represented by formula (6) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 5% by mass or more is more preferred, and 8% by mass or more is even more preferred.
  • the upper limit of the content of the solvent represented by formula (6) is preferably 90% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the non-aqueous adhesive composition. It is even more preferable to have
  • the content of the solvent represented by formula (7) is not particularly limited, but the lower limit of the content of the solvent represented by formula (7) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 3% by mass or more is more preferred, and 5% by mass or more is even more preferred.
  • the upper limit of the content of the solvent represented by formula (7) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the non-aqueous adhesive composition. It is more preferable that the content is 20% by mass or less.
  • the general formula (8) A solvent represented by the general formula (9), a solvent represented by the general formula (9), a solvent represented by the general formula (10), or a solvent represented by the general formula (11) It is preferable to contain at least one or more selected from the group consisting of solvents. As a result, a solvent-based non-aqueous adhesive composition that effectively exhibits the above effects is obtained.
  • R 8 is hydrogen or an alkyl group having 1 to 4 carbon atoms
  • R 9 represents an alkylene group having 1 to 3 carbon atoms.
  • R 10 , R 11 and R 12 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 13 represents an alkylene group having 1 to 4 carbon atoms. .
  • R 14 represents an optionally branched alkyl group or unsaturated hydrocarbon group having 1 to 4 carbon atoms
  • R 15 represents an alkylene group having 1 to 4 carbon atoms.
  • R 16 and R 17 are each independently an alkyl group having 1 to 4 carbon atoms and may be branched, and R 18 represents an alkylene group having 2 to 4 carbon atoms.
  • solvent represented by formula (8) include carbonate esters such as propylene carbonate and ethylene carbonate.
  • solvent represented by formula (9) examples include 3-methoxypropanamide, 3-butoxypropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dibutyl Propanamide, 3-butoxy-N,N-dibutylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethyl-3-methoxypropanamide, N,N-dibutyl-3-methoxypropanamide , N,N-dibutyl-3-butoxypropanamide and N,N-dimethyl-3-butoxypropanamide.
  • solvent represented by formula (10) include oxazolidinone-based solvents such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, and N-vinylmethyloxazolidinone.
  • Solvents represented by formula (11) include 1,3-dimethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and the like. and imidazolidinone-based solvents.
  • the content of the solvent represented by formula (8) is not particularly limited, but the lower limit of the content of the solvent represented by formula (8) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 3% by mass or more is more preferred, and 5% by mass or more is even more preferred.
  • the upper limit of the content of the solvent represented by formula (8) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the non-aqueous adhesive composition. It is more preferable that the content is 20% by mass or less, and it is even more preferable that the content is 20% by mass or less.
  • the content of the solvent represented by formula (9) is not particularly limited, but the lower limit of the content of the solvent represented by formula (9) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 3% by mass or more is more preferred, and 5% by mass or more is even more preferred.
  • the upper limit of the content of the solvent represented by formula (9) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the non-aqueous adhesive composition. It is more preferable that the content is 20% by mass or less, and it is even more preferable that the content is 20% by mass or less.
  • the content of the solvent represented by formula (10) is not particularly limited, but the lower limit of the content of the solvent represented by formula (10) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 3% by mass or more is more preferred, and 5% by mass or more is even more preferred.
  • the upper limit of the content of the solvent represented by formula (10) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the non-aqueous adhesive composition. It is more preferable that the content is 20% by mass or less, and it is even more preferable that the content is 20% by mass or less.
  • the content of the solvent represented by formula (11) is not particularly limited, but the lower limit of the content of the solvent represented by formula (11) is 1% by mass or more in the total amount of the non-aqueous adhesive composition. is preferred, 3% by mass or more is more preferred, and 5% by mass or more is even more preferred.
  • the upper limit of the content of the solvent represented by formula (11) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the non-aqueous adhesive composition. It is more preferable that the content is 20% by mass or less, and it is even more preferable that the content is 20% by mass or less.
  • a solvent represented by the formula (8), or a solvent represented by the formula (9)” is preferable, and “a solvent represented by the formula (5), a solvent represented by the formula (6) A solvent, or one containing a solvent represented by formula (7)” is more preferred.
  • the acrylic resin is easily dissolved in the alkylamide-based solvent represented by the formula (5), and by containing a predetermined amount of the alkylamide-based solvent, the ejection stability of the non-aqueous adhesive composition from the nozzle is improved. improves.
  • the non-aqueous adhesive composition according to the present embodiment is used as an inkjet non-aqueous adhesive composition for inkjet ejection, it is necessary to effectively improve the ejection stability from the ink head nozzle. becomes possible. Two or more of these organic solvents may be mixed.
  • solvents glycol ether solvents, solvents represented by formula (5), solvents represented by formula (6), solvents represented by formula (7), solvents represented by formula (8) , the solvent represented by the formula (9), the solvent represented by the formula (10), and the solvent represented by the formula (11)
  • a solvent with a high flash point for example, a flash point of 70° C. or higher
  • a non-aqueous pressure-sensitive adhesive composition having high recovery from cleaning can be obtained.
  • a solvent with a low flash point for example, a flash point of less than 70° C.
  • the non-aqueous adhesive composition according to the present embodiment includes the above glycol ether solvent, the solvent represented by formula (5), the solvent represented by formula (6), and the solvent represented by formula (7). , the solvent represented by the formula (8), the solvent represented by the formula (9), the solvent represented by the formula (10), even if it contains an organic solvent other than the solvent represented by the formula (11) good.
  • diols diols
  • glycerin trimethylolethane, trimethylolpropane, triols such as 1,2,6-hexanetriol: tetrahydric alcohols such as mesoerythritol and pentaerythritol, monoethanolamine, diethanolamine, triethanolamine, N -Alkanolamines such as methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine; methyl acetate, ethyl acetate, -n-propyl acetate, acetic acid Acetate esters such as isopropyl, n-butyl acetate, isobutyl acetate, hexyl acetate, and octyl acetate; Saturated hydrocarbons such as hexane, isohexane, n
  • the content of other organic solvents is not particularly limited, but the lower limit of the content of other organic solvents is preferably in the range of 10% by mass or more in the total amount of the non-aqueous adhesive composition, and 20% by mass or more. and more preferably 30% by mass or more.
  • the upper limit of the content of other organic solvents is preferably in the range of 85% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the non-aqueous adhesive composition. is more preferable.
  • the purpose is to suppress volatilization and solidification of the non-aqueous adhesive composition in devices such as nozzles and tubes, and to re-dissolve when solidified.
  • a surfactant may be incorporated for the purpose of lowering the surface tension to improve the wettability with the recording medium (substrate) and for the purpose of improving the abrasion resistance of the coating film.
  • surfactants include polyoxyalkylene alkyl ethers such as nonionic P-208, P-210, P-213, E-202S, E-205S, E-215, K-204, K-220, S -207, S-215, A-10R, A-13P, NC-203, NC-207 (manufactured by NOF Corporation), Emulgen 106, 108, 707, 709, A-90, A-60 (Kao ( Co., Ltd.), Floren G-70, D-90, TG-740W (manufactured by Kyoeisha Chemical Co., Ltd.), Poem J-0081HV (manufactured by Riken Vitamin Co., Ltd.), and as aliphatic phosphates, Adekatol NP -620, NP-650, NP-660, NP-675, NP-683, NP-686, Adekacol CS-141E, TS-230E (manufactured by Adeka Co., Ltd.
  • polyester-modified silicone or polyether-modified silicone as the silicone-based surfactant having a siloxane skeleton.
  • acetylene glycol surfactants such as BYK-UV3500, 3510, 3530, 3570 (all manufactured by BYK-Chemie Japan) include Surfynol (registered trademark) 82, 104, 465, 485, TG (any (also manufactured by Air Products Japan), Olfin (registered trademark) STG, E1010 (both manufactured by Nissin Kagaku Co., Ltd.), and the like.
  • Surfactants are not limited to those described above, and any of anionic, cationic, amphoteric or nonionic surfactants can be used.
  • the surfactant preferably contains a surfactant having a siloxane skeleton.
  • polyester-modified silicone or polyether-modified silicone As the surfactant having a siloxane skeleton, it is preferable to use polyester-modified silicone or polyether-modified silicone. Specific examples include BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500 and 3510. , 3530, 3570 (both manufactured by BYK-Chemie Japan) and the like can be used.
  • the non-aqueous adhesive composition according to the present embodiment may contain a surfactant having a siloxane skeleton and a surfactant different from the surfactant having a siloxane skeleton.
  • the content of the surfactant is not particularly limited, but the lower limit of the content of the surfactant is It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, based on the total amount of the composition.
  • the upper limit of the surfactant content is preferably 1.0% by mass or less, more preferably 0.9% by mass or less, and 0.8% by mass or less in the total amount of the non-aqueous adhesive composition. is more preferable.
  • the non-aqueous adhesive composition according to this embodiment may contain a coloring material.
  • the coloring material is not particularly limited, and may be dye-based or pigment-based.
  • organic pigments include, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine-based organic pigments, quinacridone-based organic pigments, perylene-based organic pigments, perinone-based organic pigments, azomethine-based organic pigments, and anthraquinone-based pigments.
  • Organic pigments (anthrone-based organic pigments), xanthene-based organic pigments, diketopyrrolopyrrole-based organic pigments, dioxazine-based organic pigments, nickel azo-based pigments, isoindolinone-based organic pigments, pyranthrone-based organic pigments, thioindigo-based organic pigments, condensed azo organic solid solution pigments such as organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments, isoindoline organic pigments, quinacridone solid solution pigments, perylene solid solution pigments, and other pigments such as lake pigments and carbon black. be done.
  • C.I. color index
  • inorganic pigments that can be used in the non-aqueous adhesive composition according to the present embodiment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, Alumina, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (iron(III) oxide), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, aluminum, titanium, indium, synthetic Iron black, inorganic solid solution pigments and the like can be mentioned.
  • titanium oxide barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, Alumina, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (iron(III) oxide), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, aluminum, titanium, indium
  • coloring materials be appropriately selected according to the base material (recording medium), the type and shape of the solid matter, the function and properties of the recorded matter, and the like.
  • the non-aqueous adhesive composition according to the present embodiment is used to transfer a metal foil or fix a metal powder to a substrate, the inclusion of a black pigment improves the brightness of the metal foil (or metal powder). It is possible to
  • the average dispersed particle size of the pigment that can be contained in the non-aqueous adhesive composition according to the present embodiment is not particularly limited as long as the desired color development is possible. Although it varies depending on the type of pigment used, the volume average particle diameter is preferably 5 nm or more, preferably 20 nm or more, from the viewpoint of good dispersibility and dispersion stability of the pigment and obtaining sufficient coloring power. is more preferable, and 30 nm or more is even more preferable. When the volume average particle size is at least the above lower limit, the light resistance of the non-aqueous adhesive composition can be improved.
  • the volume average particle size is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 350 nm or less.
  • the volume-average particle size of the pigment is equal to or less than the above upper limit, so that the inkjet ejection stability can be made extremely high.
  • the volume-average particle size of the pigment is measured at 25° C. using a particle size distribution measuring device (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.). diameter (D50).
  • volume-based cumulative 50% particle diameter (D50) means a particle diameter at which the cumulative volume calculated from the smaller diameter side becomes 50%.
  • “Volume-based cumulative 50% particle size (D50)” may also be referred to as “volume average particle size D50" or "median (median) size”.
  • the content of the coloring material (pigment) is not particularly limited, but the lower limit of the content of the coloring material (pigment) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount of the non-aqueous adhesive composition.
  • the lower limit of the content of the coloring material (pigment) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount of the non-aqueous adhesive composition.
  • a black pigment or white pigment is contained as a coloring material, it is possible to improve the concealability of the adhesive layer.
  • the black pigment containing 0.01% by mass or more as a coloring material is more It is possible to effectively improve the brightness of the metal foil (or metal powder).
  • the upper limit of the content of the coloring material (pigment) is preferably 20.0% by mass or less, more preferably 10.0% by mass or less, and 5.0% by mass in the total amount of the non-aqueous adhesive composition. % or less, and even more preferably 1.0 mass % or less.
  • the content of the resin in the non-aqueous pressure-sensitive adhesive composition is relatively increased in the same viscosity range, so that the fixability of the solid matter to be fixed on the substrate is more effectively improved.
  • a pigment dispersant When the non-aqueous adhesive composition according to the present embodiment contains a coloring material (pigment), a pigment dispersant may be used. Any pigment dispersant used in non-aqueous ink compositions can be used as the dispersant. A polymer dispersant may be used as the pigment dispersant. Such a dispersant has a polyester-based, polyacrylic-based, polyurethane-based, polyamine-based, polycaprolactone-based, or the like main chain, and has a polar group such as an amino group, a carboxyl group, a sulfone group, or a hydroxyl group as a side chain. is.
  • polyacrylic dispersants for example, Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131 , 9132, 9133, 9151 (manufactured by Vic Chemie), Efka PX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF), TREPLUS D-1200, D-1410, D-1420, MD-1000 (manufactured by Otsuka Chemical Co., Ltd.), Floren DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like are used.
  • Polycaprolactone-based dispersants include, for example, Ajisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 ( Kawaken Fine Chemicals Co., Ltd.), Solsperse 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J10 TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan) and the like are used.
  • the content of the pigment dispersant is not particularly limited, but the lower limit of the content of the pigment dispersant is preferably 5 parts by mass or more with respect to 100 parts by mass of the pigment in the non-aqueous adhesive composition, It is more preferably 20 parts by mass or more, more preferably 20 parts by mass or more.
  • the upper limit of the content of the pigment dispersant is preferably 150 parts by mass or less, more preferably 125 parts by mass or less, and 100 parts by mass or less with respect to 100 parts by mass of the pigment in the non-aqueous adhesive composition. is more preferable.
  • a dispersing aid may be used as necessary in the non-aqueous adhesive composition according to the present embodiment.
  • the dispersing aid is adsorbed on the surface of the coloring material (pigment), and the functional group increases the affinity with the organic solvent and dispersant in the non-aqueous adhesive composition, thereby improving the dispersion stability.
  • a known pigment derivative having a functional group such as an acidic group, a basic group, or a neutral group in the organic pigment residue can be used.
  • the non-aqueous adhesive composition according to the present embodiment includes light stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface conditioners, slip agents, leveling agents (acrylic and silicon system, etc.), antifoaming agents, pH adjusters, bactericides, preservatives, deodorants, charge control agents, wetting agents, and other known additives as optional components.
  • light stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface conditioners, slip agents, leveling agents (acrylic and silicon system, etc.), antifoaming agents, pH adjusters, bactericides, preservatives, deodorants, charge control agents, wetting agents, and other known additives as optional components.
  • Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like.
  • Specific examples include BHA (2,3-butyl-4-oxyanisole) and BHT (2,6-di-t-butyl-p-cresol).
  • a benzophenone-based compound or a benzotriazole-based compound can be used as the ultraviolet absorber.
  • Specific examples of the epoxidized product include epoxy glyceride, epoxy fatty acid monoester, and epoxy hexahydrophthalate, and specific examples include ADEKA CIZER O-130P and ADEKA CIZER O-180A (manufactured by ADEKA). exemplified.
  • Specific examples of polycarboxylic acids include citric acid and maleic acid.
  • the viscosity of the non-aqueous adhesive composition according to the present embodiment is not particularly limited, and is preferably selected as appropriate according to the discharge method.
  • the viscosity at 25° C. should be 15.0 mPa ⁇ s or less from the viewpoint of inkjet ejection property and ejection stability. is preferred, 13.0 mPa ⁇ s is more preferred, and 10.0 mPa ⁇ s or less is even more preferred.
  • the viscosity of the non-aqueous adhesive composition according to the present embodiment is preferably 1.0 mPa ⁇ s or more, more preferably 2.0 mPa ⁇ s or more, and 3.0 mPa ⁇ s or more. It is even more preferable to have
  • the surface tension of the non-aqueous adhesive composition according to the present embodiment is not particularly limited, and is preferably selected as appropriate according to the discharge method.
  • the surface tension at 25° C. is It is preferably 20 mN/m or more, more preferably 22 mN/m or more, and even more preferably 24 mN/m or more.
  • the surface tension of the non-aqueous adhesive composition according to the present embodiment is preferably 40 mN/m or less, more preferably 37 mN/m or less, and even more preferably 35 mN/m or less. .
  • the method for producing a non-aqueous adhesive composition according to the present embodiment comprises mixing an organic solvent, a resin, and optionally other components (for example, a surfactant, etc.) using a paint shaker. can be done. At this time, each component may be dispersed with zirconia beads. Moreover, the obtained non-aqueous pressure-sensitive adhesive composition may be adjusted to a desired dissolved oxygen content and dissolved nitrogen content by performing a deaeration treatment or the like as necessary.
  • the organic solvent in advance.
  • a method for drying the organic solvent for example, a method of spraying an inert gas (e.g., nitrogen gas) dried in an inert gas atmosphere such as nitrogen for a predetermined time, a method of distilling and refining the organic solvent, and water are selected. Examples include a method of allowing the organic solvent to permeate through a semi-permeable membrane that selectively permeates the organic solvent, and a method of selectively adsorbing water mixed in the organic solvent with a water adsorbent that adsorbs water.
  • an inert gas e.g., nitrogen gas
  • a method for producing a recorded matter according to the present embodiment is a method for producing a recorded matter in which the non-aqueous adhesive composition described above is ejected from a nozzle. By volatilizing the solvent, the above non-aqueous adhesive composition becomes adhesive at a predetermined temperature, and the adhesiveness allows solid substances such as powders and foils to be fixed to the substrate. Therefore, the method of manufacturing a recorded matter according to the present embodiment can also manufacture a recorded matter on which a solid matter is fixed. The same applies to a recording method using a non-aqueous adhesive composition, which will be described later.
  • an inkjet method or a dispenser method As a recording method for ejecting from a nozzle, an inkjet method or a dispenser method is preferable, and among these, an inkjet method is particularly preferable. If it is an inkjet method or a dispenser method, it is possible to discharge to a desired position on the surface of the object (base material), so solid objects such as powders and foils can be applied to the desired position on the surface of the object (base material). It can be fixed. Therefore, for example, it is possible to obtain a patterned recorded matter in which a solid object is fixed at a desired position.
  • a non-aqueous adhesive composition is ejected onto a substrate by an inkjet method, and a metal foil is transferred (fixed) to the substrate to produce a recorded matter.
  • a manufacturing method will be described.
  • the method for producing a recorded matter of the present invention is not limited to this method.
  • a recorded matter may be produced by fixing a solid substance different from the metal foil to the substrate.
  • Step 1 the non-aqueous adhesive composition is discharged onto a substrate by an inkjet method. If it is an inkjet method, it is possible to eject to a desired position on the surface of the object (base material), so it is possible to transfer the metal foil to a desired position on the base material surface. It is also possible to obtain a patterned recorded matter in which a metal foil is fixed at a desired position. In addition, in order to transfer the metal foil to the entire surface of the substrate, the non-aqueous adhesive composition may be discharged onto the entire surface of the substrate.
  • non-aqueous adhesive composition may be ejected onto a desired position on the surface of the body (substrate), and a so-called normal inkjet ink composition may also be ejected.
  • a so-called normal inkjet ink composition may also be ejected.
  • an ink composition containing colors such as yellow, magenta, cyan, and black
  • a conventional non-aqueous (sometimes referred to as non-aqueous or oily) ink for inkjet is used as an inkjet recording apparatus used in the inkjet method.
  • An inkjet recording device used for the composition can be used.
  • inkjet printers such as Roland DG VersaArt RE-640 and MasterMind MMP-F13 can be used.
  • the method of ejecting ink by the inkjet method may be a piezo method using a piezoelectric element or a thermal method using a heating element, and is not particularly limited.
  • the inkjet recording device preferably has a heating mechanism.
  • the substrate surface temperature is controlled by a heating mechanism provided in the inkjet recording apparatus, and the non-aqueous adhesive composition ejected onto the substrate (recording medium) is dried to remove components such as resins. It becomes possible to fix on the material (recording medium). Furthermore, it becomes possible to easily control the temperature at which the resin contained in the non-aqueous adhesive composition has adhesiveness by means of the heating mechanism.
  • Step 2 the metal foil is transferred to the surface of the substrate coated with the non-aqueous adhesive composition. At this time, it is preferable to heat the non-aqueous adhesive composition so that the non-aqueous adhesive composition reaches a predetermined temperature.
  • the heating temperature at this time is preferably determined by the glass transition temperature of the resin A contained in the non-aqueous adhesive composition. Specifically, when the heating temperature is T1 and the glass transition temperature of resin A is T2 , the difference ( T1 - T2 ) between T1 ° C and T2 °C is 0°C or more and 60°C or less. It is preferable to determine the heating temperature so as to fall within the range of By heating the non-aqueous adhesive composition at such a temperature, the resin A reaches the glass transition temperature, so that the flexibility is improved. can be transferred (fixed) to transfer the metal foil more effectively.
  • the lower limit of the difference between T 1 °C and T 2 °C (T 1 -T 2 ) is more preferably 5°C or higher, more preferably 10°C or higher.
  • the upper limit of the difference between T 1 °C and T 2 °C (T 1 -T 2 ) is more preferably 55°C or less, more preferably 50°C or less.
  • a method of heating the non-aqueous adhesive composition includes a method of heating a substrate including the non-aqueous adhesive composition by a heating mechanism provided in an inkjet recording apparatus.
  • the heating mechanism provided in the inkjet recording apparatus may be a preheater, a platen heater, an afterheater, or the like, or may be a mechanism for blowing warm air to the composition on the substrate. Also, a plurality of these heating mechanisms may be combined.
  • a metal foil containing a release paper When transferring the metal foil to the surface of the substrate with the non-aqueous adhesive composition, for example, a metal foil containing a release paper is prepared, the metal foil is superimposed on the surface of the non-aqueous adhesive composition of the substrate, and the metal is A method of applying a predetermined pressure from the foil side or the base material side for a predetermined period of time and then peeling off the release paper can be used. Alternatively, the metal foil can be effectively fixed to the base material from the base material side or the metal foil side.
  • a method of applying pressure includes a method of applying pressure from the metal foil side or the base material side with a transfer roll or the like.
  • the pressure applied to the metal foil at this time is not particularly limited, it is preferably 10 kPa or more and 800 kPa or less.
  • the time for applying pressure is not particularly limited, but is preferably 0.1 seconds or more, for example.
  • the material of the transfer roll is not particularly limited, and examples thereof include metals (including alloys) and resins (including elastomers).
  • the degree of drying of the non-aqueous adhesive composition is not particularly limited. There is a tendency for the surface condition to deteriorate, such as the occurrence of cracks in the foil. On the other hand, if the non-aqueous adhesive composition is too dry, there is a tendency for uneven transfer to occur on the metal foil. Therefore, when the metal foil is placed on the non-aqueous adhesive composition on the substrate, the non-aqueous adhesive composition on the substrate is almost dry, but not completely dry. preferable.
  • the metal foil on the solvent-based non-aqueous adhesive composition as the substrate in a state where the volatilization amount of all the solvents contained in the non-aqueous adhesive composition is 30% or more and 99% or less.
  • the non-aqueous adhesive composition is discharged onto the surface of the base material, it is preferable to heat it at a predetermined temperature within the range of 1 minute or more and 6 minutes or less.
  • a recorded matter having a metal foil can be obtained through such steps 1 and 2.
  • the method for producing a recorded matter using the non-aqueous adhesive composition can also be defined as a recording method.
  • the above non-aqueous adhesive composition becomes adhesive at a predetermined temperature, and the adhesiveness allows solid substances such as powders and foils to be fixed to the substrate. Therefore, a recorded matter on which a solid matter is fixed can be obtained also in the recording method according to the present embodiment.
  • a set of compositions according to the present embodiment includes the above non-aqueous adhesive composition as a first composition, and an ink composition as a second composition.
  • Such a composition set includes, for example, a color ink composition as the second composition, and the non-aqueous adhesive composition is ejected onto the substrate and the color ink composition is ejected. By doing so, it is possible to produce a recorded matter on which a color image containing the metal foil is recorded.
  • the second composition which is an ink composition, refers to a plurality of ink compositions containing colors such as yellow, magenta, cyan, black, white, and intermediate colors thereof, even if there is only one composition. may be used as a concept including all of them.
  • the first composition has adhesiveness and the second composition (ink composition) does not have adhesiveness at a predetermined temperature.
  • the first composition non-aqueous adhesive composition
  • the second composition ink composition, does not have adhesiveness at a predetermined temperature.
  • a second composition containing an organic solvent and a resin
  • the resin B By containing the resin B with a high glass transition temperature, it becomes possible to prevent the second composition (ink composition) from having adhesiveness at a predetermined temperature, and the first composition (non-aqueous adhesive A solid object such as a metal foil can be adhered only to the surface of the substrate coated with the adhesive composition).
  • this second composition is a composition that does not intentionally contain water
  • this second composition also contains an organic solvent, It is preferably a non-aqueous (sometimes referred to as non-aqueous or oily) ink composition that does not intentionally contain water.
  • the content of the resin B contained in the second composition is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. preferable.
  • the type of resin in the second composition can be the same as the resin contained in the non-aqueous adhesive composition described above.
  • the lower limit of the content of the resin in the second composition (ink composition) is preferably in the range of 1.0% by mass or more based on the total amount of the second composition (ink composition), and 2.0% by mass. It is more preferably contained in the range of 3.0% by mass or more, more preferably in the range of 3.0% by mass or more.
  • the upper limit of the content of the resin in the second composition (ink composition) is preferably in the range of 30.0% by mass or less based on the total amount of the second composition (ink composition), and 20.0% by mass. It is more preferably contained in the range of 15.0% by mass or less, more preferably in the range of 15.0% by mass or less.
  • organic solvent contained in the second composition examples include those contained in conventional non-aqueous ink compositions for inkjet (sometimes referred to as non-aqueous or oil-based ink compositions) are used.
  • non-aqueous or oil-based ink compositions sometimes referred to as non-aqueous or oil-based ink compositions
  • an organic solvent contained in the non-aqueous adhesive composition described above may be used.
  • the second composition may contain a coloring material, for example, the coloring material that may be contained in the non-aqueous adhesive composition described above can be used.
  • the apparatus according to this embodiment is an apparatus for discharging the non-aqueous adhesive composition from a nozzle onto a substrate.
  • the above non-aqueous adhesive composition becomes adhesive at a predetermined temperature, and the adhesiveness allows solid substances such as powders and foils to be fixed to the substrate. Therefore, the apparatus according to the present embodiment can also produce recorded matter on which a solid matter is fixed.
  • such an apparatus may be an inkjet recording apparatus used for the inkjet method, and the above non-aqueous adhesive composition is ejected by a dispenser method.
  • a dispenser recording device used for the dispenser method may be used.
  • These devices preferably have a heating mechanism.
  • a non-aqueous adhesive composition ejected onto a substrate (recording medium) is dried by controlling the surface temperature of the substrate with a heating mechanism to fix components such as a resin onto the substrate (recording medium). becomes possible. Furthermore, it becomes possible to easily control the temperature at which the resin contained in the non-aqueous adhesive composition has adhesiveness by means of the heating mechanism.
  • the term "recorded matter” includes any adhesive layer formed by ejecting a non-aqueous adhesive composition onto the surface of a substrate (substrate), and is particularly limited. isn't it.
  • the "layer” described later may be formed on the entire surface of the substrate (recording medium), or may be formed on a part of it (patterned). good.
  • a solid layer is formed on the adhesive layer.
  • the material of the solid substance described later it is possible to form a recorded matter having a layer of the solid substance. For example, it is possible to obtain a recorded matter having desired characteristics by using a recorded matter having a layer of a solid material.
  • the substrate is not particularly limited, and may be a non-absorbent substrate such as a resin substrate or metal plate glass, or an absorbent substrate such as paper or fabric, and the receiving layer may be used. It may be a substrate with a surface coating, such as a substrate provided, and various substrates can be used.
  • Non-absorbent base materials include polyester-based resin, polypropylene-based synthetic paper, polyolefin-based resin (polypropylene-based resin, polyethylene-based resin, etc.), acrylic-based resin, styrene-based resin, polycarbonate-based resin, ABS resin, and vinyl chloride-based resin. , resin substrates such as polyimide resin, metals, metal foil-coated paper, glass, synthetic rubber, natural rubber, and the like.
  • absorbent substrates include dry paper, medium-quality paper, high-quality paper, synthetic paper, cotton, synthetic fiber fabric, silk, hemp, fabric, non-woven fabric, leather, and the like.
  • Examples of surface-coated substrates include coated paper, art paper, cast paper, lightweight coated paper, and lightly coated paper.
  • the non-aqueous adhesive composition is a non-aqueous adhesive composition that does not intentionally contain water, it is preferable that the surface is mainly made of a resin.
  • resins include polyvinyl chloride-based polymers, acryl, PET, polycarbonate, PE, and PP. Further, it may be used for a resin base material (so-called resin base material for lamination) on the premise that a film is attached to the recording surface of a recorded matter.
  • the non-aqueous adhesive composition contains "an alkylamide solvent represented by formula (5), a cyclic amide solvent represented by formula (6), and a lactone solvent represented by formula (7)".
  • these organic solvents have particularly high permeability to the polyvinyl chloride polymer, and dry quickly on the resin substrate after ejection.
  • the non-aqueous adhesive composition according to the present embodiment is discharged onto a resin substrate and the metal foil is transferred (fixed) to the resin substrate by the non-aqueous adhesive composition, drying on the resin substrate Since the transfer speed is fast, it is possible to transfer the metal foil particularly cleanly, and the surface shape of the metal foil on the obtained recorded matter is good, and the fineness is also good. Fine fixing is possible.
  • the substrate (recording medium) whose surface is made of a polyvinyl chloride polymer include polyvinyl chloride substrates (films or sheets).
  • the adhesive layer is a layer formed by volatilization of the organic solvent contained in the above-mentioned non-aqueous adhesive composition, and its adhesiveness allows solid substances such as powders and foils to be fixed to the substrate. have a function.
  • This adhesive layer contains a resin derived from the non-aqueous adhesive composition, and the resin contains resin A having a glass transition temperature of -50°C or higher and 40°C or lower. By containing such a resin A, it is possible to fix solid substances such as powders and foils to the base material.
  • the adhesive layer may be formed on the entire surface of the base material, or may be patterned on part of the surface of the base material.
  • the layer of solid matter is a layer formed on the surface of the adhesive layer, and is a layer of solid matter such as powder or foil fixed by the adhesive layer.
  • the solid material is not particularly limited, and may be metal (either a single metal or an alloy, may or may not be a magnetic substance, or may be a semiconductor, etc.), metal compounds. (It may be a metal oxide, metal sulfide, metal nitride, etc., may or may not be a magnetic material, may be a semiconductor, etc.), resin (organic compound polymer or silicone) including, thermoplastic resins, thermosetting resins, elastomers, etc.), glittering materials (pearls, etc.), coloring materials (colored or colorless coloring materials (pigments), phosphors, etc.), paper, glitter , Cloth, hologram, powder such as sand (which may be spherical, flat, or scaly) and foil (including film-like ones.
  • the film thickness is not particularly limited, and a uniform It may be a foil with a film thickness or a foil with a non-uniform film thickness.).
  • the solid object may be surface-treated.
  • the recorded matter according to the present embodiment may contain an ink composition layer.
  • the layer of the ink composition is a layer formed by volatilization of the solvent contained in the ink composition, and is a layer that forms a desired image.
  • the ink composition for example, colored ink compositions such as yellow, magenta, cyan, and black can be used.
  • a recorded matter in which a layer of a solid material and a layer of an ink composition are patterned is a recorded matter on which a color image containing a metal foil is recorded. Note that such a layer of the ink composition is not an essential component in the recorded matter according to the present embodiment.
  • the recorded matter according to the present embodiment may further include a layer having a desired function on the medium (recording medium) or on the upper surface of the entire recorded matter.
  • a layer having a desired function on the medium (recording medium) or on the upper surface of the entire recorded matter For example, an overcoat layer containing at least one of resin and wax may be formed on the entire upper surface of the recorded matter for the purpose of further imparting abrasion resistance and glossiness to the recorded matter.
  • a layer expressing unevenness (matte surface) may be formed on the upper surface of the entire recorded matter by including a filler or changing the film thickness in units of pixels.
  • a weather resistant layer containing an ultraviolet absorber, a light stabilizer, etc., a glittering layer containing a glittering pigment, or the like may be formed on the upper surface of the entire recorded matter. . It should be noted that such other layers are not essential for the recorded matter of the present invention.
  • non-aqueous adhesive composition the recording method, the method for producing the recorded matter, the composition set, and the recorded matter of the present invention have been described above. It is not limited, and can be implemented with appropriate modifications within the scope of the object of the present invention.
  • a non-aqueous adhesive composition for obtaining a recorded matter such that the recorded matter is attached to another object is within the scope of the present invention.
  • a mixture of Monomer 3 and Monomer 4 (total amount of monomers: 59.2 g) was injected under pressure for 6 hours to carry out a copolymerization reaction.
  • the internal pressure of the autoclave reached 0.3 MPa, the residual pressure was released, the autoclave was cooled, and the resin slurry was taken out, filtered and dried to obtain a vinyl chloride copolymer resin.
  • Tables 1 and 2 list the ratio of the monomer (a) constituting each synthetic resin and the value of the glass transition temperature (Tg) obtained by the FOX formula.
  • non-aqueous adhesive composition Each organic solvent, resin, surface modifier (surfactant), dispersant, and pigment are mixed in the proportions shown in the table below.
  • An adhesive composition was made. Specifically, each component was dispersed with zirconia beads using a paint shaker to prepare a non-aqueous adhesive composition. The unit is % by mass.
  • the non-aqueous adhesive compositions of Examples and Comparative Examples were evaluated for foil transferability. Specifically, the non-aqueous adhesive compositions of Examples and Comparative Examples were printed on a recording medium (polyvinyl chloride film with adhesive (IMAGin JT5829R (manufactured by MACtac Co.) was ejected from the nozzle. The resolution at this time was 720 ⁇ 2880 dpi, and the printing pattern was solid at a printing rate of 100%.A separate heater was provided at the bottom of this inkjet printer. , A recording medium was placed thereon, and inkjet ejection was performed while maintaining the substrate surface temperature shown in Tables 2 to 7. The substrate surface temperature was measured using a non-contact radiation thermometer MT7 manufactured by Mother Tool. and measured.
  • a recording medium polyvinyl chloride film with adhesive (IMAGin JT5829R (manufactured by MACtac Co.) was ejected from the nozzle. The resolution at this time was 720
  • the metal foil is superimposed on the non-aqueous adhesive composition ejection surface of the substrate, and after 3 minutes, the metal foil (Murata Gold Leaf Co., Ltd. Greem Foil Standard Metallic A foil No. 3 gold) was superimposed on the non-aqueous adhesive composition discharge surface of the base material, and a pressure of 50 kPa was applied to the metal foil for 3 seconds to transfer the metal foil to the surface of the base material to obtain a recorded matter. Then, the transferability of the metal foil on the surface of the recorded matter was visually confirmed (denoted as "foil transferability" in the table). Evaluation Criteria Evaluation 5: The foil was transferred to the entire printed surface.
  • Rating 4 The foil was transferred to almost the entire printed surface. Evaluation 3: The foil was mostly transferred to the printed surface, but some portions were not transferred. Evaluation 2: Almost no foil was transferred to the printed surface, but some foil transfer was possible. Rating 1: The foil did not transfer at all.
  • a metal foil (Glee foil standard metallic foil No. 3 gold manufactured by Murata Gold Leaf Co., Ltd.) is superimposed on the non-aqueous adhesive composition ejection surface of the substrate, and the metal foil A pressure of 50 kPa was applied to the substrate for 3 seconds to transfer the metal foil to the surface of the substrate.
  • the edge of the metal foil was visually confirmed (indicated as "metal foil definition" in the table).
  • Evaluation Criteria Evaluation 5 Edges and corners of the foil were clean.
  • Evaluation 4 The edges of the foil were clean, but the corners were partially chipped or excess foil was observed.
  • Evaluation 3 The edges of the foil were clean, but the corners were chipped or excess foil was found.
  • Evaluation 2 A part of the edge of the foil was chipped or excessive foil was observed, and many chipped or excessive foil was observed at the corners.
  • Evaluation 1 The edges and corners of the foil were chipped off or excess foil was observed.
  • the metal foil surface shape was evaluated for the non-aqueous adhesive compositions of Examples and Comparative Examples. Specifically, the surface shape of the metal foil was visually checked for the recorded matter (transferred at a substrate surface temperature of 50° C.) obtained in the above (1) foil transferability test, and the metal foil was checked for cracks. It was confirmed whether there was any deviation (indicated as "surface shape" in the table). Evaluation Criteria Evaluation 5: No cracks or deviations are observed in the foil. Evaluation 4: Almost no cracks or deviations can be observed in the foil. Evaluation 3: Some cracks and deviations were observed in the foil. Evaluation 2: Cracks and deviations were observed over the entire foil, but within the practically acceptable range. Evaluation 1: A large number of cracks and deviations were observed throughout the foil.
  • Evaluation 4 Although peeling is slightly observed, it is generally within the allowable range.
  • Evaluation 3 The area of the release surface is less than a quarter of the surface to which the adhesive tape is adhered.
  • Evaluation 2 The area of the release surface is less than half of the surface to which the adhesive tape is adhered.
  • Evaluation 1 The area of the release surface is 1/2 or more of the surface to which the pressure-sensitive adhesive tape is adhered.
  • metal foil abrasion resistance of the non-aqueous adhesive compositions of Examples and Comparative Examples was evaluated. Specifically, the recorded matter obtained in the above (1) foil transferability test (transferred at a substrate surface temperature of 50 ° C.) was left for 12 hours under conditions of a temperature of 25 ° C. and a humidity of 50%. The surface of the foil was rubbed with a dry cloth (Kanakin No. 3) with a load of 500 g, and the presence or absence of peeling of the surface of the metal foil was visually confirmed (indicated as "metal foil abrasion resistance" in the table).
  • Evaluation Criteria Evaluation 5 Neither peeling of the foil surface nor adhesion of the foil to the cloth surface is confirmed even after 50 reciprocating rubbings.
  • Evaluation 4 When rubbed 50 times back and forth, no peeling of the foil surface was observed, but slight adherence of the foil to the cloth surface was confirmed.
  • Evaluation 3 Peeling of the foil surface was observed when the fabric was rubbed back and forth 50 times, and adhesion of the foil to the cloth surface was confirmed.
  • Evaluation 2 When rubbed back and forth 30 times, peeling of the foil surface was observed, and adhesion of the foil to the cloth surface was confirmed.
  • Evaluation 1 When rubbed back and forth 20 times, peeling of the foil surface was observed, and adhesion of the foil to the cloth surface was confirmed.
  • Ejectability was evaluated for the non-aqueous adhesive compositions of Examples and Comparative Examples. Specifically, the non-aqueous adhesive compositions of Examples and Comparative Examples were printed on a recording medium (polyvinyl chloride film with adhesive (IMAGin JT5829R : manufactured by MACtac)), solid and fine lines are printed by continuous printing at a resolution of 720 x 2880 dpi at a substrate surface temperature of 50 ° C., and the presence or absence of dot missing, flight bending, and scattering of the non-aqueous adhesive composition is visually checked. Observation was made and the number of occurrences was counted (denoted as "dischargeability" in the table).
  • a recording medium polyvinyl chloride film with adhesive (IMAGin JT5829R : manufactured by MACtac)
  • solid and fine lines are printed by continuous printing at a resolution of 720 x 2880 dpi at a substrate surface temperature of 50 ° C.
  • Evaluation Criteria Evaluation 5 Fine lines are correctly reproduced. Evaluation 4: Fine lines are generally correctly reproduced. Evaluation 3: A slight bend is observed in the thin wire. Evaluation 2: The landing position is displaced and bending is observed. Evaluation 1: The displacement of the landing position is severe, and fine lines cannot be reproduced.
  • a non-aqueous adhesive composition containing a resin A having a glass transition temperature of ⁇ 50° C. or higher and 40° C. or lower can be inkjet-discharged from a nozzle onto a substrate, and a metal foil can be transferred to the substrate.
  • the non-aqueous adhesive composition of the present invention is not limited to the inkjet method, it can be discharged by a method of discharging onto a substrate from a nozzle, and is not limited to the transfer of a metal foil. can be fixed to the substrate.
  • the content of the resin A of Examples 1 to 5 contained in the range of 50% by mass or more in the total amount of the resin Compared with the non-aqueous adhesive composition of Example 6, the non-aqueous adhesive composition had good transfer film definition.
  • the resin content was 5% by mass or more of the total amount of the non-aqueous adhesive composition Examples containing The non-aqueous adhesive compositions of 1 and 18 to 21 are superior to the non-aqueous adhesive composition of Example 17 in terms of foil transferability, transfer film definition, transfer film surface shape, transfer film peeling resistance, transfer The abrasion resistance of the film was good.
  • the non-aqueous adhesive compositions of Examples 1 and 17 to 20 containing the resin content in the range of 20.0% by mass or less in the total amount of the non-aqueous adhesive composition are the non-aqueous adhesive compositions of Example 21.
  • the jettability was also good compared to the composition.
  • ⁇ -butyrolactone contained in the non-aqueous adhesive composition of Example 1 was used as a solvent represented by formula (5) (alkylamide solvent), a solvent represented by formula (6) (cyclic amide solvent ), in the non-aqueous adhesive compositions of Examples 33 to 40 in which the solvent (lactone-based solvent other than ⁇ -butyrolactone) represented by (7) was changed, as in the non-aqueous adhesive composition of Example 1. It was a composition exhibiting the effects of the present invention.
  • the non-aqueous adhesive compositions of Comparative Examples 1 to 5 which do not contain the resin A having a glass transition temperature of ⁇ 50° C. or more and 40° C. or less, could not transfer the foil at all in the foil transfer test. It is not an effective non-aqueous adhesive composition. In the foil transfer test, the non-aqueous adhesive compositions of Comparative Examples 1 to 5 could not be transferred at all, so other tests other than "dischargeability" were not evaluated.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une nouvelle composition adhésive qui peut être éjectée sur une matière de base à partir d'une buse et qui permet de fixer une matière solide telle qu'une poudre et une feuille sur la matière de base.　La présente invention concerne une composition adhésive non aqueuse qui doit être éjectée à partir d'une buse et qui contient un solvant organique et une résine. Par rapport à cette composition adhésive non aqueuse, la résine contient une résine A qui présente une température de transition vitreuse de -50 °C à 40 °C.
PCT/JP2022/036178 2021-09-30 2022-09-28 Composition adhésive non aqueuse, procédé d'impression, procédé destiné á la production de matière imprimée, jeu de compositions, dispositif et matière imprimée WO2023054473A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169492A (ja) * 2005-12-22 2007-07-05 Seiko Epson Corp インクジェット記録用油性インク組成物
WO2016013644A1 (fr) * 2014-07-25 2016-01-28 コニカミノルタ株式会社 Procédé de formation d'image de feuille
JP2016182675A (ja) * 2015-03-25 2016-10-20 帝人コードレ株式会社 金属薄膜加飾シート状物およびその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169492A (ja) * 2005-12-22 2007-07-05 Seiko Epson Corp インクジェット記録用油性インク組成物
WO2016013644A1 (fr) * 2014-07-25 2016-01-28 コニカミノルタ株式会社 Procédé de formation d'image de feuille
JP2016182675A (ja) * 2015-03-25 2016-10-20 帝人コードレ株式会社 金属薄膜加飾シート状物およびその製造方法

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