[go: up one dir, main page]

WO2025018039A1 - Article imprimé et procédé de production d'un matériau de base recyclé - Google Patents

Article imprimé et procédé de production d'un matériau de base recyclé Download PDF

Info

Publication number
WO2025018039A1
WO2025018039A1 PCT/JP2024/019911 JP2024019911W WO2025018039A1 WO 2025018039 A1 WO2025018039 A1 WO 2025018039A1 JP 2024019911 W JP2024019911 W JP 2024019911W WO 2025018039 A1 WO2025018039 A1 WO 2025018039A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
mgkoh
resin
pigment
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/019911
Other languages
English (en)
Japanese (ja)
Inventor
圭佑 若原
朋美 浅見
貴之 久保田
裕季 小林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2024560305A priority Critical patent/JP7683833B1/ja
Publication of WO2025018039A1 publication Critical patent/WO2025018039A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • 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
    • 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
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D9/00—Chemical paint or ink removers
    • C09D9/04—Chemical paint or ink removers with surface-active agents

Definitions

  • the present invention relates to a printed material having a coating that can be detached from a substrate, and a method for producing a recycled substrate from the printed material.
  • Patent Document 1 a method is disclosed in which a coating containing a styrene-acrylic acid resin, a phenolic resin, or a styrene-maleic acid resin as a vehicle printed on a heat-shrinkable PET film is removed with alkaline water.
  • Patent Document 2 a coating layer containing a styrene-maleic acid resin, a rosin-maleic acid resin, or an acrylic acid copolymer resin is formed on a heat-shrinkable PET film by arranging the coating layer between the coating layers, and the coating layer is removed with alkaline water
  • the problem that the present invention aims to solve is to provide a method for producing recycled substrates that can suppress coloration of the alkaline solution after detachment of a coating from a plastic substrate by treatment with an alkaline solution, and to provide a printed material having a detachable coating that can be suitably used in the method for producing recycled substrates.
  • the inventors discovered that the above problems could be solved by arranging a removable primer layer between the substrate and the ink layer as a coating that detaches from the substrate when treated with an alkaline solution, and then arranging a varnish layer on top of the ink layer, resulting in a printed matter in which the substrate, primer layer, ink layer, and varnish layer are layered in that order, thus completing the present invention.
  • the present invention includes the following aspects.
  • a substrate a primer layer that can be removed from the substrate by treatment with an alkaline solution; an ink layer containing a colorant and at least one resin selected from the group consisting of an acrylic resin, a urethane resin, a polyamide resin, a rosin resin, and a polyester resin;
  • the varnish layer contains a resin selected from the group consisting of urethane resins, cellulose derivatives, and polyester resins.
  • the varnish layer is (i) containing at least a urethane resin and a cellulose derivative, or (ii) containing at least a urethane resin, a cellulose derivative, and a polyisocyanate;
  • a method for producing a recycled substrate comprising treating the printed matter according to [1] with an alkaline solution to remove the primer layer from the substrate, thereby obtaining a recycled substrate.
  • the method for producing a recycled substrate according to [6] wherein the alkaline solution has a pH of 9 or more and contains a nonionic surfactant.
  • the present invention provides a method for producing recycled substrates that can suppress coloration of the alkaline solution after detachment of a coating from a plastic substrate by treatment with an alkaline solution, and a printed material having a removable coating that can be suitably used in the method for producing recycled substrates.
  • the substrate is preferably a plastic substrate, and examples thereof include films and laminates made of polyamide resins such as nylon 6, nylon 66, and nylon 46; polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate; biodegradable resins such as polyhydroxycarboxylic acids such as polylactic acid, aliphatic polyester resins such as poly(ethylene succinate) and poly(butylene succinate); thermoplastic resins such as polyolefin resins such as polypropylene and polyethylene, polyimide resins, polyarylate resins, and mixtures thereof.
  • polyamide resins such as nylon 6, nylon 66, and nylon 46
  • polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene
  • films and laminates made of polyethylene terephthalate, polyester, polyamide, polyethylene, and polypropylene can be preferably used, and polyethylene terephthalate, polypropylene, or polyethylene are more preferable when the releasability of the composition according to the present invention is considered.
  • These substrate films may be unstretched or stretched films, and the manufacturing method thereof is not limited.
  • the thickness of the substrate film is also not particularly limited, but it is usually sufficient to be in the range of 1 to 500 ⁇ m.
  • the printing surface of the substrate is preferably surface-modified by corona discharge treatment or chemical treatment, and may be vapor-deposited with silica, alumina, etc.
  • the ink layer is formed using a composition for forming an ink layer.
  • the composition for forming the ink layer contains a colorant.
  • the composition for forming the ink layer further contains at least one type of resin A selected from the group consisting of acrylic resins, urethane resins, polyamide resins, rosin resins, and polyester resins.
  • the composition for forming the ink layer may contain other resins in addition to the above-mentioned resin A.
  • the composition for forming the ink layer may contain an organic solvent, and may also contain other components such as auxiliaries and acidic additives. The components of the ink layer forming composition will be described below.
  • the colorant component may be a color dye and/or a color pigment, and among these, a color pigment (hereinafter, simply referred to as a pigment) is preferred.
  • the pigment used in the present invention may be an inorganic pigment or an organic pigment that is used in general inks, paints, recording materials, etc. From the viewpoint of effectively suppressing coloring of the alkaline solution after desorption, an organic pigment is preferred.
  • Organic pigments include soluble azo pigments, insoluble azo pigments, azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthraquinone pigments, anthanthrone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, flavanthrone pigments, diketopyrrolopyrrole pigments, isoindoline pigments, indanthrone pigments, and carbon black pigments.
  • Examples include carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophthalic yellow, chromophthalic red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigments. Both non-acid-treated pigments and acid-treated pigments can be used. Specific examples of preferred organic pigments are listed below.
  • indigo pigments examples include C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:5, C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 17:1, C.I. Pigment Blue 22, C.I. Pigment Blue 24:1, C.I. Pigment Blue 25, C.I. Pigment Blue 26, C.I. Pigment Blue 60, C.I. Pigment Blue 61, C.I. Pigment Blue 62, C.I. Pigment Blue 63, C.I. Pigment Blue 64, C.I. Pigment Blue 75, C.I. Pigment Blue 79, C.I. Pigment Blue 80, etc.
  • green pigments examples include C.I. Pigment Green 1, C.I. Pigment Green 4, C.I. Pigment Green 7, C.I. Pigment Green 8, C.I. Pigment Green 10, and C.I. Pigment Green 36.
  • Red pigments include, for example, C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 20, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 31, C.I.
  • Pigment Red 32 C.I. Pigment Red 38, C.I. Pigment Red 41, C.I. Pigment Red 43, C.I. Pigment Red 46, C.I. Pigment Red 48, C.I. Pigment Red 48:1, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 48:4, C.I. Pigment Red 48:5, C.I. Pigment Red 48:6, C.I. Pigment Red 49, C.I. Pigment Red 49:1, C.I. C.I. Pigment Red 49:2, C.I. Pigment Red 49:3, C.I. Pigment Red 52, C.I. Pigment Red 52:1, C.I. Pigment Red 52:2, C.I.
  • Pigment Red 53 C.I. Pigment Red 53:1, C.I. Pigment Red 53:2, C.I. Pigment Red 53:3, C.I. Pigment Red 54, C.I. Pigment Red 57, C.I. Pigment Red 57:1, C.I. Pigment Red 58, C.I. Pigment Red 58:1, C.I. Pigment Red 58:2, C.I. Pigment Red 58:3, C.I. Pigment Red 58:4, C.I. C.I. Pigment Red 60:1, C.I. Pigment Red 63, C.I. Pigment Red 63:1, C.I. Pigment Red 63:2, C.I. Pigment Red 63:3, C.I. Pigment Red 64:1, C.I.
  • purple pigments examples include C.I. Pigment Violet 1, C.I. Pigment Violet 2, C.I. Pigment Violet 3, C.I. Pigment Violet 3:1, C.I. Pigment Violet 3:3, C.I. Pigment Violet 5:1, C.I. Pigment Violet 13, C.I. Pigment Violet 19 ( ⁇ type, ⁇ type), C.I. Pigment Violet 23, C.I. Pigment Violet 25, C.I. Pigment Violet 27, C.I. Pigment Violet 29, C.I. Pigment Violet 31, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 37, C.I. Pigment Violet 38, C.I. Pigment Violet 42, C.I. Pigment Violet 50, etc.
  • yellow pigments examples include C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, Pigment Yellow 17, C.I. Pigment Yellow 24, C.I. Pigment Yellow 42, C.I. Pigment Yellow 55, C.I. Pigment Yellow 62, C.I. Pigment Yellow 65, C.I. Pigment Yellow 74, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I.
  • Examples of the pigments include C.I. Pigment Yellow 174, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, and C.I. Pigment Yellow 213.
  • orange pigments examples include C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 16, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 37, C.I. Pigment Orange 38, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Range 55, C.I. Pigment Orange 59, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 71, and C.I. Pigment Orange 74.
  • brown pigments examples include C.I. Pigment Brown 23, C.I. Pigment Brown 25, and C.I. Pigment Brown 26.
  • preferred pigments include C.I. Pigment Black 7 as a black pigment, C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6 as an indigo pigment, C.I. Pigment Green 7 as a green pigment, and C.I. Pigment Red 57:1, C.I. Pigment Red 48:1, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 146, C.I.
  • the pigments include C.I. Pigment Red 122, C.I. Pigment Red 178, C.I. Pigment Red 149, C.I. Pigment Red 144, C.I. Pigment Red 166, purple pigments include C.I. Pigment Violet 23 and C.I. Pigment Violet 37, yellow pigments include C.I. Pigment Yellow 83, C.I. Pigment Yellow 14, C.I. Pigment Yellow 180, and C.I. Pigment Yellow 139, and orange pigments include C.I. Pigment Orange 38, C.I. Pigment Orange 13, C.I. Pigment Orange 34, and C.I. Pigment Orange 64. It is preferable to use at least one or more selected from these groups.
  • Inorganic pigments include carbon black, titanium oxide, red ocher, aluminum, mica, zinc oxide, barium sulfate, calcium carbonate, and silica. Also usable is a lustrous pigment (Metashine; Nippon Sheet Glass Co., Ltd.) made of glass flakes or clumped flakes as a base material coated with a metal or metal oxide. From the standpoint of cost and coloring power, it is preferable to use carbon black for black ink, titanium oxide for white ink, aluminum for gold and silver ink, and mica for pearl ink.
  • the total pigment content is not particularly limited, but for example, in an ink layer forming composition, from the viewpoint of ensuring the coloring power of the composition, the pigment content is preferably 1 to 60 parts by mass, and more preferably 5 to 40 parts by mass, per 100 parts by mass of the total amount of the composition.
  • the total white pigment content may be 15 to 60 parts by mass, or may be 20 to 40 parts by mass, per 100 parts by mass of the total amount of the composition.
  • the total colored organic pigment content may be 1 to 30 parts by mass, or may be 5 to 25 parts by mass, per 100 parts by mass of the total amount of the pigment composition. Any combination of these upper and lower limits may be used.
  • the composition for forming the ink layer contains at least one type of resin A selected from the group consisting of acrylic resins, urethane resins, polyamide resins, rosin resins, and polyester resins.
  • the composition for forming the ink layer may contain a resin other than the resin A.
  • it may contain other resins such as a cellulose-based resin, a ketone resin, a chlorinated polypropylene resin, an ethylene-vinyl acetate copolymer resin, a vinyl acetate resin, an alkyd resin, a polyvinyl chloride resin, a cyclized rubber, a chlorinated rubber, a butyral resin, and a petroleum resin. These may be used in appropriate combination.
  • the number average molecular weight of the urethane resin is preferably within the range of 15,000 to 100,000. If the number average molecular weight of the urethane resin is less than 15,000, the blocking resistance, chemical resistance, etc. of the ink layer forming composition tend to be low, whereas if it exceeds 100,000, the viscosity of the composition tends to be high, making it difficult to obtain a desired print density.
  • the urethane resin contained in the ink layer forming composition preferably uses polyester polyol and/or polyether polyol as its reaction raw material.
  • the number average molecular weight of the polyester polyol is a value measured by gel permeation chromatography (GPC) under the following conditions.
  • Measurement device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used, connected in series. "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mm I.D.
  • polyester polyols for example, those obtained by a known esterification reaction between a compound having two or more hydroxyl groups and a polybasic acid can be used.
  • the above compounds having two or more hydroxyl groups are used as chain extenders, and examples of such compounds include glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol; 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol,
  • polybasic acid examples include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, and anhydrides of these acids. These polybasic acids may be used alone or in combination of two or more.
  • the polyether polyol preferably has a number average molecular weight of 100 to 4000.
  • the polyether polyol include polyether polyols which are polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc.
  • known general-purpose polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used, and among these, polyethylene glycol is preferred.
  • the number average molecular weight of the polyether polyol is less than 100, the urethane resin film tends to become hard and the adhesion to the polyester film is likely to decrease. If the number average molecular weight is more than 4000, the urethane resin film tends to become brittle and the blocking resistance of the film is likely to decrease.
  • the number average molecular weight of the polyether polyol can be determined by measuring it under the same conditions using gel permeation chromatography (GPC) as for the polyester polyols described above.
  • Diisocyanate compounds used in the urethane resin in the composition for forming the ink layer include various known aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, etc. that are commonly used in the production of urethane resins.
  • Chain extenders used in the urethane resin in the ink layer forming composition include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, etc., as well as amines having a hydroxyl group in the molecule such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. These chain extenders can be used alone or in combination of two or more.
  • the amine value of the urethane resin used in the ink layer forming composition is preferably 10.0 mgKOH/g or less. If the amine value exceeds 10.0 mgKOH/g, blocking resistance tends to deteriorate, and the stability of the second liquid after the addition of the curing agent decreases. From the viewpoint of maintaining good blocking resistance and second liquid stability while maintaining plate fogging resistance, adhesion, and extrusion lamination strength, a range of 1.0 to 5.0 mgKOH/g is more preferable, and a range of 1.0 to 3.5 mgKOH/g is even more preferable.
  • the acrylic resin can be obtained by copolymerizing various (meth)acrylate monomers and, if necessary, other polymerizable unsaturated group-containing compounds.
  • the monomer constituting the acrylic resin is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-pentafluoropropyl (meth)acrylate, perflu
  • (Meth)acrylic monomers such as ricidyl (meth)acrylate, allyl glycidyl ether, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, (meth)acrylamide, N-monoalkyl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N-methylol (meth)acrylamide, N-isopropoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide, 2-aziridinylethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, acrolein, diacetone (meth)acrylamide, and acetoacetoxyethyl (meth)acrylate can be used.
  • the polymerizable unsaturated group-containing compound may also be vinyl monomers such as vinyl acetate, vinyl propionate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, (meth)acrylonitrile, styrene, ⁇ -methylstyrene, divinylstyrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, and N-vinylpyrrolidone. These may be used alone or in combination of two or more.
  • vinyl monomers such as vinyl acetate, vinyl propionate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, (meth)acrylonitrile, styrene, ⁇ -methylstyrene, divinylstyrene, isoprene, chlor
  • the number average molecular weight of the acrylic resin is not particularly limited, but is preferably 3,000 to 50,000, and more preferably 10,000 to 30,000.
  • the polyamide resin can be obtained by reacting a polycarboxylic acid compound with a polyamine or a polyisocyanate compound.
  • the polycarboxylic acid compound include succinic acid, maleic acid, fumaric acid, itaconic acid, azelaic acid, mesaconic acid, citraconic acid, sebacic acid, glutaconic acid, adipic acid, malonic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, nadic acid, methylnadic acid, octyl succinic acid, and anhydrides of these acids, polymerized fatty acids such as linoleic acid dimers and trimers, dodecanedioic acid, C21 dibasic acid, and dimer acids (polymerized fatty acids obtained by polymerizing unsaturated fatty acids such as oleic acid and linoleic acid), etc.
  • aliphatic polycarboxylic acids having 7 to 20 carbon atoms such as 1,2,4-butanetricarboxylic acid and 1,2,5-hexanetricarboxylic acid
  • alicyclic polycarboxylic acids having 9 to 20 carbon atoms such as 1,2,4-cyclohexanetricarboxylic acid
  • aromatic polycarboxylic acids having 9 to 20 carbon atoms such as 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid and pyromellitic acid, as well as trivalent or higher polycarboxylic acids, such as their anhydrides and lower alkyl (methyl, butyl, etc.) esters.
  • Polyamines used to obtain polyamide resins include diamines such as ethylenediamine, propylenediamine, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminodecane, and diaminododecane; and amines with three or more valences such as diethylenetriamine and triethylenetetramine.
  • the number average molecular weight of the polyamide resin is not particularly limited, but is preferably 5,000 to 20,000, and more preferably 500 to 10,000.
  • the rosin resin may have 20% by mass or more of a rosin-derived structure, and preferably has a softening point (ring and ball method) of 30°C to 180°C, more preferably 50 to 170°C.
  • Suitable examples of the rosin resin include polymerized rosin resin, rosin-modified maleic acid resin, and rosin-modified fumaric acid resin.
  • the acid value of the rosin resin is preferably 50 to 350 (mgKOH/g).
  • Suitable examples of the rosin resin include Aradigm R-95 and Malquid No. 32 manufactured by Arakawa Chemical Industries, Ltd.
  • the weight average molecular weight of the rosin-modified maleic acid resin or rosin-modified fumaric acid resin is preferably 500 or more, more preferably 700 or more, and even more preferably 1000 or more.
  • the weight average molecular weight of the rosin modified maleic acid resin or rosin modified fumaric acid resin is preferably 50,000 or less, more preferably 30,000 or less, more preferably 10,000 or less, more preferably 5,000 or less, and more preferably 2,000 or less.
  • the weight average molecular weight of the rosin modified maleic acid resin or rosin modified fumaric acid resin is preferably 500 to 50,000, more preferably 700 to 520,000, more preferably 1,000 to 10,000, and even more preferably 1,000 to 5,000. By keeping it within the above range, printability can be improved.
  • the polyester resin can be any of various known polyester resins.
  • the polyester resin can be obtained by reacting glycol with a dibasic acid or its derivative as an essential component.
  • the polyester resin can be obtained by using an ester-forming derivative such as a dibasic acid anhydride or a dibasic acid lower alkyl ester instead of the dibasic acid, not only by polycondensation reaction but also by addition reaction or transesterification reaction.
  • polyester resins examples include aliphatic polyester polyols obtained by reacting an aliphatic glycol such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, decanediol, or cyclohexanedimethanol with an aliphatic dibasic acid such as succinic acid, adipic acid, sebacic acid, fumaric acid, suberic acid, azelaic acid, 1,10-decamethylenedicarboxylic acid, or cyclohexanedicarboxylic acid as an essential raw material component; and aromatic polyester polyols obtained by reacting an aliphatic glycol such as ethylene glycol, propylene glycol, or butanediol with an aromatic dibasic acid such as terephthalic acid, isophthalic acid, or naphthalenedicarboxylic acid as an essential raw material component.
  • the content of the resin in the composition for forming the ink layer is not particularly limited, but is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more, based on 100 parts by mass of the total amount of the composition.
  • the total content is preferably 60 parts by mass or less, and more preferably 55 parts by mass or less.
  • the preferable range of the content is the total amount of those resins contained.
  • the composition for forming the ink layer may contain an organic solvent.
  • the organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbon organic solvents such as toluene, xylene, Solvesso #100, Solvesso #150, etc.; aliphatic hydrocarbon organic solvents such as hexane, methylcyclohexane, heptane, octane, decane, etc.; and various ester-based organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, etc.
  • water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, butanol, isopropyl alcohol, and normal propyl alcohol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; and glycol ethers such as ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl
  • the content of the organic solvent is not particularly limited, but is preferably 20% by mass or more, and more preferably 30% by mass or more, based on 100 parts by mass of the total amount of the composition for forming the ink layer. It is also preferably 70% by mass or less, more preferably 65% by mass or less, more preferably 60% by mass or less, and more preferably 55% by mass or less.
  • composition for forming the ink layer may further contain other components such as auxiliaries and acidic additives, if necessary.
  • waxes such as paraffin wax, polyethylene wax, carnauba wax, etc. for imparting abrasion resistance, slipperiness, etc.
  • fatty acid amide compounds such as oleic acid amide, stearic acid amide, erucic acid amide, etc.
  • silicone-based and non-silicone-based defoamers for suppressing foaming during printing
  • dispersants etc.
  • dispersants nonionic dispersants are preferred.
  • the acid value of the dispersant is preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, and even more preferably 20 mgKOH/g or less. It may also be, for example, 1 mgKOH/g or more, or even 3 mgKOH/g or more.
  • the content of the dispersant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, more preferably 75 parts by mass or less, more preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and more preferably 60 parts by mass or less.
  • the acidic additive for example, an organic acid or a resin having an acidic group can be used.
  • the acid value of the acidic additive is preferably 1 mgKOH/g or more, more preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, and more preferably 50 mgKOH/g or more.
  • the acid value is preferably 900 mgKOH/g or less, more preferably 850 mgKOH/g or less, more preferably 800 mgKOH/g or less, more preferably 750 mgKOH/g or less, more preferably 700 mgKOH/g or less, more preferably 650 mgKOH/g or less, more preferably 600 mgKOH/g or less, and more preferably 550 mgKOH/g or less.
  • the acid value is preferably in the range of 1 to 900 mgKOH/g, more preferably 3 to 850 mgKOH/g, more preferably 5 to 800 mgKOH/g, more preferably 10 to 750 mgKOH/g, more preferably 20 to 700 mgKOH/g, more preferably 30 to 650 mgKOH/g, more preferably 40 to 600 mgKOH/g, and more preferably 50 to 550 mgKOH/g.
  • 50 to 900 mgKOH/g is preferred, 65 to 900 mgKOH/g is preferred, 80 to 900 mgKOH/g is preferred, 100 to 900 mgKOH/g is more preferred, 200 to 900 mgKOH/g is more preferred, 300 to 900 mgKOH/g is more preferred, 400 to 900 mgKOH/g is more preferred, 500 to 900 mgKOH/g is more preferred, and 550 to 900 mgKOH/g is more preferred.
  • 1 to 550 mgKOH/g is preferred, 1 to 500 mgKOH/g is more preferred, 1 to 400 mgKOH/g is more preferred, 1 to 300 mgKOH/g is more preferred, and 1 to 200 mgKOH/g is more preferred.
  • the molecular weight of the acidic additive is preferably 50 or more, more preferably 60 or more, more preferably 80 or more, more preferably 100 or more, more preferably 150 or more, more preferably 200 or more, more preferably 250 or more, and more preferably 300 or more. Also, it is preferably 2000 or less, more preferably 1800 or less, more preferably 1500 or less, more preferably 1200 or less, and more preferably 1000 or less.
  • the molecular weight range is preferably 50 to 2000, more preferably 50 to 1800, more preferably 50 to 1500, more preferably 60 to 1500, more preferably 80 to 1500, more preferably 100 to 1500, more preferably 150 to 1500, more preferably 200 to 1500, more preferably 250 to 1500, more preferably 300 to 1500, more preferably 300 to 1200, and more preferably 300 to 1000.
  • the above organic acid refers to a low molecular weight organic compound having an acidic group.
  • Preferred examples of low molecular weight compounds having an acidic group include saturated fatty acids, unsaturated fatty acids, hydroxy acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, oxocarboxylic acids, and carboxylic acid derivatives, and these can be used singly or in combination.
  • saturated fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, decanoic acid, undecanoic acid, and dodecanoic acid.
  • unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid.
  • hydroxy acids include lactic acid, malic acid, and citric acid.
  • aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid
  • dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, azelaic acid, etc.
  • tricarboxylic acids include aconitic acid and trimer acid, etc.
  • oxocarboxylic acids include pyruvic acid and oxaloacetic acid, etc.
  • carboxylic acid derivatives include amino acids and nitrocarboxylic acids, and these can be used singly or in combination.
  • citric acid, butyric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid, arachidic acid, sebacic acid, etc. are compatible with the so-called Swiss Ordinance, and it is preferable to use substances that comply with various regulations.
  • the acid value of the above organic acid is preferably 1 mgKOH/g or more, more preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more, more preferably 60 mgKOH/g or more, more preferably 70 mgKOH/g or more, more preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, and particularly preferably 100 mgKOH/g or more.
  • the acid value is preferably 900 mgKOH/g or less, more preferably 850 mgKOH/g or less, more preferably 800 mgKOH/g or less, more preferably 750 mgKOH/g or less, more preferably 700 mgKOH/g or less, more preferably 650 mgKOH/g or less, more preferably 600 mgKOH/g or less, and more preferably 550 mgKOH/g or less.
  • 100 mgKOH/g or more is preferable, 150 mgKOH/g or more is more preferable, 200 mgKOH/g or more is more preferable, 250 mgKOH/g or more is more preferable, 300 mgKOH/g or more is more preferable, 350 mgKOH/g or more is more preferable, 400 mgKOH/g or more is more preferable, 450 mgKOH/g or more is more preferable, 500 mgKOH/g or more is more preferable, and 550 mgKOH/g or more is more preferable.
  • 550 mgKOH/g or less is preferable, 500 mgKOH/g or less is more preferable, 400 mgKOH/g or less is more preferable, 300 mgKOH/g or less is more preferable, and 200 mgKOH/g or less is more preferable.
  • the acid value is preferably in the range of 1 to 900 mgKOH/g, more preferably 3 to 850 mgKOH/g, more preferably 10 to 800 mgKOH/g, more preferably 20 to 750 mgKOH/g, more preferably 30 to 700 mgKOH/g, more preferably 50 to 650 mgKOH/g, more preferably 80 to 600 mgKOH/g, and more preferably 100 to 550 mgKOH/g.
  • 100 to 900 mgKOH/g is preferred, 150 to 900 mgKOH/g is more preferred, 200 to 900 mgKOH/g is more preferred, 250 to 900 mgKOH/g is more preferred, 300 to 900 mgKOH/g is more preferred, 350 to 900 mgKOH/g is more preferred, 400 to 900 mgKOH/g is more preferred, 450 to 900 mgKOH/g is more preferred, 500 to 900 mgKOH/g is more preferred, and 550 to 900 mgKOH/g is more preferred.
  • 1 to 550 mgKOH/g is preferred, 1 to 500 mgKOH/g is more preferred, 1 to 400 mgKOH/g is more preferred, 1 to 300 mgKOH/g is more preferred, and 1 to 200 mgKOH/g is more preferred.
  • the number of carbon atoms in the organic acid is preferably 3 or more, more preferably 4 or more, more preferably 5 or more, more preferably 6 or more, more preferably 7 or more, and more preferably 8 or more.
  • the number of carbon atoms in the organic acid is preferably 20 or less, more preferably 18 or less, and more preferably 16 or less.
  • the range of the number of carbon atoms in the organic acid is preferably 3 to 20, more preferably 3 to 18, more preferably 4 to 18, more preferably 5 to 18, more preferably 6 to 18, more preferably 6 to 16, more preferably 7 to 16, and more preferably 8 to 16.
  • the solubility of the organic acid in 100 g of water at 25°C is preferably less than 2 g, more preferably less than 1.8 g, even more preferably less than 1.5 g, and particularly preferably less than 1.2 g.
  • the above-mentioned resins having acidic groups include, for example, resins having an acid value such as cellulose resins, ketone resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubbers, chlorinated rubbers, butyral resins, and petroleum resins; radical copolymers such as styrene-(meth)acrylic resins, styrene-(anhydride)maleic acid resins, and terpene-(anhydride)maleic acid resins, which are copolymerized with polymerizable monomers having acidic groups, such as polymerizable monomers having carboxyl groups, such as itaconic acid, maleic acid, fumaric acid, cinnamic acid, or their acid anhydrides; polymerizable monomers having sulfonic acid groups, such as sulfonated
  • the acid value of the resin having the acidic group is preferably 1 mgKOH/g or more, more preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, and particularly preferably 50 mgKOH/g or more.
  • the acid value is preferably 300 mgKOH/g or less, more preferably 280 mgKOH/g or less, more preferably 260 mgKOH/g or less, more preferably 240 mgKOH/g or less, more preferably 220 mgKOH/g or less, and more preferably 200 mgKOH/g or less.
  • the acid value is preferably in the range of 1 to 300 mgKOH/g, more preferably 3 to 300 mgKOH/g, more preferably 5 to 280 mgKOH/g, more preferably 10 to 260 mgKOH/g, more preferably 20 to 240 mgKOH/g, more preferably 30 to 220 mgKOH/g, more preferably 40 to 200 mgKOH/g, and more preferably 50 to 200 mgKOH/g.
  • the weight average molecular weight of the resin having an acidic group is preferably 500 or more, more preferably 700 or more, and even more preferably 1000 or more.
  • the weight average molecular weight of the resin having an acidic group is preferably 100,000 or less, more preferably 70,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.
  • the weight average molecular weight range of the resin having an acidic group is preferably 500 to 100,000, more preferably 700 to 30,000, more preferably 1,000 to 50,000, and even more preferably 1,000 to 30,000.
  • printability can be improved.
  • the content of the acidic additive as solids is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more, preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and more preferably 50 parts by mass or less, based on 100 parts by mass of the total amount of the ink layer forming composition, from the viewpoints of resolubility of the ink layer forming composition, suppression of blocking of the printed matter, improvement of print density, and adhesion to other layers.
  • the content of the acidic additive as solids is preferably in the range of 0.1 to 60 parts by mass, more preferably 0.5 to 55 parts by mass, more preferably 1 to 50 parts by mass, more preferably 1.5 to 45 parts by mass, and more preferably 2 to 40 parts by mass.
  • the content of the organic acid as a solid content is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more, preferably 20 parts by mass or less, more preferably 18 parts by mass or less, more preferably 16 parts by mass or less, more preferably 14 parts by mass or less, more preferably 12 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the total amount of the composition for forming the ink layer.
  • the content of the organic acid as a solid content is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 18 parts by mass, more preferably 0.3 to 16 parts by mass, more preferably 0.5 to 14 parts by mass, more preferably 1 to 12 parts by mass, more preferably 1.5 to 10 parts by mass, and more preferably 2 to 10 parts by mass.
  • the content of the resin having an acidic group as a solid content is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more, preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and more preferably 50 parts by mass or less, relative to 100 parts by mass of the total amount of the composition for forming the ink layer.
  • the content of the acidic additive as a solid content is preferably in the range of 0.1 to 60 parts by mass, more preferably 0.5 to 55 parts by mass, more preferably 1 to 50 parts by mass, more preferably 1.5 to 45 parts by mass, and more preferably 2 to 40 parts by mass.
  • water, wetting agents, adhesive aids, leveling agents, antistatic agents, viscosity modifiers, metal chelates, trapping agents, antiblocking agents, isocyanate-based hardeners, and silane coupling agents can also be used as needed.
  • the viscosity of the ink layer forming composition is preferably 6 seconds or more, more preferably 10 seconds or more, and even more preferably 13 seconds or more. It is also preferably 25 seconds or less, more preferably 20 seconds or less, and even more preferably 18 seconds or less.
  • the surface tension of the ink layer forming composition is preferably 25 mN/m or more, more preferably 33 mN/m or more. Also, it is preferably 50 mN/m or less, more preferably 43 mN/m or less.
  • the primer layer is a coating that can be removed from the substrate by treatment with an alkaline solution.
  • the primer layer may be any known layer that can be detached from the substrate by treatment with an alkaline solution, and may be dissolved or swelled in the alkaline solution by hydrolysis, etc., to be detached from the substrate.
  • the type of primer layer-forming composition that forms the primer layer is not particularly limited, but for example, a composition containing a urethane resin or polyvinyl alcohol is preferred, or a composition containing a resin having an acidic group is also preferred.
  • the resin having an acidic group examples include resins having an acid value, such as polyurethane resins having an acid value, rosin-modified maleic acid resins and rosin-modified fumaric acid resins; radical copolymer resins such as (meth)acrylic resins, styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins and terpene-maleic acid (anhydride) resins, which are copolymerized with polymerizable monomers having an acidic group, such as polymerizable monomers having a carboxyl group, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, or acid anhydrides thereof, polymerizable monomers having a sulfonic acid group, such as sulfonated styrene, and polymerizable monomers having a sulfonamide group, such as vinylbenzen
  • a composition containing a urethane resin or polyvinyl alcohol is more preferred, and a composition containing a urethane resin or polyvinyl alcohol having an acid value of 8 to 45 mgKOH/g is more preferred.
  • the composition for forming a primer layer may contain, in addition to the above-mentioned resin, a solvent such as an organic solvent or an aqueous solvent, an additive, etc.
  • a solvent such as an organic solvent or an aqueous solvent
  • an additive etc.
  • the additive include the same auxiliary agent and acidic additive that can be added to the composition for forming an ink layer described above.
  • a first embodiment of the primer layer forming composition which is an aqueous urethane resin composition
  • a second embodiment of the primer layer forming composition which contains polyvinyl alcohol. The primer layer forming compositions of these embodiments will be described below.
  • composition for forming a primer layer comprising an aqueous urethane resin composition.
  • the aqueous urethane resin composition according to the present invention contains a urethane resin (A) and an aqueous medium (B).
  • the aqueous urethane resin composition according to the present invention is a dispersion of a urethane resin (A) obtained by reacting an aromatic polyester polyol (a1) containing an aromatic dicarboxylic acid (a1-1) as a raw material monomer with a polyisocyanate (a2), and optionally a chain extender, etc., in an aqueous medium (B).
  • the aromatic ring concentration derived from the raw material monomer of the aromatic dicarboxylic acid (a1-1) in the urethane resin (A) is, for example, 1 mmol/g or more.
  • the concentration of ester bond groups in the urethane resin (A) is, for example, 1 mmol/g or more.
  • the acid value of the urethane resin (A) is, for example, 8 to 45 mgKOH/g.
  • the urethane resin (A) is a general term for a polymeric compound having a urethane bond (-NHCOO-), and in the present invention, is made of a reaction product obtained by reacting (crosslinking/curing reaction) an aromatic polyester polyol (a1) with a polyisocyanate (a2).
  • the urethane resin (A) may contain, in addition to the aromatic polyester polyol (a1) and the polyisocyanate (a2), another polyol (a3), or may be a reaction product of the aromatic polyester polyol (a1), the polyisocyanate (a2), and the other polyol (a3).
  • the aromatic polyester polyol (a1) can be produced, for example, by subjecting an aromatic dicarboxylic acid (a1-1) and a polyol (a1-2) to an esterification reaction.
  • Aromatic dicarboxylic acids (a1-1) that can be used in producing aromatic polyester polyol (a1) include, for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-P,P'-dicarboxylic acid, as well as their acid anhydrides or ester-forming derivatives; aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid, as well as their ester-forming derivatives; and sulfonic acid group-containing aromatic dicarboxylic acids such as 5-sulfoisophthalic acid, as well as their ester-forming derivatives.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid,
  • an aliphatic carboxylic acid or an alicyclic carboxylic acid can be used in combination.
  • examples include aliphatic dicarboxylic acids such as succinic acid, succinic anhydride, adipic acid, suberic acid, azelaic acid, sebacic acid, dimer acid, maleic anhydride, and fumaric acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and their anhydrides or ester-forming derivatives. These may be used alone or in combination of two or more.
  • polyols examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, and neopentyl glycol.
  • aromatic dicarboxylic acid (a1-1) and polyol (a1-2) can be reacted in the presence of a catalyst as necessary in a reaction vessel purged with an inert gas such as nitrogen under normal or reduced pressure.
  • the reaction is preferably carried out in the range of 100°C to 300°C.
  • the catalyst for example, acetates of alkali metals or alkaline earth metals, or compounds containing zinc, manganese, cobalt, antimony, germanium, titanium, tin, zirconium, etc. can be used. Among them, it is preferable to use tetraalkyl titanates or tin oxalate, which are effective for transesterification reactions and polycondensation reactions.
  • the aromatic polyester polyol (a1) and the polyisocyanate (a2) can also be used in combination with other polyols (a3), etc.
  • polyols (a3) that can be used include polyols similar to the polyols (a1-2) above, such as relatively low molecular weight polyols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, and neopentyl glycol.
  • relatively low molecular weight polyols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butaned
  • -Polyisocyanate (a2)- As the polyisocyanate (a2) which reacts with the polyol (a1) to form the urethane resin (A), for example, aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, and aliphatic or aliphatic cyclic structure-containing diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used alone or in combination of two or more.
  • aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenyl
  • the viewpoint of improving the adhesion to the substrate and the deinking property of the resulting primer layer it is more preferable to use one or more selected from the group consisting of isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate from the viewpoint of improving the adhesion to the substrate and the deinking property of the resulting primer layer.
  • the urethane resin (A) can be produced, for example, in the absence of a solvent or in the presence of an organic solvent, by reacting the aromatic polyester polyol (a1), the polyisocyanate (a2), and, if necessary, the polyol (a3), and, if necessary, a chain extender.
  • organic solvent it is preferable to remove the organic solvent by a method such as distillation when dispersing the urethane resin (A) in the aqueous medium (B).
  • Organic solvents that can be used when producing urethane resin (A) include, for example, ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; dimethylformamide and N-methylpyrrolidone, which can be used alone or in combination of two or more.
  • the chain extender that can be used when producing the urethane resin (A) can be used for the purpose of increasing the molecular weight of the urethane resin (A) and improving the durability of the resulting film or the like.
  • the chain extender that can be used in producing the urethane resin (A) polyamines and other compounds containing active hydrogen atoms can be used.
  • the chain extender can be used when reacting the aromatic polyester polyol (a1) with the polyisocyanate (a2) or after the reaction.
  • the chain extender can also be used when dispersing the urethane resin (A) in the aqueous medium (B) to make it aqueous.
  • the concentration of aromatic rings derived from the raw material monomer of the aromatic dicarboxylic acid (a1-1) in the urethane resin (A) is preferably 1 mmol/g or more.
  • the aromatic ring concentration can be determined by calculating the number of moles of aromatic rings contained in 1 g of the urethane resin (A). The specific calculation method will be described later.
  • the aromatic ring concentration is preferably 1.5 mmol/g or more, and more preferably 2 mmol/g or more, and from the viewpoint of good film-forming properties of the primer layer, the aromatic ring concentration is preferably 6 mmol/g or less, and more preferably 5 mmol/g or less.
  • the concentration of ester bond groups in the urethane resin (A) is preferably 1 mmol/g or more.
  • the ester bond concentration can be determined by calculating the number of moles of the ester bond groups contained in 1 g of the urethane resin (A). The specific calculation method will be described later.
  • the ester bond group concentration is preferably 2 mmol/g or more, and more preferably 4 mmol/g or more, and from the viewpoint of good blocking resistance of the primer layer, the ester bond group concentration is preferably 9 mmol/g or less, and more preferably 7 mmol/g or less.
  • the acid value of the urethane resin (A) is preferably 8 to 45 mgKOH/g.
  • the acid value is the amount of acid in 1 g of resin calculated by titrating the acid with an alkali, converted into mg of potassium hydroxide, according to JIS K0070. If the acid value is 8 mgKOH/g or more, the aqueous dispersion stability can be improved, and is preferably 15 mgKOH/g or more, and more preferably 20 mgKOH/g or more. If the acid value is 45 mgKOH/g or less, the adhesion to the polyester substrate can be well ensured, and is preferably 40 mgKOH/g or less, and more preferably 30 mgKOH/g or less.
  • the value obtained by dividing the mass of the raw material monomer of the polyisocyanate (a2) contained in 1 g of the urethane resin (A) by the NCO equivalent weight of the raw material monomer of the polyisocyanate (a2) is preferably 1.0 to 6.0 mmol/g. If this value is 1.0 mmol/g or more, the substrate adhesion and deinking properties of the obtained primer layer can be improved, and it is more preferable that the value is 1.5 mmol/g or more, and even more preferable that the value is 1.8 mmol/g or more. If it is 6.0 mmol/g or less, the film-forming properties of the primer layer can be ensured, and it is more preferably 5.0 mmol/g or less, and even more preferably 4.0 mmol/g or less.
  • the weight average molecular weight of the urethane resin (A) is preferably 10,000 to 100,000. From the viewpoints of blocking resistance to the substrate and hydrolysis stability of the resin, the weight average molecular weight of the urethane resin (A) is preferably 20,000 or more, and more preferably 30,000 or more. Also, from the viewpoints of low viscosity during aqueous dispersion and productivity, the weight average molecular weight is preferably 80,000 or less, and more preferably 60,000 or less.
  • the weight average molecular weight was measured by gel permeation chromatography (GPC). The measurement conditions were as described above.
  • the glass transition temperature of the urethane resin (A) is preferably 0 to 110°C.
  • aqueous medium (B) that serves as a solvent for the urethane resin (A)
  • examples of the aqueous medium (B) that serves as a solvent for the urethane resin (A) include water, organic solvents that are miscible with water, and mixtures thereof.
  • organic solvents that are miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; Alkyl ethers; N-methyl-2-pyrrolidone, etc.
  • water only water may be used, or a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From this viewpoint, water alone or a mixture of water and an organic solvent miscible with water is preferred, and water alone is particularly preferred.
  • a machine such as a homogenizer can be used as necessary.
  • the aqueous urethane resin composition of the present invention preferably contains urethane resin (A) in the range of 5% by mass to 50% by mass, and more preferably in the range of 10% by mass to 25% by mass, based on the total amount of the aqueous urethane resin composition.
  • the aqueous medium (B) is preferably contained in the range of 50% by mass to 95% by mass, and more preferably in the range of 75% by mass to 90% by mass, based on the total amount of the aqueous urethane resin composition.
  • various additives such as a film-forming assistant, a crosslinking agent, a curing accelerator, a plasticizer, an antistatic agent, a wax, a light stabilizer, a flow control agent, a dye, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant, a photocatalytic compound, an inorganic pigment, an organic pigment, and an extender pigment can be used as necessary.
  • emulsifiers and leveling agents can cause a decrease in the durability of the resulting film, etc., so when high durability is required for the film, etc., it is preferable to use them in an amount of 5 mass% or less based on the total amount of the aqueous urethane resin composition.
  • the aqueous urethane resin composition of the present invention can be used in combination with various crosslinking agents.
  • the crosslinking agent that can be used include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, amino-based crosslinking agents, aziridine-based crosslinking agents, silane coupling agent-based crosslinking agents, carbodiimide-based crosslinking agents, and oxazolidine-based crosslinking agents.
  • the crosslinking agent is preferably used in an amount of 30% by mass or less, and more preferably 20% by mass or less, based on the total amount of the urethane resin (A) from the viewpoints of improving adhesion to the substrate, improving deinking properties, etc.
  • the crosslinking agent is preferably mixed and used immediately before coating the aqueous urethane resin composition of the present invention.
  • a second embodiment of the primer layer-forming composition is a primer layer-forming composition containing polyvinyl alcohol.
  • the primer layer containing polyvinyl alcohol is preferably a resin layer containing at least 25% by mass of polyvinyl alcohol.
  • the resin layer containing polyvinyl alcohol may be referred to as a PVA resin layer.
  • Polyvinyl alcohol is a colorless powder obtained by saponifying polyvinyl acetate. It is a water-soluble thermoplastic resin and is the raw material for the synthetic fiber vinylon. It is generally abbreviated to poval or PVA.
  • Commercially available products include Poval, Elvanol, and Exeval manufactured by Kuraray Co., Ltd., Gohsenol manufactured by Mitsubishi Chemical Corporation, and Nippon Vinyl Acetate & Poval Co., Ltd.
  • the degree of saponification of polyvinyl alcohol is determined by the ratio of vinyl groups in polyvinyl acetate substituted with hydroxyl groups, and is preferably 90% or more.
  • Examples of polyvinyl alcohol having a degree of saponification of 90% or more include, but are not limited to, the following commercially available products: Kuraray Co., Ltd. Poval "3-98, 5-98, 28-98, 60-98, 27-96", Kuraray Co., Ltd. Elvanol "71-30, 90-50, T-25, T-66", Kuraray Co., Ltd. Exeval "AQ-4104, HR-3010, RS-2117, RS-1717", Mitsubishi Chemical Co., Ltd.
  • the composition for forming a primer layer containing polyvinyl alcohol can be obtained by mixing the above-mentioned aqueous medium (B) with polyvinyl alcohol (C). Furthermore, the polyvinyl alcohol-containing resin composition according to the present invention may contain various additives, etc., as necessary. Examples of additives include those described in the above section ⁇ Other Additives>>>.
  • the primer layer-forming composition of the present invention can be used to form a primer layer by coating the primer layer-forming composition on a substrate.
  • an ink layer made of an ink layer-forming composition can be formed on the primer layer.
  • the primer layer can be easily removed by treatment with an alkaline solution. Since the primer layer can be easily peeled off from the substrate, the ink layer formed on the primer layer can also be easily removed from the substrate. The method for removing the primer layer will be described in detail later.
  • the varnish layer is formed using a varnish layer forming composition.
  • the composition for forming a varnish layer generally contains a binder resin, a solvent such as an organic solvent or an aqueous solvent, and additives.
  • the varnish layer according to the present invention has the function of suppressing coloration of the alkaline solution by the ink layer.
  • the type of varnish layer-forming composition that forms the varnish layer there are no particular restrictions on the type of varnish layer-forming composition that forms the varnish layer; however, it is preferable for the composition to contain at least one type of resin (hereinafter also referred to as resin (B)) selected from the group consisting of urethane resins, cellulose derivatives, and polyester resins.
  • resin (B) a type of resin selected from the group consisting of urethane resins, cellulose derivatives, and polyester resins.
  • the cellulose derivative include cellulose acetate propionate resin, cellulose acetate butyrate resin, and nitrocellulose resin.
  • Cellulose acetate propionate resin (hereinafter sometimes referred to as CAP) is a resin obtained by triesterifying cellulose with acetic acid and propionic acid, followed by hydrolysis. Since there is a tendency for a composition having excellent coloration suppression effect to be obtained, per 100 parts by mass of the total amount of CAP, one having 0.3 to 2.5 parts by mass of acetyl groups, 42 to 46 parts by mass of propionyl groups, and 1.8 to 5 parts by mass of hydroxyl groups can be suitably used.
  • CAP Cellulose acetate propionate resin
  • Cellulose acetate butyrate resin (hereinafter sometimes referred to as CAB) is a resin obtained by triesterifying cellulose with acetic acid and butyric acid, followed by hydrolysis. Since there is a tendency for a composition having excellent coloration suppression effect to be obtained, per 100 parts by mass of the total amount of CAB, one having 2 to 30 parts by mass of acetyl groups, 17 to 53 parts by mass of butyryl groups, and 1 to 5 parts by mass of hydroxyl groups can be suitably used.
  • CAB Cellulose acetate butyrate resin
  • nitrocellulose resin a general cellulose nitrate obtained by treating cellulose with a mixed acid of nitric acid and sulfuric acid can be used.
  • a mixed acid of nitric acid and sulfuric acid can be used.
  • two or more types of products having different viscosity standards according to JIS K-6703 (industrial nitrocellulose) (e.g., H20 equivalent and L1/4 equivalent) may be mixed and used.
  • the varnish layer forming composition may contain other resins in addition to at least one type of resin (B) selected from the group consisting of the above-mentioned urethane resins, cellulose derivatives, and polyester resins.
  • the varnish layer-forming composition according to the present invention is preferably a composition capable of forming a varnish layer having a heat-resistant coating function. Because the varnish layer has a heat-resistant coating function, it can effectively suppress coloration of the alkaline solution when the ink layer detaches from the substrate.
  • a varnish forming composition that forms a varnish layer having a heat-resistant coating function
  • resins contained in the varnish forming composition include cellulose derivatives such as nitrocellulose (nitrocellulose), cellulose acetate, cellulose propionate, and cellulose butyrate; polyester resins having a benzene ring, such as phthalic acid, naphthalene dicarboxylic acid, and an ethylene oxide (hereinafter sometimes referred to as EO) adduct of bisphenol A, and/or an alicyclic skeleton, such as cyclopentanediol and dimethyloltricyclodecane; aromatic isocyanates such as diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, and naphthalene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate and norbornene diisocyanate; and/or urethane resins in which isocyanuric triisocyanate is bonded to a polyol,
  • the varnish forming composition may contain a polyisocyanate using the above-mentioned isocyanate as a curing agent (crosslinking agent).
  • the varnish forming composition may preferably contain a compound having a benzene ring and an unsaturated double bond, such as styrene or phenoxydiethylene glycol acrylate, and/or a compound having an alicyclic structure and an unsaturated double bond, such as isobornyl acrylate or dicyclopentanyl acrylate, and a radical copolymer such as (meth)acrylate.
  • a resin with a low Tg may be mixed and used.
  • the total content of the cellulose skeleton, benzene ring skeleton, isocyanuric ring skeleton, and alicyclic skeleton of the above-mentioned compound is preferably 20 to 90% by mass, and more preferably 30 to 80% by mass, of the solid content of the varnish forming composition.
  • the varnish layer forming composition examples include (i) a composition for forming a varnish layer that contains at least a urethane resin and a cellulose derivative, or (ii) a composition for forming a varnish layer that contains at least a urethane resin, a cellulose derivative, and a polyisocyanate.
  • the varnish layer-forming composition according to the present invention preferably contains a polyisocyanate curing agent (crosslinking agent), and the varnish layer according to the present invention is preferably a crosslinked coating film formed by the varnish layer-forming composition.
  • crosslinking agent polyisocyanate curing agent
  • the varnish layer according to the present invention is preferably a crosslinked coating film formed by the varnish layer-forming composition.
  • the solvent contained in the varnish layer forming composition may be an organic solvent or water.
  • organic solvents and aqueous media as those described in the ⁇ Organic Solvent>> section above or those described in the ⁇ Aqueous Medium (B)>>> section in ⁇ Primer Layer>> can be used.
  • the additives contained in the composition for forming the varnish layer are not particularly limited, and may include, for example, extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, antiblocking agents, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, etc. Also, various additives described in the ⁇ Other Additives>>> section in the ⁇ Primer Layer>> above may be contained.
  • the content of resin B is, for example, 2 parts by mass or more, more preferably 4 parts by mass or more, based on 100 parts by mass of the total amount of the composition for forming a varnish layer.
  • the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less. If the content of resin B is equal to or more than the lower limit, a composition having excellent coloring suppression effect tends to be obtained. If the content of resin B is equal to or less than the upper limit, a composition having excellent stability tends to be obtained.
  • the preferable range of the content is the total amount of those resins contained.
  • the method for producing the various compositions according to the present invention is not particularly limited, and a conventionally known method can be used.
  • the components of the composition may all be mixed together at once, or may be mixed in portions, such as by first mixing a portion to prepare a premix and then mixing it with the other components.
  • the mixing method is not particularly limited, and examples thereof include a method of stirring and mixing with a mixer or the like, a method using a three-roll mill, and a method using a dispersing machine such as a bead mill.
  • the composition according to the present invention can be used for any of the known and commonly used applications, such as printing ink, paint, and water-based ink for inkjet recording.
  • an ink layer forming composition is necessarily used to form an ink layer, but in the present invention, both the primer layer formed from the primer layer forming composition and the varnish layer formed from the varnish layer forming composition are used for printing ink, etc. together with the ink layer, so in the present invention, the meaning of the "composition" used for printing ink, etc. includes not only the ink layer forming composition, but also the primer layer forming composition and the varnish layer forming composition.
  • the composition according to the present invention can be used as a printing ink.
  • the printing ink is not particularly limited as long as it contains the composition according to the present invention, and can be obtained with a known composition.
  • the printing ink may contain various additives that are normally contained in printing inks, such as organic or inorganic fillers, antistatic agents, defoamers, viscosity modifiers, polymerization inhibitors, light resistance stabilizers, weather resistance stabilizers, heat resistance stabilizers, UV absorbers, antioxidants, leveling agents, pigment dispersants, waxes, etc., as necessary.
  • additives such as organic or inorganic fillers, antistatic agents, defoamers, viscosity modifiers, polymerization inhibitors, light resistance stabilizers, weather resistance stabilizers, heat resistance stabilizers, UV absorbers, antioxidants, leveling agents, pigment dispersants, waxes, etc., as necessary.
  • the printing ink using the composition according to the present invention has excellent adhesion to substrates and can be used for printing on paper, synthetic paper, cloth, thermoplastic resin films, plastic products, steel plates, etc., and is useful as an ink for gravure printing using a gravure printing plate made by electronic engraving or the like, or for flexographic printing using a flexographic printing plate made by a resin plate or the like.
  • the thickness of the printing ink formed by the gravure printing method or the flexographic printing method is preferably, for example, 10 ⁇ m or less, and more preferably 5 ⁇ m or less.
  • a primer layer, an ink layer, and a varnish layer can be laminated on the substrate in that order, thereby obtaining a printed item consisting of a laminate of the substrate and these layers.
  • the other layer is not particularly limited, and may be a single layer or multiple layers.
  • each of the primer layer, the ink layer, and the varnish layer may be composed of two or more layers.
  • the printed matter and laminate of the present invention may have the following configurations. ⁇ Base material/Primer layer/Ink layer/Varnish layer
  • the laminate according to the present invention can be produced, for example, by the following method.
  • a primer layer forming composition is printed on a plastic substrate by a printing method such as gravure printing or flexographic printing.
  • an ink layer is formed as a printed layer by printing an ink layer forming composition on the primer layer by a printing method such as gravure printing or flexographic printing.
  • a varnish layer forming composition is printed on the ink layer by a printing method such as gravure printing or flexographic printing to form a varnish layer. This makes it possible to obtain a laminate (substrate/primer layer/ink layer/varnish layer).
  • compositions according to the present invention can be applied to a substrate by using a known printing method such as gravure printing, flexographic printing, etc.
  • known printing methods include, for example, a T-die coater, a lip coater, a knife coater, a curtain, an inkjet, a bar coater, a roll coater, a spray coater, a comma coater, a reverse roll coater, a direct gravure coater, a reverse gravure coater, an offset gravure coater, a roll kiss coater, a reverse kiss coater, a kiss gravure coater, a reverse kiss gravure coater, an air doctor coater, a wire bar coater, a dip coater, a blade coater, a brush coater, a die slot coater, an offset printing machine, a screen printing machine, etc., or a combination of two or more coating methods can be used.
  • the ink When printing, the ink is diluted with an aqueous solution, for example, a diluting solvent obtained by mixing water with an alcohol-based organic solvent such as ethyl alcohol, isopropyl alcohol, or normal propyl alcohol, to a viscosity and concentration suitable for various printing methods such as gravure printing and flexographic printing, and then supplied to each printing unit either alone or in a mixture.
  • a diluting solvent obtained by mixing water with an alcohol-based organic solvent such as ethyl alcohol, isopropyl alcohol, or normal propyl alcohol
  • the method of applying the primer layer-forming composition onto the substrate can be an in-line coating method in which the primer layer-forming composition is applied during the substrate stretching process (e.g., biaxial stretching process) and then a further stretching process is performed, or an offline coating method in which the primer layer-forming composition is applied and dried after the substrate stretching process (e.g., biaxial stretching process) to form a primer layer.
  • an in-line coating method in which the primer layer-forming composition is applied during the substrate stretching process (e.g., biaxial stretching process) and then a further stretching process is performed
  • an offline coating method in which the primer layer-forming composition is applied and dried after the substrate stretching process (e.g., biaxial stretching process) to form a primer layer.
  • the primer layer formed from the primer layer-forming composition of the present invention has good adhesion to the substrate, and the laminate of the present invention has excellent adhesion between the substrate and the printed layer.
  • the laminate of the present invention can remove the primer layer in a simple manner by using an alkaline solution, and the substrate and the printing layer, which is the ink layer, can be easily peeled off.
  • the primer layer of the laminate of the present invention will not be peeled off even if an alkaline solution is applied under temperature conditions in which it is normally used. Therefore, under temperature conditions in which it is normally used, even if an alkaline solution happens to adhere to the laminate, it can be used without worrying about peeling.
  • the primer layer of the printed matter of the present invention described above is removed from the substrate by treatment with an alkaline solution, and the ink layer and varnish layer are also removed at the same time, thereby producing a recycled substrate.
  • “Detachment” refers to the peeling off of the coating by the alkaline solution treatment through swelling, dissolution, erosion, etc.
  • the primer layer can be peeled off by swelling, dissolution, erosion, etc. through the alkaline solution treatment.
  • a primer layer provided on a substrate is detached by an alkaline solution treatment. The detachment of the primer layer causes the ink layer and the varnish layer to be detached from the substrate together with the primer layer.
  • the ink layer dissolves in an alkaline solution, the alkaline solution is colored, but the varnish layer that is detached together with the ink layer can contribute to suppressing coloration of the alkaline solution.
  • the detachment step includes a step of immersing the printed matter in an alkaline solution while heating and stirring at 20 to 90° C. or ultrasonically vibrating the printed matter. Heating and stirring and ultrasonic vibration may be performed simultaneously.
  • the heating temperature is preferably 30° C. or higher, more preferably 40° C. or higher, more preferably 50° C. or higher, and more preferably 60° C. or higher, and it is more preferable to perform heating and stirring and ultrasonic vibration simultaneously.
  • the alkaline solution used in the desorption step is not limited, but preferably has a pH of 9 or higher, and is preferably an aqueous solution of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium dihydrogen carbonate, potassium dihydrogen carbonate, etc.
  • the aqueous solutions of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium dihydrogen carbonate, potassium dihydrogen carbonate, etc. are preferably aqueous solutions with a concentration of 0.5% to 10% by mass, more preferably 1% to 5% by mass.
  • the alkaline solution may also contain a water-soluble organic solvent.
  • the water-soluble organic solvent include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dibutyl ether, diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol dimethyl ether, diethylene glycol monoethyl ether (carbitol), diethylene glycol diethyl ether (diethyl carbitol), diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dibutyl ether, and triethylene glycol.
  • alkyl ether examples include glycol monomethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methylene dimethyl ether (methylal), propylene glycol monobutyl ether, tetrahydrofuran, acetone, diacetone alcohol, acetonylacetone, acetylacetone, ethylene glycol monomethyl ether acetate (methyl cellosolve acetate), diethylene glycol monomethyl ether acetate (methyl carbitol acetate), diethylene glycol monoethyl ether acetate (carbitol acetate), ethyl hydroxyisobutyrate, and ethyl lactate. These may be used alone or in combination of two or more.
  • the content of the water-soluble organic solvent in the alkaline solution is preferably 0.1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass.
  • the alkaline solution may also contain a water-insoluble organic solvent.
  • the water-insoluble organic solvent include alcohol-based solvents such as n-butanol, 2-butanol, isobutanol, and octanol; aliphatic hydrocarbon-based solvents such as hexane, heptane, and normal paraffin; aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, and alkylbenzene; halogenated hydrocarbon-based solvents such as methylene chloride, 1-chlorobutane, 2-chlorobutane, 3-chlorobutane, and carbon tetrachloride; ester-based solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone
  • the alkaline solution may also contain a surfactant.
  • surfactants include various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc., and among these, anionic surfactants, nonionic surfactants, and amphoteric surfactants are preferred, with nonionic surfactants being more preferred.
  • anionic surfactants include alkylbenzenesulfonates, alkylphenylsulfonates, alkylnaphthalenesulfonates, higher fatty acid salts, sulfates of higher fatty acid esters, sulfonates of higher fatty acid esters, sulfates and sulfonates of higher alcohol ethers, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, and polyoxyethylene alkyl ether phosphates.
  • dodecylbenzenesulfonates include dodecylbenzenesulfonates, isopropylnaphthalenesulfonates, monobutylphenylphenol monosulfonates, monobutylbiphenylsulfonates, and dibutylphenylphenol disulfonates.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylol amides, alkyl alkanol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, and the like.
  • polyoxyethylene nonylphenyl ether polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymers are preferred.
  • surfactants that can be used include silicon-based surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers; and biosurfactants such as spiculisporic acid, rhamnolipids, and lysolecithin.
  • silicon-based surfactants such as polysiloxane oxyethylene adducts
  • fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers
  • biosurfactants such as spiculisporic acid, rhamnolipids, and lysolecithin.
  • surfactants can be used alone or in combination of two or more.
  • the amount added is preferably in the range of 0.001 to 2 mass % of the total amount of the alkaline solution, more preferably 0.001 to 1.5 mass %, and even more preferably 0.01 to 1 mass %.
  • the alkaline solution after detachment tends to become more colored than when the alkaline solution is used alone, but when the primer layer detaches from the substrate, the varnish layer detaches together with the ink layer, effectively suppressing coloration of the treatment solution.
  • the target printed matter or laminate is immersed in the alkaline solution, for example in a treatment tank, while the alkaline solution is heated to 20-90°C or ultrasonically vibrated.
  • the heating method There are no particular limitations on the heating method, and known heating methods using heat rays, infrared rays, microwaves, etc. can be used.
  • Ultrasonic vibration can be achieved, for example, by attaching an ultrasonic vibrator to the treatment tank and applying ultrasonic vibration to the warm water or alkaline solution.
  • the alkaline solution is stirred during immersion.
  • stirring methods include mechanical stirring of the dispersion of the printed matter or laminate contained in the treatment tank using a stirring blade, water flow stirring using a water flow pump, and bubbling with an inert gas such as nitrogen gas. These methods may be used in combination to achieve efficient peeling.
  • the time for which the printed matter or laminate is immersed in the alkaline solution varies depending on the composition of the printed matter, but is generally in the range of 2 minutes to 48 hours. In the present invention, it is not necessary for 100% of the coating on the printed matter to be completely detached from the substrate, but it is preferable for 60% or more of the 100% by weight of the coating to be detached, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more.
  • the film may be immersed in the alkaline solution once or several times. That is, the film may be immersed once and then the separated film substrate may be recovered, or the film may be immersed several times and then the film substrate may be recovered.
  • the concentration of the alkaline solution may be changed.
  • known processes such as washing with water and drying may be added as appropriate.
  • the printed matter of the present invention has a film formed on a substrate, which is a laminate of a removable primer layer, an ink layer containing a colorant, and a varnish layer.
  • a substrate which is a laminate of a removable primer layer, an ink layer containing a colorant, and a varnish layer.
  • the presence of the varnish layer effectively prevents discoloration of the alkaline treatment solution when the film is removed in the removal process.
  • a represents the number of moles of carboxylic acid in 1 g of aromatic polyester polyol (a1).) After the ester bond group concentration in 1 g of aromatic polyester polyol (a1) is determined, the product of the ester bond group concentration in 1 g of aromatic polyester polyol (a1) and the proportion of aromatic polyester polyol (a1) in 1 g of urethane resin is determined to calculate the ester bond group concentration in 1 g of urethane resin.
  • ⁇ Acid value (mgKOH/g)> The number of COOH groups contained in 1 g of urethane resin is determined in terms of the number of mg of KOH required when titrated by the potassium hydroxide method.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC).
  • the glass transition temperature is measured by differential scanning calorimetry.
  • the layer-forming compositions used in the examples and comparative examples are as follows.
  • [Ink composition] [[Ink A]] ⁇ Pigments> Pigment: Phthalocyanine blue pigment (FASTOGEN BLUE FA5380 manufactured by DIC Corporation) ⁇ Resin> Nitrocellulose resin 30% solution: Nitrocellulose DLX5-8 manufactured by Nobel, 30% non-volatile content, ethyl acetate: IPA solution
  • Table 1-1 The mixing ratio of each of the above raw materials is as shown in Table 1-1 below.
  • Pigment Phthalocyanine blue pigment (FASTOGEN BLUE FA5380 manufactured by DIC Corporation) ⁇ Resin> ⁇ 50% acrylic resin solution: DIC Corporation's ACRYDIC WCL-1419, number average molecular weight 16,000, non-volatile content 50%, ethyl acetate:IPA solution ⁇ 25% vinyl chloride-vinyl acetate copolymer resin solution: Nissin Chemical Industry Co., Ltd.'s Solvine A, non-volatile content 25%, methyl ethyl ketone solution ⁇ 20% cellulose acetate butyrate solution: Cellulose acetate butyrate resin (Eastman Chemical Company's CAB-381-0.1), non-volatile content 20%, ethyl acetate solution ⁇ organic solvent> Isopropyl alcohol, methyl ethyl ketone, ethyl acetate, toluene, normal propyl a
  • Primer composition 1 (also referred to as primer 1) to primer composition 2 (also referred to as primer 2) are as follows. [[Primer 1]] 100 parts of urethane resin 1 was mixed with 9 parts of "Carbodilite SV-02" manufactured by Nisshinbo Chemical Inc., and then diluted with isopropyl alcohol (IPA) to a solid content of 10% to obtain a primer-forming composition consisting of an aqueous urethane resin composition containing a crosslinking agent. ⁇ Urethane resin 1> Urethane resin 1 was synthesized as follows.
  • a four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 0.74 g of polyol a, 0.20 g of isophorone diisocyanate, and 0.06 g of 2,2'-dimethylolpropionic acid in a ratio of 0.74 g, and reacted at 75°C for 8 hours under a nitrogen stream to obtain urethane resin 1.
  • Polyol a was prepared by mixing and reacting 0.32 g of terephthalic acid (TPA), 0.32 g of isophthalic acid (IPA), 0.13 g of ethylene glycol (EG), and 0.23 g of diethylene glycol (DEG) in a ratio of 0.32 g to 0.23 g, to produce an aromatic polyester polyol.
  • TPA terephthalic acid
  • IPA isophthalic acid
  • EG ethylene glycol
  • DEG diethylene glycol
  • the aromatic ring concentrations shown in Table 2 were determined as follows.
  • the urethane resin 1 will be taken as an example for explanation.
  • the aromatic ring concentration in 1 g of polyol a is calculated.
  • the mass ratio of the raw material monomer of the aromatic dicarboxylic acid (a1-1) containing an aromatic ring to the molecular weight of that monomer is calculated (when there are multiple raw material monomers of the aromatic dicarboxylic acid (a1-1), the sum is calculated).
  • the ester bond group concentrations shown in Table 2 were determined as follows.
  • the urethane resin 1 will be taken as an example for explanation.
  • the concentration of ester bond groups in 1 g of polyol a is calculated.
  • a can be calculated as follows.
  • the urethane + urea functional group concentrations shown in Table 2 were determined as follows.
  • the urethane resin 1 will be used as an example.
  • Varnish composition 1 (also referred to as Varnish 1) to varnish composition 3 (also referred to as Varnish 3) were prepared as shown in Table 3 below.
  • Table 3 the abbreviations are as follows: CAP-504-0.2: Cellulose acetate propionate manufactured by Eastman Chemical Company CAB-1000: Cellulose acetate butyrate manufactured by Eastman Chemical Company NITROCELLULOSE DLX5-8: Nitrocellulose manufactured by Nobel NC LX-470EL: Polyurethane polyol manufactured by DIC Corporation KW-75: Aromatic polyisocyanate manufactured by DIC Corporation
  • Example 1 ⁇ Production of printed matter>
  • the prepared primer composition was printed on a substrate (PE film) using a bar coater #4 as a solid layer measuring 240 mm in length and 80 mm in width, and then dried with a dryer. The resulting layer was then left at room temperature for at least one day to form a primer layer.
  • the prepared ink composition was printed on the dried primer layer using a bar coater #4, and after printing, it was dried with a dryer to form an ink layer.
  • the prepared varnish composition was printed on the ink layer using a bar coater #4, and after printing, it was dried with a dryer to form an OP varnish layer, which was then aged at 40° C. for 3 days.
  • a printed matter was obtained consisting of a laminate in which a primer layer, an ink layer, and an OP varnish layer were laminated on a substrate.
  • the surfactant used was a nonionic surfactant (Triton X-100).
  • the coloring inhibition test was performed by setting the treatment time of the alkaline solution to 10 minutes.
  • the printed matter was cut into 20 mm x 20 mm test pieces, and 50 pieces were immersed in 500 mL of an alkaline solution and stirred with a stirrer.
  • the transparency of the alkaline solution after stirring was measured using a transparency meter according to the method of JIS (Japanese Industrial Standards) K0102.
  • the transparency meter was made of a glass cylinder with a bottom opening and graduations every 10 mm, and a sign plate with a double cross on the bottom.
  • the alkali solution was filled into the transparency meter, and the bottom was viewed from the top.
  • the blank samples used in Examples 1 to 3 were 50 test pieces cut to a size of 20 mm x 20 mm from the printed matter obtained using the ink composition of Comparative Example 1, immersed in 500 mL of alkaline solution, and stirred with a stirrer.
  • the blank samples used in Examples 4 to 6 were 50 test pieces cut to a size of 20 mm x 20 mm from the printed matter obtained using the ink composition of Comparative Example 4, immersed in 500 mL of alkaline solution, and stirred with a stirrer.
  • the blank samples used in Examples 7 to 9 were 50 test pieces cut to a size of 20 mm x 20 mm from the printed matter obtained using the ink composition of Comparative Example 7, immersed in 500 mL of alkaline solution, and stirred with a stirrer.
  • the blank samples used in Examples 10 to 12 were 50 test pieces cut to a size of 20 mm x 20 mm from the printed matter obtained using the ink composition of Comparative Example 10, immersed in 500 mL of alkaline solution, and stirred with a stirrer.
  • test pieces were cut to a size of 20 mm x 20 mm from the printed matter obtained using the ink composition of Comparative Example 13, and the samples were used after immersing them in 500 mL of alkaline solution and stirring with a stirrer.
  • Examples 2 to 15, Comparative Examples 1 to 15 A printed matter was obtained in the same manner as in Example 1, except that the layer structure in Example 1 was changed to those shown in Tables 4-1 to 4-5 below. The obtained prints were evaluated in the same manner as in Example 1. The results are shown in Tables 4-1 to 4-5.
  • the printed matter according to the present invention can easily remove the ink layer from the substrate by treatment with an alkaline solution, and can effectively suppress discoloration of the alkaline solution when the ink layer is removed.
  • the printed matter according to the present invention has an effect of suppressing the coloring of the alkaline treatment solution, and therefore can prevent water pollution and environmental load caused by colored wastewater.
  • raw materials and manufacturing equipment for decolorization of colored wastewater are not required, it is possible to reduce manufacturing costs when recycling substrates.
  • no step for decolorization is required and the recycling efficiency of substrates is excellent, it is very useful industrially.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne : un procédé de production d'un panneau recyclé, le procédé permettant de supprimer la coloration d'une solution alcaline après qu'un film de revêtement a été retiré d'un matériau de base en matière plastique par un traitement par la solution alcaline ; et un article imprimé ayant un film de revêtement pouvant être retiré, l'article imprimé étant approprié pour être utilisé dans le procédé de production du panneau recyclé.　L'invention concerne un article imprimé dans lequel sont laminés, dans l'ordre indiqué : un matériau de base ; une couche de primaire qui peut être retirée du matériau de base par traitement avec une solution alcaline ; une couche d'encre contenant un colorant et au moins une résine choisie dans le groupe constitué par les résines acryliques, les résines d'uréthane, les résines de polyamide, les résines de colophane et les résines de polyester ; et une couche de vernis.
PCT/JP2024/019911 2023-07-19 2024-05-30 Article imprimé et procédé de production d'un matériau de base recyclé Pending WO2025018039A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2024560305A JP7683833B1 (ja) 2023-07-19 2024-05-30 印刷物、及びリサイクル基材の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023-117298 2023-07-19
JP2023117298 2023-07-19

Publications (1)

Publication Number Publication Date
WO2025018039A1 true WO2025018039A1 (fr) 2025-01-23

Family

ID=94281826

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/019911 Pending WO2025018039A1 (fr) 2023-07-19 2024-05-30 Article imprimé et procédé de production d'un matériau de base recyclé

Country Status (2)

Country Link
JP (1) JP7683833B1 (fr)
WO (1) WO2025018039A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0985778A (ja) * 1995-09-22 1997-03-31 Nissha Printing Co Ltd アクリルインサートフィルムとアクリルインサート成形品の製造方法
JP7143962B1 (ja) * 2022-05-16 2022-09-29 東洋インキＳｃホールディングス株式会社 積層体、積層体の製造方法、及び、積層体の脱墨方法
WO2023282003A1 (fr) * 2021-07-07 2023-01-12 Dic株式会社 Composition pour formation de film de revêtement pouvant être éliminé
WO2023282004A1 (fr) * 2021-07-07 2023-01-12 Dic株式会社 Composition pour formation de film de revêtement pouvant être éliminé
JP2023030236A (ja) * 2021-08-23 2023-03-08 東洋インキＳｃホールディングス株式会社 シュリンクフィルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0985778A (ja) * 1995-09-22 1997-03-31 Nissha Printing Co Ltd アクリルインサートフィルムとアクリルインサート成形品の製造方法
WO2023282003A1 (fr) * 2021-07-07 2023-01-12 Dic株式会社 Composition pour formation de film de revêtement pouvant être éliminé
WO2023282004A1 (fr) * 2021-07-07 2023-01-12 Dic株式会社 Composition pour formation de film de revêtement pouvant être éliminé
JP2023030236A (ja) * 2021-08-23 2023-03-08 東洋インキＳｃホールディングス株式会社 シュリンクフィルム
JP7143962B1 (ja) * 2022-05-16 2022-09-29 東洋インキＳｃホールディングス株式会社 積層体、積層体の製造方法、及び、積層体の脱墨方法

Also Published As

Publication number Publication date
JP7683833B1 (ja) 2025-05-27
JPWO2025018039A1 (fr) 2025-01-23

Similar Documents

Publication Publication Date Title
JP7407159B2 (ja) 裏刷り用溶剤型グラビア印刷インキ組成物、印刷層、および積層体
EP3858908B1 (fr) Procédé de séparation/récupération pour film stratifié
JP7693681B2 (ja) 脱離可能な皮膜を形成するための有機溶剤系組成物
JP5937285B1 (ja) 軟包装用ラミネートインキ組成物
WO2017022640A1 (fr) Composition d'encre d'impression destinée à des stratifiés et stratifié facilement déchirable
TW202136434A (zh) 可脫離之水性油墨及其脫離方法
WO2023032997A1 (fr) Matériau d'emballage, matériau de moulage recyclé et leurs procédés de fabrication
JP7082740B2 (ja) 表刷り印刷用リキッドインキ組成物
JP7327702B2 (ja) 脱離可能な皮膜形成用組成物
JP7364109B2 (ja) 脱離可能な皮膜形成用組成物
JP2023075977A (ja) 積層体の分離回収方法
JP7364120B2 (ja) 脱離可能な皮膜形成用組成物
WO2024071019A1 (fr) Procédé de séparation et de récupération pour stratifié
JP2021187871A (ja) ラミネート用グラビアインキ、印刷物および積層体
JP7683833B1 (ja) 印刷物、及びリサイクル基材の製造方法
WO2023090397A1 (fr) Procédé de séparation et de récupération de stratifié
JP7708334B2 (ja) 印刷物、及びリサイクル基材の製造方法
JP7601285B2 (ja) 脱離可能な皮膜形成用組成物
JP7343077B2 (ja) 顔料組成物
JP7740451B1 (ja) 積層体
JP7416320B1 (ja) 積層体の製造方法
JP7679343B2 (ja) プラスチック基材の分離回収方法
CN114761234A (zh) 液体油墨组合物、印刷物和层压层叠体
JP2022183764A (ja) 脱離可能な皮膜形成用組成物
WO2025239198A1 (fr) Stratifié, procédé de fabrication d'un stratifié, procédé de fabrication d'un substrat recyclé et procédé de fabrication de pastilles de plastique recyclé

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2024560305

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24842835

Country of ref document: EP

Kind code of ref document: A1