[go: up one dir, main page]

WO2024252925A1 - Article imprimé et procédé de production de panneau recyclé - Google Patents

Article imprimé et procédé de production de panneau recyclé Download PDF

Info

Publication number
WO2024252925A1
WO2024252925A1 PCT/JP2024/018769 JP2024018769W WO2024252925A1 WO 2024252925 A1 WO2024252925 A1 WO 2024252925A1 JP 2024018769 W JP2024018769 W JP 2024018769W WO 2024252925 A1 WO2024252925 A1 WO 2024252925A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
layer
acid
resins
mgkoh
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/JP2024/018769
Other languages
English (en)
Japanese (ja)
Inventor
圭佑 若原
朋美 浅見
雅之 寺川
知生 岡田
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 JP2024563828A priority Critical patent/JP7708334B2/ja
Priority to CN202480018848.9A priority patent/CN120882563A/zh
Publication of WO2024252925A1 publication Critical patent/WO2024252925A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • 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

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
  • imparting an acid value to the urethane resin increases the viscosity of the resin, making it necessary to use solvents that have significant impacts on health and the environment to adjust the viscosity.
  • the coexistence of an amine value and an acid value is avoided in order to reduce viscosity, resulting in problems such as reduced suitability for lamination applications. For these reasons, challenges remain before the resin can be used universally as a material from which a coating can be detached.
  • 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 forming a coating that detaches from the substrate when treated with an alkaline solution by laminating at least two layers, a first layer having a colorant and a second layer in contact with the first layer, and by incorporating a specific coloring inhibitor in the second layer, thereby completing the present invention.
  • a printed matter comprising a laminate of a substrate and a coating that can be removed from the substrate by treatment with an alkaline solution, the coating has a first layer containing a colorant and at least one resin A selected from the group consisting of an acrylic resin, a urethane resin, a polyamide resin, a rosin resin, and a polyester resin, and a second layer in contact with the first layer;
  • the second layer contains at least one resin B selected from the group consisting of vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, cellulose acetate propionate resins, and cellulose acetate butyrate resins.
  • the first layer is (i) Contains at least a urethane resin and a nitrocellulose resin; (ii) Contains at least an acrylic resin and a nitrocellulose resin;
  • 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 printed matter of the present invention comprises a laminate of a substrate and a coating that can be removed from the substrate by treatment with an alkaline solution.
  • the coating has a two-layer structure including a first layer and a second layer in contact with the first layer.
  • the first layer contains a colorant and at least one resin A selected from the group consisting of an acrylic resin, a urethane resin, a polyamide resin, a rosin resin, and a polyester resin.
  • the second layer contains at least one resin B selected from the group consisting of vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, cellulose acetate propionate resins, and cellulose acetate butyrate resins.
  • the coating of the present invention has a first layer and a second layer in contact with the first layer.
  • the alkaline solution after removal is colored because the first layer contains a colorant, but in the embodiment of the present invention, the resin B contained in the second layer exhibits a coloration suppression effect, so that coloration of the alkaline solution after removal is significantly suppressed, and a clear alkaline solution can be obtained.
  • the alkaline solution used to remove the film is classified as a strong alkali, so the resin contained in the film is decomposed by the alkaline solution (particularly when the film contains nitrocellulose resin (so-called nitrocellulose), the nitrocellulose resin is decomposed in a short time), and the colorant diffuses into the alkaline solution, and the alkaline solution is colored with the color derived from the colorant.
  • the film according to the present invention contains at least one type of resin B selected from the group consisting of vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, cellulose acetate propionate resin, and cellulose acetate butyrate resin. These resins B adhere to resins such as nitrocellulose resin and colorants, and effectively protect the resins and colorants from alkali, which is thought to suppress coloring of the alkaline solution.
  • the coating according to the present invention When the coating according to the present invention is detached from the substrate by treatment with an alkaline solution, it exhibits a remarkable effect of suppressing discoloration of the alkaline solution after detachment. This makes it possible to prevent water pollution and environmental load caused by colored wastewater.
  • no raw materials or manufacturing equipment are required for the decolorization treatment of colored wastewater, it is possible to reduce manufacturing costs when recycling substrates.
  • no step for decolorization treatment is required and the substrate is highly recycled efficiently, it is extremely useful industrially.
  • the first layer is formed using a composition for forming the first layer (in this specification, such a composition is also referred to as composition (I)).
  • the composition (I) forming the first layer contains a colorant.
  • the composition (I) also contains at least one resin A selected from the group consisting of acrylic resins, urethane resins, polyamide resins, rosin resins, and polyester resins.
  • the composition (I) may further contain nitrocellulose resin (soluble nitrocellulose).
  • the composition (I) may further contain a vinyl chloride-vinyl acetate copolymer resin (also called vinyl chloride-vinyl acetate resin).
  • composition (I) may contain other resins in addition to the above-mentioned resin A, nitrocellulose resin, and vinyl chloride-vinyl acetate copolymer resin.
  • Composition (I) may also contain an organic solvent, and composition (I) may also contain other components such as auxiliaries and acidic additives. The components of composition (I) 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.
  • 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.
  • black pigments examples include C.I. Pigment Black 1, C.I. Pigment Black 6, C.I. Pigment Black 7, C.I. Pigment Black 9, and C.I. Pigment Black 20.
  • 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.
  • 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.
  • 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, C.I. Pigment Violet 37, yellow pigments include C.I. Pigment Yellow 83, C.I. Pigment Yellow 14, C.I. Pigment Yellow 180, C.I. Pigment Yellow 139, orange pigments include C.I. Pigment Orange 38, C.I. Pigment Orange 13, C.I. Pigment Orange 34, C.I. Pigment Orange 64, and it is preferable to use at least one or more selected from these groups.
  • the composition (I) may contain other resins 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 (excluding resin B described below). These may be used in appropriate combination.
  • resins 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 (excluding resin B described below).
  • 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 composition forming the first layer tends to have reduced blocking resistance, chemical resistance, etc., whereas if it exceeds 100,000, the viscosity of the composition becomes high, making it difficult to obtain a desired print density.
  • the urethane resin contained in the composition that forms the first layer preferably uses polyester polyol and/or polyether polyol as its reaction raw material.
  • the number average molecular weight of the polyester polyol is 3000 to 7000. If the number average molecular weight of the polyester polyol is less than 3000, the urethane resin film tends to become hard and the adhesion to the polyester film is easily reduced. If the number average molecular weight is more than 7000, the urethane resin film tends to become fragile and the blocking resistance of the film is easily reduced. On the other hand, it is preferable that the polyester polyol is 1 to 50 parts by mass per 100 parts by mass of the urethane resin.
  • the polyester polyol is less than 1 part by mass, the solubility of the polyurethane resin in ketone, ester, and alcohol-based solvents decreases, and the adhesion, especially on high-performance barrier films, tends to decrease. In addition, the resolubility of the film in the solvent decreases, and the reproducibility of the printed matter tends to decrease. If the amount exceeds 50 parts by mass, the film tends to become excessively soft and the blocking resistance tends to be poor.
  • 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 first 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 composition for forming the first layer 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-hydroxyethylenediamine, 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 composition for forming the first layer 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 nitrocellulose resin contained in the composition for forming the first layer according to the present invention may be a general cellulose nitrate obtained by treating cellulose with a mixed acid of nitric acid and sulfuric acid.
  • two or more types of nitrocellulose resins having different viscosity standards e.g., H20 equivalent and L1/4 equivalent
  • JIS K-6703 industrial nitrocellulose
  • the content of the nitrocellulose resin is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, per 100 parts by mass of the total amount of the composition (I) for forming the first layer, from the viewpoint of contributing to the promotion of detachment of the film. Also, from the viewpoint of the film-forming properties of the ink film and the ink viscosity, the content is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.
  • the layer may contain a resin B such as a vinyl chloride-vinyl acetate copolymer resin.
  • the resin B will be described in detail in the section "Second Layer" below.
  • resin B which has the effect of suppressing coloration of the alkaline processing solution, is contained in a layer (so-called second layer) other than the first layer, so as to ensure the freedom of selection of the type and content of the components of the first layer.
  • resin B in the first layer is not excluded, and resin B may be contained in the first layer as long as the freedom of selection of the type and content of the components of the first layer is not hindered.
  • the content of resin B is preferably 0.1 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and particularly preferably 0.3 parts by mass or more, relative to 100 parts by mass of the total amount of composition (I) forming the first layer.
  • the content is preferably 10 parts by mass or less, and more preferably 6 parts by mass or less.
  • composition (I) forming the first layer preferably contains at least two or more types of resins as shown in the following (i) to (iii).
  • (i) Contains at least a urethane resin and a nitrocellulose resin;
  • (ii) Contains at least an acrylic resin and a nitrocellulose resin;
  • (iii) Contains at least a polyamide resin and a nitrocellulose resin.
  • resin B which has the effect of suppressing coloration of the alkaline treatment solution, is contained in a layer (so-called second layer) other than the first layer.
  • resin B may be contained in the first layer as long as compatibility with other resins contained in the first layer does not become an issue. Therefore, it is also preferable that the composition (I) forming the first layer contains at least two or more types of resins as shown in the following (iv).
  • (iv) Contains at least an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, and a cellulose acetate butyrate resin
  • the content of the resin in the composition (I) 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 (I) 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 composition (I). 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 (I) 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.
  • 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 copolymer resins 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 sulf
  • 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 viscosity of composition (I) can be reduced, and a balance can be achieved between adhesion to the substrate and releasability in an alkaline solution.
  • 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 composition (I), from the viewpoints of re-dissolving property of composition (I), suppression of blocking of the printed matter, improvement of print density, and adhesion to the substrate.
  • 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 composition (I).
  • 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 composition (I).
  • 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 surface tension of composition (I) 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 second layer is formed using a composition for forming the second layer (in this specification, such a composition is also referred to as composition (II)).
  • the composition (II) forming the second layer contains at least one resin B selected from the group consisting of vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, cellulose acetate propionate resins, and cellulose acetate butyrate resins. It is preferable that the content ratio of resin B relative to the total amount of resins contained in the second layer, i.e., the content ratio of resin B relative to the total amount of resins contained in composition (II), is 30 mass% or more.
  • composition (II) may contain a resin other than the above-mentioned resin B.
  • the composition (II) may contain the resin A described in the above section "First Layer” or other resins.
  • the composition (II) may contain various additives as other components. The components of composition (II) will be described below.
  • Resin B adheres to the resin contained in the coating (particularly the first layer) (particularly, if the coating contains a nitrocellulose resin, the nitrocellulose resin) or to the colorant (e.g., a pigment) and protects the resin or colorant from alkali, thereby suppressing coloration in an alkaline solution.
  • the coating particularly the first layer
  • the coating contains a nitrocellulose resin, the nitrocellulose resin
  • the colorant e.g., a pigment
  • Resin B which exhibits a coloration suppression effect, is at least one resin selected from the group consisting of vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, cellulose acetate propionate resin, and cellulose acetate butyrate resin. These resins may be used alone or in combination of two or more types.
  • vinyl chloride-vinyl acetate copolymer resin and polyvinyl butyral resin are preferred from the viewpoint of excellent coloration suppression effect, and polyvinyl butyral resin is even more preferred from the viewpoint of excellent viscosity stability.
  • Vinyl chloride-vinyl acetate copolymer resin Vinyl chloride-vinyl acetate copolymer resin
  • Vinyl chloride-vinyl acetate copolymer resin is a polymer mainly composed of structural units derived from vinyl chloride monomer and structural units derived from vinyl acetate monomer. As long as the effects of the present invention are not impaired, the vinyl chloride-vinyl acetate resin may contain one or more structural units other than vinyl chloride and vinyl acetate.
  • the molecular weight of the vinyl chloride acetate resin is not particularly limited, but a weight average molecular weight of 5,000 to 100,000 is preferred, and 20,000 to 80,000 is even more preferred.
  • the structure derived from vinyl acetate monomer is preferably 1 to 30 parts by mass, and the structure derived from vinyl chloride monomer is preferably 70 to 95 parts by mass, out of a total of 100 parts by mass of vinyl chloride acetate resin.
  • the glass transition temperature of the vinyl chloride-vinyl acetate resin is not particularly limited, but is preferably between 50°C and 90°C.
  • Polyvinyl butyral resin is a resin in which the hydroxyl groups of polyvinyl alcohol resin are butyralized by reacting polyvinyl alcohol with butylaldehyde, and has a structure having butyral groups, acetyl groups, and hydroxyl groups.
  • the molecular weight of the polyvinyl butyral resin is not particularly limited, but a weight average molecular weight of 5,000 to 100,000 is preferred, and 10,000 to 60,000 is more preferred. Although not particularly limited, a polyvinyl butyral resin with a higher weight average molecular weight within the above range tends to provide a composition (I) with a more excellent coloration suppression effect.
  • the glass transition temperature of the polyvinyl butyral resin is not particularly limited, but is preferably 50°C to 90°C.
  • Cellulose acetate propionate resin Cellulose acetate propionate resin
  • CAP Cellulose acetate propionate resin
  • composition with excellent discoloration suppression effects it is preferable to use one that contains 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 per 100 parts by mass of the total amount of CAP.
  • CAB Cellulose acetate butyrate resin
  • CAB Cellulose acetate butyrate resin
  • compositions Since there is a tendency for a composition to be obtained that has excellent discoloration suppression effects per 100 parts by mass of total CAB, it is preferable to use one that has 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.
  • 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 (II) forming the second 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.
  • compositions (I) and (II) are collectively referred to simply as the composition
  • the method for producing the composition (I) and composition (II) 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 at once, or may be mixed in portions, such as by mixing a portion of the components first to prepare a premix and then mixing it with the other components.
  • the mixing method is not particularly limited, and examples of the method 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.
  • composition of the present invention can be used for any of the known and commonly used applications, such as printing inks, paints, and water-based inks for inkjet recording.
  • the composition according to the present invention can be used as a printing ink for forming a printed layer.
  • the composition (I) is preferably 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 various 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.
  • 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.
  • a coating having a first layer and a second layer can be laminated onto the substrate, thereby obtaining a printed matter consisting of a laminate including the substrate and the coating.
  • the other layer is not particularly limited, and may be a single layer or multiple layers.
  • a third layer that promotes desorption may be disposed between the substrate and the coating.
  • the form of the printed matter and laminate in the present invention is not particularly limited, but examples thereof include the following forms.
  • Substrate/ink layer (first layer)/OP varnish layer (second layer) Substrate/Primer layer (second layer)/Ink layer (first layer)
  • Substrate/ink layer 1 (second layer)/ink layer 2 (first layer) Substrate/ink layer 1 (first layer)/ink layer 2 (second layer)
  • a second layer when an ink layer consisting of a first layer containing a colorant is formed on a substrate, a second layer can be formed as a varnish layer not containing a colorant.
  • the layer that serves as the underprint of the ink layer i.e., the layer between the substrate and the ink layer of the first layer
  • the layer that serves as the overprint of the ink layer i.e., the layer that is arranged on the opposite side of the substrate from the ink layer of the first layer
  • OP varnish layer overprint varnish layer
  • a layer containing a colorant e.g., a colored pigment
  • an ink layer a layer not containing the colorant
  • a primer layer or an OP varnish layer both are collectively referred to as varnish layers
  • the second layer may contain a colorant or may not contain a colorant.
  • the ink layer is made of multiple printed layers (e.g., white and color layers)
  • one layer may be an ink layer made of the first layer and the other layer may be an ink layer made of the second layer, as shown in the above embodiment.
  • an ink layer consisting of a first layer and a second layer may further be provided with a primer layer or an OP varnish layer separate from the first layer and the second layer, for example, in the following embodiments.
  • a third layer that promotes detachment may be disposed between the substrate and the coating.
  • the following aspects may be mentioned.
  • an OP varnish layer may be further disposed on the primer layer (second layer) and the ink layer (first layer), and examples thereof include the following embodiments.
  • a varnish layer such as a primer layer or an OP varnish layer can be formed using a composition for forming a varnish layer.
  • a composition for forming the varnish layer a generally known composition can be used.
  • the varnish layer forming composition that forms the primer layer or the OP varnish layer contains the above-mentioned resin B.
  • the varnish layer-forming composition in addition to resin B, the components of varnish layer-forming compositions for forming primer layers or OP varnish layers that are commercially available without any particular limitation can be used.
  • 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 composition for forming the primer layer or the OP varnish layer is a composition that does not contain resin B and is generally known as a composition for forming a varnish layer.
  • binder resins examples include cellulose resins, urethane resins, polyamide resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, and petroleum resins (excluding resin B); radical copolymers of polymerizable monomers such as (meth)acrylic resins, styrene-(meth)acrylic resins, styrene-maleic acid (anhydride) resins, and terpene-maleic acid (anhydride) resins, copolymerized with polymerizable monomers such as polymerizable monomers having a carboxyl group, such as itaconic acid, maleic acid,
  • the solvent may be an organic solvent or water, for example, the same organic solvents as those described in the ⁇ Organic Solvent>> section above can be used.
  • the additives include extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, antiblocking agents, infrared absorbing agents, ultraviolet absorbing agents, fragrances, and flame retardants.
  • the amount of resin added can be determined appropriately within a range that does not impair the properties of the varnish layer, but it is preferable that the amount be in the range of 0.1 to 10 mass % relative to the total mass of the varnish layer composition, for example.
  • a varnish layer to which a resin having an acidic group or a low molecular weight compound has been added can be preferably used.
  • the resin having an acidic group or the low molecular weight compound that can be used as long as it can be easily mixed with the resin B, which is the main component of the varnish layer, or with an organic solvent, etc.
  • resins having acidic groups include cellulose resins, urethane resins, polyamide resins, ketone resins, polyester resins, (meth)acrylic resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, cyclized rubber, chlorinated rubber, butyral resins, and petroleum resins to which an acid value has been imparted; resins that are radical copolymers of (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 acidic groups, such as polymerizable monomers having carboxyl groups, such as it
  • low molecular weight compounds having an acidic group include organic acids such as 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.
  • Examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and sorbic acid.
  • Examples of hydroxy acids include lactic acid, malic acid, and citric acid.
  • Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, and ketone.
  • Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, undecane diacid, dodecane diacid, dimer acid, fumaric acid, maleic acid, azelaic acid, etc.
  • Examples of the tricarboxylic acid include aconitic acid and trimer acid, etc.
  • Examples of the oxocarboxylic acid include pyruvic acid and oxaloacetic acid, etc.
  • Examples of the carboxylic acid derivative include amino acid and nitrocarboxylic acid, 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. can comply with the so-called Swiss Ordinance, and it is preferable to use substances that comply with various regulations.
  • the laminate according to the present invention can be produced, for example, by the following method.
  • a printing ink of a composition (I) for forming the first layer is printed on the plastic substrate by a printing method such as gravure printing or flexographic printing to form the ink layer 1 (first layer), which is a printed layer.
  • a printing ink of a composition (II) for forming the second layer is printed on the ink layer 1 by a printing method such as gravure printing or flexographic printing to form the ink layer 2 (second layer), which is a printed layer.
  • the coating film of the printed matter of the present invention described above can be removed from the substrate by treating it with an alkaline solution to produce a recycled substrate.
  • Decoration refers to the peeling off of the coating due to swelling, dissolution, erosion, etc. caused by the alkaline solution treatment.
  • the layer directly provided on the substrate must have a detachment function. For example, when an ink layer (first layer) is provided on the substrate, the first layer must have the detachment function, or when a primer layer (second layer) is provided on the substrate, the second layer must have the detachment function.
  • the detachment of the layer provided on the substrate causes the other layers to detach together, and since the second layer contains resin B, coloring of the alkaline solution after detachment is suppressed.
  • the first layer may be a layer having a releasing function
  • the second layer may be a layer not having a releasing function.
  • 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 tends to become more colored after detachment than when the alkaline solution is used alone, but by configuring the printed matter of the present invention in such a way that a second layer containing resin B is laminated adjacent to a first layer containing a colorant as a film that can be detached from the substrate, coloring of the treatment solution can be effectively suppressed.
  • 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 coating formed on a substrate, in which a first layer containing a colorant and a second layer containing resin B are laminated adjacent to each other. Therefore, the presence of resin B can effectively suppress coloration of the alkaline treatment solution when the coating is removed in the removal step.
  • 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
  • varnish composition The raw materials used in varnish composition 1 (also referred to as Varnish 1) to varnish composition 15 (also referred to as Varnish 15) are as follows.
  • ⁇ Resin> CAB1 Cellulose acetate butyrate resin (Eastman Chemical Company, CAB-381-0.1)
  • CAB2 Cellulose acetate butyrate resin Eastman Chemical Company, CAB-151-202
  • Vinyl chloride-vinyl acetate copolymer resin Solvin A, manufactured by Nissin Chemical Co., Ltd.
  • Vinyl chloride-vinyl acetate copolymer resin Non-volatile content 25%, methyl ethyl ketone soluble, PVB1 Polyvinyl butyral resin (Mowital B14S manufactured by Kuraray), non-volatile content 15%, ethanol
  • Varnish Compositions 1 to 15 are as shown in Tables 2-1 to 2-3 below.
  • Example 1 ⁇ Production of printed matter>
  • the prepared ink composition (also simply called ink) was printed on a substrate using a bar coater #4 to form a solid pattern of 240 mm length x 80 mm width, and then dried with a dryer to form an ink layer.
  • the prepared varnish composition (also simply called varnish) was printed on the dried ink layer using a bar coater #4, and after printing, was dried with a dryer to form an OP varnish layer, and a printed matter having the following configuration was obtained, which is a laminate in which an ink layer (first layer) and an OP varnish layer (second layer) are laminated on a substrate.
  • the surfactant used was a nonionic surfactant.
  • 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 13 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 sample used in Example 14 was 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 15 to 27 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 5, immersed in 500 mL of alkaline solution, and stirred with a stirrer.
  • the blank samples used in Examples 28 to 40 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 8, 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 print obtained using the ink composition of Comparative Example 11, and the samples were used after immersing them in 500 mL of alkaline solution and stirring with a stirrer.
  • Example 2 to 53 Comparative Examples 1 to 13
  • 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 3-1 to 3-9 below.
  • the obtained prints were evaluated in the same manner as in Example 1. The results are shown in Tables 3-1 to 3-9.
  • the varnish composition prepared was printed on the substrate using bar coater #4 in the same manner as in Example 1, and after printing, it was dried with a dryer to form a primer layer.
  • the prepared ink composition was printed on the dried primer layer using bar coater #4, and after printing, it was dried with a dryer to form an ink layer, and a printed matter having the following configuration was obtained, which is a laminate in which a primer layer (second layer) and an ink layer (first layer) are laminated in this order on a substrate.
  • a printed matter having the following configuration was obtained, which is a laminate in which a primer layer (second layer) and an ink layer (first layer) are laminated in this order on a substrate.
  • the printed matter of the examples has a coating that can be easily detached from the substrate by treatment with an alkaline solution, and it is clear that the coating has an excellent discoloration suppression effect against the discoloration of the alkaline solution treatment liquid.

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)
  • Laminated Bodies (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 substrat en plastique par un traitement avec 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'article imprimé comprend un stratifié d'un substrat et un film de revêtement qui peut être retiré du substrat par un traitement avec une solution alcaline, le film de revêtement comprenant : une première couche qui contient un colorant et au moins une résine A choisie dans le groupe constitué de résines acryliques, résines d'uréthane, résines de polyamide, résines de colophane et résines de polyester ; et une seconde couche qui est en contact avec la première couche. La seconde couche contient au moins une résine B choisie dans le groupe constitué de résines de copolymère de chlorure de vinyle/acétate de vinyle, résines de poly(butyral de vinyle), résines de propionate d'acétate de cellulose et résines de butyrate d'acétate de cellulose.
PCT/JP2024/018769 2023-06-08 2024-05-22 Article imprimé et procédé de production de panneau recyclé Pending WO2024252925A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2024563828A JP7708334B2 (ja) 2023-06-08 2024-05-22 印刷物、及びリサイクル基材の製造方法
CN202480018848.9A CN120882563A (zh) 2023-06-08 2024-05-22 印刷物及再循环基材的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023-094632 2023-06-08
JP2023094632 2023-06-08

Publications (1)

Publication Number Publication Date
WO2024252925A1 true WO2024252925A1 (fr) 2024-12-12

Family

ID=93795472

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/018769 Pending WO2024252925A1 (fr) 2023-06-08 2024-05-22 Article imprimé et procédé de production de panneau recyclé

Country Status (3)

Country Link
JP (1) JP7708334B2 (fr)
CN (1) CN120882563A (fr)
WO (1) WO2024252925A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031899A (ja) * 1999-07-21 2001-02-06 Dainichiseika Color & Chem Mfg Co Ltd 脱離性インキ組成物及び該インキ組成物を印刷物から脱離する方法
JP2021088408A (ja) * 2019-11-25 2021-06-10 東洋インキＳｃホールディングス株式会社 包装材、包装容器及びリサイクル基材製造方法
JP2022101885A (ja) * 2020-12-25 2022-07-07 東洋インキＳｃホールディングス株式会社 リサイクルオレフィン基材製造方法
WO2023032997A1 (fr) * 2021-09-02 2023-03-09 東洋インキＳｃホールディングス株式会社 Matériau d'emballage, matériau de moulage recyclé et leurs procédés de fabrication
JP2023075977A (ja) * 2021-11-22 2023-06-01 東洋インキＳｃホールディングス株式会社 積層体の分離回収方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031899A (ja) * 1999-07-21 2001-02-06 Dainichiseika Color & Chem Mfg Co Ltd 脱離性インキ組成物及び該インキ組成物を印刷物から脱離する方法
JP2021088408A (ja) * 2019-11-25 2021-06-10 東洋インキＳｃホールディングス株式会社 包装材、包装容器及びリサイクル基材製造方法
JP2022101885A (ja) * 2020-12-25 2022-07-07 東洋インキＳｃホールディングス株式会社 リサイクルオレフィン基材製造方法
WO2023032997A1 (fr) * 2021-09-02 2023-03-09 東洋インキＳｃホールディングス株式会社 Matériau d'emballage, matériau de moulage recyclé et leurs procédés de fabrication
JP2023075977A (ja) * 2021-11-22 2023-06-01 東洋インキＳｃホールディングス株式会社 積層体の分離回収方法

Also Published As

Publication number Publication date
JPWO2024252925A1 (fr) 2024-12-12
CN120882563A (zh) 2025-10-31
JP7708334B2 (ja) 2025-07-15

Similar Documents

Publication Publication Date Title
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
JP7197054B2 (ja) 脱離可能な水性インキ及びその脱離方法
JP7364120B2 (ja) 脱離可能な皮膜形成用組成物
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
WO2024071019A1 (fr) Procédé de séparation et de récupération pour 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
JP7683833B1 (ja) 印刷物、及びリサイクル基材の製造方法
JP7343077B2 (ja) 顔料組成物
JP7608681B2 (ja) リキッドインキ用バインダー樹脂、該バインダー樹脂を含むリキッドインキ、及び印刷物
JP7679343B2 (ja) プラスチック基材の分離回収方法
JP7416320B1 (ja) 積層体の製造方法
JP2022183764A (ja) 脱離可能な皮膜形成用組成物
JP7722223B2 (ja) 積層体
JP7401019B1 (ja) 積層体の分離回収方法
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
JP2025025753A (ja) 脱離可能な皮膜を有する積層体及びリサイクル基材の製造方法
JP2025033323A (ja) 積層体の分離回収方法

Legal Events

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

Ref document number: 2024563828

Country of ref document: JP

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

Ref document number: 24819158

Country of ref document: EP

Kind code of ref document: A1