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WO2025239198A1 - Stratifié, procédé de fabrication d'un stratifié, procédé de fabrication d'un substrat recyclé et procédé de fabrication de pastilles de plastique recyclé - Google Patents

Stratifié, procédé de fabrication d'un stratifié, procédé de fabrication d'un substrat recyclé et procédé de fabrication de pastilles de plastique recyclé

Info

Publication number
WO2025239198A1
WO2025239198A1 PCT/JP2025/016278 JP2025016278W WO2025239198A1 WO 2025239198 A1 WO2025239198 A1 WO 2025239198A1 JP 2025016278 W JP2025016278 W JP 2025016278W WO 2025239198 A1 WO2025239198 A1 WO 2025239198A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
resin
laminate
primer layer
substrate
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/JP2025/016278
Other languages
English (en)
Japanese (ja)
Inventor
達哉 神山
朋美 浅見
辰弥 山本
典幸 杉山
浩平 沖野
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
Publication of WO2025239198A1 publication Critical patent/WO2025239198A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • C09D11/10—Printing inks based on artificial resins
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a laminate, a method for manufacturing a laminate, a method for manufacturing a recycled substrate, and a method for manufacturing recycled plastic pellets.
  • Prior art discloses a method of removing a coating printed on a heat-shrinkable PET film containing a styrene-acrylic acid resin, a phenolic resin, or a styrene-maleic acid resin as a vehicle using alkaline water (Patent Document 1).
  • Patent Document 1 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 layers, and the coating layer is then removed using 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 health and environmental impacts to adjust the viscosity.
  • the coexistence of an amine value and an acid value will be avoided in order to reduce viscosity, resulting in problems such as reduced suitability for laminating applications. Therefore, challenges remain before the resin can be used generally as a material with a removable coating.
  • few of the technologies developed to promote the removal of the printing film mentioned above take into consideration the release of the removed film into the cleaning solution.In particular, the colored pigments contained in the ink are released into the cleaning solution during cleaning, causing coloration, which leads to wastewater treatment problems and actually increases the environmental load, but no effective solution has been clearly stated.
  • the problem that the present invention aims to solve is to provide a laminate that can remove a printed film from a plastic substrate by treatment with an alkaline solution, and that can suppress discoloration of the alkaline solution after removal.
  • the inventors discovered that the above problems could be solved by configuring a printed film that detaches from the substrate when treated with an alkaline solution, having a substrate (A), a primer layer, and a printed layer in that order, and by ensuring that the relationship between the glass transition points of the primer layer and the printed layer, etc., falls within an appropriate range, thereby completing the present invention.
  • the present invention includes the following aspects.
  • a substrate (A), a primer layer, and a printing layer in this order contains a urethane resin (B) having a glass transition temperature of ⁇ 40° C. or higher and 70° C. or lower, the printing layer contains a pigment and a binder resin (C), the binder resin (C) contains 10% by mass or more of a resin (D) having at least one of a glass transition point, a melting point, and a softening point of 50°C or more and 170°C or less; A laminate, wherein at least one of the glass transition point, melting point, and softening point of the resin (D) is higher than the glass transition point of the urethane resin (B).
  • the laminate further includes a substrate (E) different from the substrate (A), The laminate according to any one of [1] to [10], wherein the substrate (E) is disposed on the surface of the printed layer opposite to the surface on which the substrate (A) is disposed, and the substrate (A), the primer layer, the printed layer, and the substrate (E) are laminated together.
  • a method for manufacturing a laminate [13] A method for producing a recycled material, comprising treating the laminate according to any one of [1] to [11] with an alkaline solution to remove the primer layer and the printed layer from the substrate (A), thereby obtaining a recycled material. [14] The method for producing a recycled material according to [13], wherein the laminate is treated with an alkaline solution at 70°C or higher and 90°C or lower to obtain a recycled substrate. [15] A method for producing recycled plastic pellets, comprising melting the recycled material obtained by the method for producing recycled material according to [14] and molding it with a molding machine.
  • the present invention provides a laminate that can remove a printed film from a plastic substrate by treatment with an alkaline solution, and that can suppress discoloration of the alkaline solution after removal.
  • the glass transition point refers to the glass transition point of the thermoplastic resin to be measured, and in this specification, the measured value in accordance with JIS K 7121:2012 (Method for measuring transition temperature of plastics) is adopted.
  • the melting point refers to the temperature at which the crystalline thermoplastic resin to be measured begins to flow, and is measured in accordance with JIS K 0064:1992 (Method for measuring melting point and melting range of chemical products).
  • the softening point refers to the temperature at which the thermoplastic resin to be measured begins to soften and deform when heated, and a measurement value in accordance with JIS K 6863:1994 (Test method for softening point of hot melt adhesives) is adopted.
  • the laminate of the present invention essentially comprises a substrate (A), a primer layer, and a printed layer in this order. Each layer will be described in detail below.
  • the substrate (A) is a base on which a primer layer, a printed plastic layer, etc. are laminated, and a plastic substrate is preferred, and examples thereof include 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, polyhydroxycarboxylic acids such as polylactic acid, biodegradable resins such as aliphatic polyester resins such as poly(ethylene succinate) and poly(butylene succinate), and thermoplastic resins such as polyolefin resins such as polypropylene and polyethylene, polyimide resins, polyarylate resins, and mixtures thereof, and laminates thereof.
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • polytrimethylene terephthalate polytrimethylene terephthalate
  • films and laminates made of polyethylene terephthalate, polyester, polyamide, polyethylene, and polypropylene are preferably used, and when the release properties of the composition according to the present invention are important, polyethylene terephthalate, polypropylene, or polyethylene are more preferred.
  • the films used for these substrates may be unstretched or stretched films, and their manufacturing method is not limited.
  • the thickness of the film is not particularly limited, but is usually in the range of 1 ⁇ m to 500 ⁇ m.
  • the printing surface of the substrate (A) is preferably surface-modified by corona discharge treatment or chemical treatment, and may be vapor-deposited with silica, alumina, or the like.
  • the primer layer contains at least a urethane resin (B).
  • the glass transition point of the urethane resin (B) is ⁇ 40° C. or higher and 70° C. or lower, preferably ⁇ 30° C. or higher and 65° C. or lower, and more preferably ⁇ 20° C. or higher and 60° C. or lower.
  • the glass transition point of the urethane resin (B) used in the primer layer is 70° C. or lower, the printed layer can be detached from the substrate at low temperatures, and when the glass transition point is ⁇ 40° C. or higher, sufficient adhesion between the substrate and the printed layer can be maintained at room temperature.
  • the ester bond group concentration of the urethane resin (B) is preferably 1 mmol/g or more, more preferably 2 mmol/g or more, from the viewpoint of improving the substrate adhesion and deinking ability of the resulting primer layer. Furthermore, from the viewpoint of good blocking resistance of the primer layer, the concentration is preferably 8 mmol/g or less, more preferably 7 mmol/g or less. From the same viewpoint, the thickness of the primer layer is preferably 0.2 ⁇ m or more and 1.0 ⁇ m or less, more preferably 0.3 ⁇ m or more and 0.5 ⁇ m or less.
  • the print layer contains at least a pigment and a binder resin (C), each of which will be described in detail below.
  • Examples of the pigment used in the present invention include inorganic pigments and organic pigments used in general inks, paints, recording agents, etc. From the viewpoint of effectively suppressing coloration of the alkaline solution after desorption, organic pigments are 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, cromophtal yellow, cromophtal 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 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.
  • pigments include C.I. Pigment Blue 63, C.I. Pigment Blue 64, C.I. Pigment Blue 75, C.I. Pigment Blue 79, and C.I. Pigment Blue 80.
  • 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 examples include 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. 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.
  • pigments include C.I. Pigment Red 266, C.I. Pigment Red 268, C.I. Pigment Red 269, C.I. Pigment Red 270, C.I. Pigment Red 271, C.I. Pigment Red 272, and C.I. Pigment Red 279.
  • 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. Examples include C.I. Pigment Violet 38, C.I. Pigment Violet 42, and C.I. Pigment Violet 50.
  • 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.
  • suitable 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 Orange 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 indigo pigments, 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.
  • pigments that can be used 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 pigments selected from these groups.
  • Inorganic pigments include carbon black, titanium oxide, red iron oxide, aluminum, mica, zinc oxide, barium sulfate, calcium carbonate, and silica. Also usable are lustrous pigments (Metashine; Nippon Sheet Glass Co., Ltd.) made from glass flakes or aggregate flakes coated with a metal or metal oxide. From the standpoint of cost and coloring strength, 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 a composition that forms a printing layer, from the viewpoint of ensuring the coloring power of the composition, the pigment content is preferably 1% by mass or more and 60% by mass or less, and more preferably 5% by mass or more and 40% by mass or less, relative to 100% by mass of the total composition.
  • the total white pigment content may be 15% by mass or more and 60% by mass or less, or 20% by mass or more and 40% by mass or less, relative to 100% by mass of the total composition.
  • the total colored organic pigment content may be 1% by mass or more and 30% by mass or less, or 5% by mass or more and 25% by mass or less, relative to 100% by mass of the total pigment composition. Any combination of these upper and lower limits may be used.
  • the binder resin (C) contains 10% by mass or more of the resin (D).
  • the binder resin (C) preferably contains 20% by mass or more of the resin (D), more preferably 30% by mass or more, and even more preferably consists of only the resin (D).
  • the binder resin (C) may contain a resin (X) other than the resin (D). The details of the resin (D) and the resin (X) are described below.
  • At least one of the glass transition point, melting point, and softening point of resin (D) is 50° C. or higher and 170° C. or lower, and at least one of the glass transition point, melting point, and softening point is higher than the glass transition point of urethane resin (B), preferably by 10° C. or more, and more preferably by 20° C. or more.
  • the glass transition point or the like of resin (D) is preferably 60°C or higher and 160°C or lower, more preferably 80°C or higher and 150°C or lower.
  • resin (D) is preferably one or more resins selected from vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, cellulose-based resin, and polyamide resin.
  • the resin (X) in the binder resin (C) examples include resins such as cellulose-based 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; and radical copolymers such as (meth)acrylic resins, styrene-(meth)acrylic resins, styrene-(meth)acrylic resins, styrene-(anhydride)maleic acid resins, and terpene-(anhydride)maleic acid resins copolymerized with polymerizable mono
  • the thickness of the printing layer is preferably 0.3 ⁇ m to 7.0 ⁇ m, and more preferably 0.5 ⁇ m to 4.0 ⁇ m.
  • the preferred range of printing layer thickness varies depending on the type of coloring; more specifically, for single color printing, a thickness of 0.5 ⁇ m to 0.7 ⁇ m is preferred, for single white printing, a thickness of 1.1 ⁇ m to 1.3 ⁇ m is preferred, for color/white printing, a thickness of 1.5 ⁇ m to 2.1 ⁇ m is preferred, and for four color/white double printing, a thickness of 6 ⁇ m or less is preferred.
  • the ratio of the thickness of the primer layer to the thickness of the printed layer is preferably 0.02 or more and 3.4 or less, and more preferably 0.10 or more and 3.0 or less.
  • Each layer constituting the laminate may further contain other components such as an auxiliary agent and an acidic additive, if necessary.
  • Auxiliaries that can be used as appropriate include waxes such as paraffin wax, polyethylene wax, and carnauba wax to impart abrasion resistance and slipperiness; fatty acid amide compounds such as oleic acid amide, stearic acid amide, and erucic acid amide; silicone and non-silicone antifoaming agents to suppress foaming during printing; and dispersants.
  • waxes such as paraffin wax, polyethylene wax, and carnauba wax to impart abrasion resistance and slipperiness
  • fatty acid amide compounds such as oleic acid amide, stearic acid amide, and erucic acid amide
  • silicone and non-silicone antifoaming agents to suppress foaming during printing
  • dispersants Nonionic dispersants are preferred as dispersants.
  • water, wetting agents, adhesion promoters, leveling agents, antistatic agents, viscosity modifiers, metal chelates, trapping agents, antiblocking agents, isocyanate-based curing agents, and silane coupling agents may also be used as needed.
  • the embodiment of the laminate of the present invention is not particularly limited, but preferred examples include the following embodiment (1-A).
  • the laminate of the present invention is not limited to a laminate having a surface printing type structure in which a printed layer is formed on the surface of the laminate, as in the above-mentioned embodiment (1-A), but also encompasses a laminate having a laminate type structure in which a coating film (various layers or films) is further formed on the printed layer.
  • the laminate of the present invention also covers laminates having a laminate-type structure in which another substrate (substrate (E)) is placed on the side opposite to the side on which the substrate (substrate (A)) is placed relative to the printed layer, and the substrate (A), primer layer, printed layer, and substrate (E) are laminated together.
  • Examples of the laminate having a laminate type structure include the laminates of the following embodiments.
  • the substrate film 1 corresponds to the substrate (A) of the present invention.
  • films such as a sealant film, a metal-vapor-deposited unstretched film, or a transparent vapor-deposited stretched film may correspond to the substrate (A) of the present invention.
  • the substrate film 2 corresponds to the substrate (E) of the present invention.
  • films such as a sealant film, a metal-vapor-deposited unstretched film, or a transparent vapor-deposited stretched film may correspond to the substrate (E) of the present invention.
  • the substrate (E) refers to a film formed on the surface opposite the substrate (A) in the laminate.
  • the substrate (E) is not limited to a film disposed on the surface, and the substrate (E) may be present between layers, or multiple substrates (E) may be provided in the laminate.
  • a primer layer may be applied to both sides of the film positioned as the intermediate layer.
  • (2-7) Base film 1/primer layer/printing layer/adhesive layer 1/primer layer/transparent vapor-deposited stretched film/primer layer/adhesive layer 2/sealant film;
  • a primer layer may be applied to the film corresponding to the substrate (E) (the film located on the surface opposite to the substrate (A)).
  • (3-1) Base film 1/primer layer/printed layer/adhesive layer 1/primer layer/sealant film (3-2) Base film 1/primer layer/printed layer/adhesive layer 1/primer layer/metal-deposited unstretched film (3-3) Base film 1/primer layer/printed layer/adhesive layer 1/primer layer/metal-deposited stretched film (3-4) Base film 1/primer layer/printed layer/adhesive layer 1/base film 2/adhesive layer 2/primer layer/sealant film (3-5) Base film 1/primer layer/printed layer/adhesive layer 1/metal-deposited stretched film/adhesive layer 2/primer layer/sealant film (3-6) Base film 1/primer layer/printed layer/adhesive layer 1/metal-deposited stretched film/adhe
  • the primer layer on the surface of the vapor-deposited film (whether transparent or metallic, stretched or unstretched) facing the printed layer may be removed.
  • the vapor-deposited layer may be dissolved in an alkaline solution, allowing the primer layer formed on one surface of the vapor-deposited film to be removed.
  • one surface of the vapor-deposited film is located on the surface of the laminate, so the primer layer facing the other inner surface is removed.
  • the laminated body having a laminate type structure may have a laminate type structure in which a coating film (various layers or films) is further formed on the printed layer by extrusion lamination.
  • the laminate of the present invention also covers laminates having a laminate-type structure in which an extrusion laminate layer is placed on the side opposite to the side on which the substrate (substrate (A)) is placed relative to the printing layer, and the substrate (A), primer layer, printing layer, and extrusion laminate layer are laminated together.
  • Examples of the laminate having an extrusion laminate type structure include the laminates of the following embodiments.
  • the substrate film 1 corresponds to the substrate (A) of the present invention.
  • the extrusion laminate layer can be recovered and reused as a resin without a printed layer.
  • both the base film 1 and the extrusion laminate layer can be recovered and reused as a resin without a printed layer.
  • an “anchor layer for extrusion lamination” is provided on the printing layer, but an “extrusion lamination layer” may be provided directly on the "printing layer” without providing an “anchor layer for extrusion lamination.”
  • other layers such as a sealant layer may be disposed on the surface of the extrusion laminate layer opposite to the surface on which the base film 1 is provided.
  • the structures of the other layers are not limited to the following structures (5-1-1) to (5-1-6) and can be appropriately designed depending on the required properties.
  • the following is an example of a configuration in which another layer is provided in the configuration of (5-1) above.
  • a similar configuration is also possible in the configuration of (5-2) above.
  • Base film 1/primer layer/printed layer/extrusion laminate anchor layer/extrusion laminate layer/adhesive layer 1/sealant film (5-1-2) Base film 1/primer layer/printed layer/extrusion laminate anchor layer/extrusion laminate layer/adhesive layer 1/metal layer/adhesive layer 2/sealant film (5-1-3) Base film 1/primer layer/printed layer/extrusion laminate anchor layer/extrusion laminate layer/primer layer/adhesive layer 1/sealant film (5-1-4) Base film 1/plastic (5-1-4) Base film 1/primer layer/printing layer/extrusion laminate anchor layer/extrusion laminate layer/primer layer/adhesive layer 1/metal layer/adhesive layer 2/sealant film (5-1-5) Base film 1/primer layer/printing layer/extrusion laminate anchor layer/extrusion laminate layer/primer layer/adhesive layer 1/primer layer/sealant film 1/
  • the primer layer may be formed by an in-line coating method in which a urethane resin composition is applied during the film stretching process and then a further stretching process is performed, or the primer layer may be formed by an offline coating method in which a urethane resin composition is applied and dried after the film stretching process to form the primer layer.
  • the printed layer can be formed using various printing methods such as gravure printing, flexographic printing, offset printing, inkjet printing, and screen printing.
  • the printing ink used can be appropriate for the various printing methods, and may be either a solvent-based ink or a water-based ink. UV-curable or EB-curable ink may also be used.
  • the sealant film examples include a CPP film (unstretched polypropylene film) and an LLDPE film (linear low-density polyethylene resin film).
  • a VM-CPP film obtained by vapor-depositing a metal such as aluminum onto a CPP film can be used.
  • a metal-deposited stretched film a VM-OPP film obtained by depositing a metal such as aluminum on an OPP film can be used.
  • the transparent vapor-deposited stretched film examples include films obtained by depositing silica or alumina on OPP films, PET films, nylon films, etc.
  • a film having a coating applied to the vapor-deposited layer may also be used.
  • the metal layer may be an aluminum foil or the like.
  • the adhesive layer can be formed using a known adhesive for film lamination.
  • a known anchor coating agent for extrusion lamination can be used as an adhesive aid.
  • the use of a material having gas barrier properties for these adhesives or anchor coating agents can result in a laminate with particularly excellent barrier properties.
  • Particularly preferred adhesives with excellent gas barrier properties are those that satisfy at least one of the following conditions: an oxygen barrier property of 300 cc/ m2 /day/atm or less, or a water vapor barrier property of 120 g/ m2 /day or less, of a cured coating film of the adhesive applied at 3 g/ m2 (solid content).
  • the extrusion laminate layer can be made of a known thermoplastic resin, such as a polyolefin resin such as a polyethylene resin or a polypropylene resin, but is not limited to these materials.
  • Various known anchor coating agents can be used for the anchor layer for extrusion lamination. Examples include, but are not limited to, isocyanate-based and amine polymer-based materials.
  • the “anchor layer for extrusion lamination” may also be formed using the urethane resin composition of the present invention. Forming the "anchor layer for extrusion lamination” using the urethane resin composition of the present invention improves adhesion to the extrusion laminate layer and also improves the deinking properties of the extrusion laminate layer during peeling treatment.
  • the laminate of the present invention can be suitably used as a molding for electronic equipment, building materials, textiles, leather, home appliances, vehicles, furniture, office supplies, play equipment, sporting goods or parts thereof, or as a packaging material.
  • it can also be used as a multi-layer packaging material.
  • the layer structure can be changed depending on the contents, the environment of use, and the form of use.
  • the packaging material for example, the contents are filled through the opening, and then the opening is heat-sealed to produce a product using the packaging material formed from the laminate of the present invention.
  • the use of the packaging material is not particularly limited, but it can be used as a packaging material for, for example, food, medicine, sanitary products, cosmetics, electronic equipment, building materials, industrial materials, etc., and is particularly effectively applied to electronic equipment.
  • the printed film (primer layer and printed layer) of the laminate of the present invention When the printed film (primer layer and printed layer) of the laminate of the present invention is removed from the substrate by treatment with an alkaline solution, it exhibits a significant effect of inhibiting discoloration of the alkaline solution after removal. This makes it possible to prevent water pollution and environmental impact caused by colored wastewater. In addition, since raw materials and manufacturing equipment are not required for the decolorization treatment of colored wastewater, it is possible to reduce manufacturing costs when recycling the substrate. Furthermore, since no decolorization treatment step is required and the substrate is highly recycled efficiently, it is industrially useful.
  • the method for producing a laminate according to the present invention includes a primer layer forming step of forming a primer layer on a substrate (A), and a printing layer forming step of forming a printing layer on the primer layer following the primer layer forming step.
  • the primer layer contains a urethane resin (B) having a glass transition point of -40°C or higher and 70°C or lower, and the binder resin (C) of the printing layer contains 10 mass% or more of a resin (D) having at least one of a glass transition point, a melting point, and a softening point of 50°C or higher and 170°C or lower, and at least one of the glass transition point, the melting point, and the softening point of the resin (D) is higher than the glass transition point of the urethane resin (B).
  • the methods used in the primer layer forming step and the printing layer forming step are not particularly limited, and conventionally known methods can be used.
  • each layer may be mixed all at once, or they may be mixed in portions, such as by first mixing some of them to form a premix and then mixing it with the other components.
  • the mixing method is not particularly limited, and examples include a method of stirring and mixing using a mixer, a method using a three-roll mill, and a method using a disperser such as a bead mill.
  • Organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbon organic solvents such as toluene, xylene, Solvesso #100, and Solvesso #150; aliphatic hydrocarbon organic solvents such as hexane, methylcyclohexane, heptane, octane, and decane; and various ester organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate.
  • aromatic hydrocarbon organic solvents such as toluene, xylene, Solvesso #100, and Solvesso #150
  • aliphatic hydrocarbon organic solvents such as hexane, methylcyclohexane, heptane, octane, and decane
  • various ester organic solvents such as methyl a
  • 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 ether, and di
  • the method for producing a recycled material according to the present invention can produce a recycled material by treating the laminate of the present invention described above with an alkaline solution to remove the primer layer and the printed layer from the substrate (A).
  • Decoration refers to the peeling off of the printed film (primer layer and printed layer) due to swelling, dissolution, erosion, etc. caused by alkaline solution treatment.
  • the layer provided directly on the substrate must have a detachment function. For example, when a primer layer is provided on the substrate, the primer layer only needs to have a detachment function.
  • ⁇ Method for removing printed film from substrate> In the desorption step, although not particularly limited, it is preferable to obtain a recycled substrate by treating the laminate with an alkaline solution at 70° C. or higher and 90° C. or lower. It is more preferable to simultaneously carry out heating and stirring and ultrasonic vibration.
  • 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, or potassium dihydrogen carbonate.
  • the aqueous solutions of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium dihydrogen carbonate, or potassium dihydrogen carbonate are preferably aqueous solutions with a concentration of 0.5% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less.
  • the alkaline solution may also contain a water-soluble organic solvent.
  • water-soluble organic solvents 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.
  • 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, and these can 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 or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less.
  • the alkaline solution may also contain a water-insoluble organic solvent.
  • water-insoluble organic solvent examples 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-based solvents such as methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; and ether-based solvents such as ethyl ether and butyl ether
  • the alkaline solution may also contain a surfactant.
  • surfactants include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Of 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, sulfate ester salts of higher fatty acid esters, sulfonates of higher fatty acid esters, sulfate ester salts and sulfonates of higher alcohol ethers, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.
  • 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 alkylolamides, alkylalkanolamides, acetylene glycol, oxyethylene adducts of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymers.
  • 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 alkylolamides, acetylene glycol, oxyethylene adducts of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymers are preferred.
  • surfactants that can be used include silicone 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, rhamnolipid, and lysolecithin.
  • silicone surfactants such as polysiloxane oxyethylene adducts
  • fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers
  • biosurfactants such as spiculisporic acid, rhamnolipid, 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% by mass to 2% by mass, more preferably 0.001% by mass to 1.5% by mass, and even more preferably 0.01% by mass to 1% by mass, based on the total amount of alkaline solution.
  • the alkaline solution tends to become more discolored after detachment than when the alkaline solution is used alone.
  • the laminate 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 printing film that can be detached from the substrate, discoloration of the treatment solution can be effectively suppressed.
  • the target laminate is immersed in an alkaline solution, for example in a treatment tank, while the alkaline solution is heated or ultrasonically vibrated at a temperature of 70 to 90°C.
  • an alkaline solution for example in a treatment tank
  • ultrasonically vibrated at a temperature of 70 to 90°C.
  • heating method there are no particular limitations on the heating method, and known heating methods such as heat rays, infrared rays, and microwaves can be used.
  • Ultrasonic vibration can also be achieved by attaching an ultrasonic vibrator to the treatment tank and applying ultrasonic vibration to the warm water or alkaline solution.
  • stirring methods include, for example, mechanically stirring the dispersion of the laminate contained in the treatment tank using a stirring blade, water jet stirring using a water jet 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 laminate is immersed in the alkaline solution will vary depending on the composition of the laminate, but is generally in the range of 2 minutes to 48 hours. In the present invention, it is not necessary for 100% of the printed film in the laminate to be completely detached from the substrate; however, it is preferable for at least 60% by mass of the 100% printed film to be detached, more preferably at least 70% by mass, even more preferably at least 80% by mass, and particularly preferably at least 90% by mass.
  • 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.
  • immersion is performed multiple times in the desorption process, the concentration of the alkaline solution may be changed.
  • known processes such as washing with water and drying may also be added as appropriate.
  • the primer layer contains urethane resin (B) with a glass transition point of -40°C or higher and 70°C or lower, and is therefore easily removed by an alkaline solution of 70°C or higher and 90°C or lower.
  • a pigment-containing printing layer and a primer layer are laminated adjacent to each other, so the primer layer will be removed from the substrate along with the adjacent printing layer.
  • the printing layer contains a pigment and binder resin (C), which contains 10% by mass or more of resin (D) having at least one of a glass transition point, melting point, or softening point of 50°C or higher and 170°C or lower.
  • At least one of the glass transition point, melting point, or softening point of resin (D) is higher than the glass transition point of urethane resin (B). Therefore, binder resin (C) does not dissolve even at temperatures at which the primer layer would be removed, and coloration of the alkaline treatment solution when the printing film is removed in the removal process can be suppressed.
  • the recycled base material obtained by the above-described method for producing a recycled base material can be molded in a molding machine to obtain recycled plastic pellets.
  • the crusher used for crushing (pulverizing) is not particularly limited and any known crusher may be used.
  • the pulverized film pieces are physically blended using methods such as melt kneading, solvent cast blending, latex blending, and polymer complexing. Melt kneading is particularly common. Examples of kneading devices include tumblers, Henschel mixers, rotary mixers, super mixers, ribbon tumblers, and V-blenders.
  • the film pieces are melt-kneaded using such kneading devices and then pelletized.
  • a single-screw or multi-screw extruder is typically used for melt kneading and pelletization.
  • the film pieces may be fed as they are, or may be compressed with or without heating before being fed.
  • Banbury mixers, rollers, Ko-kneaders, blast mills, and Prabender-Bloutographs may also be used, and these may be operated batchwise or continuously.
  • the film pieces may be used as molding resins and melt-kneaded in the heating barrel of a molding machine without being melt-kneaded.
  • Polyol The compositions and physical properties of polyols 1 to 5 used in the examples and comparative examples are shown in Table 1 below.
  • TPA represents terephthalic acid
  • IPA represents isophthalic acid
  • AA represents adipic acid
  • EG represents ethylene glycol
  • DEG diethylene glycol
  • 14BG represents 1,4-butylene glycol.
  • Polyol 1 in Table 1 indicates that an aromatic polyester polyol was produced by mixing and reacting 0.32 g of terephthalic acid, 0.32 g of isophthalic acid, 0.13 g of ethylene glycol, and 0.23 g of diethylene glycol.
  • ⁇ Aromatic ring concentration (mmol/g)> The number of moles of aromatic rings contained in 1 g of polyol was calculated based on the raw materials used in the synthesis of the polyol and their blending amounts, and was determined by dividing the mass of the raw material monomer of aromatic dicarboxylic acid contained in 1 g of polyol by the molecular weight of the raw material monomer of aromatic dicarboxylic acid.
  • a represents the number of moles of carboxylic acid in 1 g of polyester polyol.
  • Primer 1 was synthesized by charging 0.74 g of Polyol 1, 0.20 g of isophorone diisocyanate, and 0.06 g of 2,2'-dimethylolpropionic acid into a four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, and reacting them at 75°C for 8 hours under a nitrogen stream.
  • the composition and physical properties of Primer 1 are shown in Table 2 below.
  • Primers 2 to 4 were prepared in the same manner as Primer 1 except that the composition was changed as shown in Table 2 below.
  • the compositions and physical properties of Primers 2 to 4 are shown in Table 2.
  • ⁇ Acid value (mgKOH/g)> The number of COOH groups contained in 1 g of primer (urethane resin) was determined in terms of the number of mg of KOH required when titrated by the potassium hydroxide method.
  • Primer 1 will be used as an example.
  • cellulose acetate propionate resin solution cellulose acetate propionate resin (CAP482-0.5 manufactured by Eastman Chemical Co.), 20% non-volatile content, dissolved in ethyl acetate and isopropyl alcohol.
  • 10% polyvinyl butyral resin solution polyvinyl butyral resin (S-LEC BL-10 manufactured by Sekisui Chemical Co., Ltd.), 10% non-volatile content, dissolved in ethyl acetate and isopropyl alcohol.
  • Polyamide resin 40% solution A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was charged with 100 parts of dimer acid (Haridimer 270S; manufactured by Harima Chemicals Co., Ltd.), 1 part of tall oil fatty acid (Hartall FA-1; manufactured by Harima Chemicals Co., Ltd.), 5 parts of sebacic acid, 10 parts of ethylenediamine, 5 parts of hexamethylenediamine, and 0.24 parts of triphenylphosphine. The system was then placed in a nitrogen atmosphere and heated slowly to 200 ° C. while stirring uniformly under a nitrogen stream. Subsequently, dehydration condensation was carried out at 200 ° C.
  • dimer acid-modified polyamide resin solution derived from tall fatty acid with a solids content of 40%, a softening point of 123 ° C., an amine value of 2, an acid value of 8, and a number average molecular weight of 10,000.
  • 30% nitrocellulose resin solution Nobel nitrocellulose DLX5-8, 30% nonvolatile content, dissolved in ethyl acetate and IPA.
  • 50% maleic acid resin solution maleic acid resin (Tomoe Engineering Co., Ltd. SMA 3000P), 50% nonvolatile content, dissolved in isopropyl alcohol.
  • 30% urethane resin solution DIC urea urethane resin, number average molecular weight 14,000, 30% nonvolatile content, dissolved in ethyl acetate and IPA.
  • 50% acrylic resin solution DIC Acrydic WCL-1419, number average molecular weight 16,000, 50% nonvolatile content, dissolved in ethyl acetate and IPA.
  • the glass transition point (Tg), melting point (MT), and softening point (SP) of each binder resin (C) are as shown in Table 3.
  • resins (D) those having at least one of the glass transition point, melting point, and softening point of 50°C or higher and 170°C or lower are specifically referred to as resins (D).
  • the blending ratios of the pigment, resin and organic solvent raw materials used in preparing inks 1 to 7 are shown in Table 4 below.
  • Tg glass transition point
  • MT melting point
  • SP softening point
  • Example 1 ⁇ Production of Laminate>
  • the primer 1 prepared as described above was printed on a substrate in a size of 240 mm length x 80 mm width using a bar coater #4, and then dried with a dryer to form a primer layer. A printed layer was then formed by drying with a dryer. Subsequently, the prepared ink 1 was printed on the dried primer layer using a bar coater #4, and after printing, the printed layer was dried with a dryer to form a printed layer, thereby obtaining a laminate having the following configuration, consisting of a primer layer (second layer) and a printed layer (first layer) laminated in this order on a substrate.
  • ⁇ Configuration of laminate>> Composition: substrate - primer layer - printing layer
  • Substrate PE film
  • peeling test was carried out for 5 to 60 minutes under each condition, and evaluation was carried out. Peeling within 5 minutes of treatment indicates excellent performance.
  • the laminate was cut into a size of 20 mm x 20 mm, and the cut test piece was immersed in the solution and stirred with a stirrer. After stirring, the state of peeling was confirmed, and then the laminate was rubbed with a finger to check whether the coating film peeled off by rubbing. The releasability of the printed layer under the above conditions was evaluated according to the following evaluation criteria.
  • the blank samples used in Examples 1 and 2 were 50 test pieces of the laminate obtained in Comparative Example 1 cut to a size of 20 mm x 20 mm, which were immersed in 500 mL of alkaline solution and stirred with a stirrer.
  • the blank samples used in Examples 3 and 4 were 50 test pieces of the laminate obtained using the ink composition of Comparative Example 4 cut to a size of 20 mm x 20 mm, which were immersed in 500 mL of alkaline solution and stirred with a stirrer.
  • the blank samples used in Examples 5 and 6 were 50 test pieces of the laminate obtained using the ink composition of Comparative Example 7 cut to a size of 20 mm x 20 mm, which were immersed in 500 mL of alkaline solution and stirred with a stirrer.
  • the blank samples used in Examples 7 and 8 were 50 test pieces of the laminate obtained using the ink composition of Comparative Example 10 cut to a size of 20 mm x 20 mm, which were immersed in 500 mL of alkaline solution and stirred with a stirrer.
  • test pieces were prepared by cutting the laminate obtained using the ink composition of Comparative Example 13 to a size of 20 mm x 20 mm, and these were immersed in 500 mL of alkaline solution and stirred with a stirrer.
  • 50 test pieces were prepared by cutting the laminate obtained using the ink composition of Comparative Example 16 to a size of 20 mm x 20 mm, and these were immersed in 500 mL of alkaline solution and stirred with a stirrer.
  • ⁇ Alkali resistance test> The laminate according to each example was immersed in 1% by mass of sodium hydroxide (without surfactant) at room temperature, and the state of decomposition after one day was visually evaluated according to the following evaluation criteria to evaluate alkali resistance.
  • the coloring of the cleaning liquid is predominantly influenced by the resin components of the printed layer, and in particular, the coloring was significant in laminates containing printed layers made of inks 1, 3, and 4, which used nitrocellulose resin, while the laminates containing inks 2, 5, and 6, which used vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, etc., showed excellent transparency. It was found that the alkali resistance tended to be poor in Primer 4, which had a Tg of -40°C or less. The pellet coloration was particularly poor in the laminate including the primer layer made of Primer 3, which had poor ink releasability, and the printed layers made of Inks 1, 3, and 4.
  • the pellet odor was particularly bad in the laminate including the primer layer made of Primer 3, which had poor ink releasability, and the printed layer made of Inks 2 and 6. Furthermore, in the laminates (Comparative Examples 19 to 23) including a printed layer consisting only of ink 7 without resin D, the Tg of the printed layer itself was low, so the ink removability was good, but the difference in glass transition temperature of the primer layer was small, so the cleaning liquid coloration characteristics were extremely poor and the alkali resistance was poor.

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Abstract

L'invention concerne un stratifié capable de désorber un film imprimé à partir d'un substrat en plastique par traitement par une solution alcaline et de supprimer la coloration de la solution alcaline après désorption. Un stratifié comprend un matériau de base (A), une couche de primaire et une couche d'impression dans cet ordre. La couche de primaire contient une résine d'uréthane (B) ayant un point de transition vitreuse de -40°C à 70°C. La couche d'impression contient un pigment et une résine liante (C), la résine liante (C) contenant 10% en masse ou plus d'une résine (D) ayant au moins l'un d'un point de transition vitreuse, d'un point de fusion ou d'un point de ramollissement de 50°C à 170°C, et au moins l'un du point de transition vitreuse, du point de fusion ou du point de ramollissement de la résine (D) étant supérieur au point de transition vitreuse de la résine d'uréthane (B).
PCT/JP2025/016278 2024-05-15 2025-04-28 Stratifié, procédé de fabrication d'un stratifié, procédé de fabrication d'un substrat recyclé et procédé de fabrication de pastilles de plastique recyclé Pending WO2025239198A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023026940A1 (fr) * 2021-08-25 2023-03-02 Dic株式会社 Composition de pigment
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
WO2023223711A1 (fr) * 2022-05-17 2023-11-23 Dic株式会社 Composition aqueuse de résine uréthane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023026940A1 (fr) * 2021-08-25 2023-03-02 Dic株式会社 Composition de pigment
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
WO2023223711A1 (fr) * 2022-05-17 2023-11-23 Dic株式会社 Composition aqueuse de résine uréthane

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