WO2023223711A1 - Aqueous urethane resin composition - Google Patents

Aqueous urethane resin composition Download PDF

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Publication number
WO2023223711A1
WO2023223711A1 PCT/JP2023/014561 JP2023014561W WO2023223711A1 WO 2023223711 A1 WO2023223711 A1 WO 2023223711A1 JP 2023014561 W JP2023014561 W JP 2023014561W WO 2023223711 A1 WO2023223711 A1 WO 2023223711A1
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WO
WIPO (PCT)
Prior art keywords
urethane resin
layer
primer layer
film
resin composition
Prior art date
Application number
PCT/JP2023/014561
Other languages
French (fr)
Japanese (ja)
Inventor
圭佑 若原
辰弥 山本
浩平 沖野
Original Assignee
Dic株式会社
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株式会社 filed Critical Dic株式会社
Priority to JP2023577805A priority Critical patent/JP7440003B1/en
Publication of WO2023223711A1 publication Critical patent/WO2023223711A1/en

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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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • 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 an aqueous urethane resin composition for forming a primer layer that is removable from a base material.
  • Patent Document 1 a method has been disclosed in which a film printed on a heat-shrinkable PET film containing a styrene-acrylic acid resin, a phenol resin, or a styrene-maleic acid resin as a vehicle is removed with alkaline water (Patent Document 1). ). Similarly, a coat layer containing a styrene-maleic acid resin, a rosin-maleic acid resin, and an acrylic acid copolymer resin is placed between the printing layers on a heat-shrinkable PET film, and the coated layer is soaked with alkaline water. A method for desorption is disclosed (Patent Document 2 and Patent Document 3).
  • Patent Document 7 a method using an aqueous composition for a removable primer layer is disclosed (Patent Document 7).
  • Patent Document 7 states that the releasability of the primer layer is strong alkali and can be removed even at low temperatures. That is, when the aqueous composition described in Patent Document 7 is used, Even under normal usage conditions, such as when strong alkaline substances such as detergents adhere to printed matter, the problem arises that the paint film, which is the primer layer, peels off.
  • the problem to be solved by the present invention is to remove the primer layer from a general-purpose plastic base material using a simple method, in order to simultaneously solve the above-mentioned marine plastic problem and the problems related to worker health and the environment. It is an object of the present invention to provide a material for forming a primer layer, which allows a printed layer to be easily removed from a substrate and which does not peel off due to strong alkaline substances under normally used temperature conditions.
  • the urethane resin (A) is made of a reaction product of an aromatic polyester polyol (a1) containing an aromatic dicarboxylic acid (a1-1) as a raw material monomer and a polyisocyanate (a2),
  • the aromatic ring concentration derived from the raw material monomer of the aromatic dicarboxylic acid (a1-1) in the urethane resin (A) is 1 mmol/g or more
  • the ester bond group concentration in the urethane resin (A) is 1 mmol/g or more
  • the value obtained by dividing the mass of the raw material monomer of the polyisocyanate (a2) contained in 1 g of the urethane resin (A) by the NCO equivalent weight of the raw material monomer of the polyisocyanate (a2) is 1.
  • the aqueous urethane resin composition according to [1] or [2] which has a content of 0 to 6.0 mmol/g.
  • the method for coating the aqueous urethane resin composition on the base material A is an in-line coating method in which the aqueous urethane resin composition is applied during the stretching process of the base material A, and then a further stretching process is performed. or the laminate according to [6], which is an offline coating method in which the aqueous urethane resin composition is applied and dried to form the primer layer after the step of stretching the base material.
  • the laminate according to [6] which is used as a molded product for electronic equipment, building materials, textiles/leather, home appliances, vehicles, furniture, office supplies, play equipment, sports equipment, or parts thereof, or as a packaging material.
  • a base material B is arranged on the surface of the printing layer opposite to the surface on which the base material A is arranged, and the base material A and the A laminate formed by laminating a primer layer, the printing layer, and the base material B.
  • a method for producing a recycled base material A which is obtained by treating the laminate according to [6] with an alkaline solution to remove the printing layer from the base material A together with the primer layer.
  • a primer layer can be easily removed from a general-purpose plastic substrate by a simple method, and a printing layer can be easily removed from a plastic substrate. This makes it possible to provide a material for forming the primer layer, which does not cause the primer layer to peel off.
  • the aqueous urethane resin composition of the present invention contains a urethane resin (A) and an aqueous medium (B).
  • the aqueous urethane resin composition of the present invention is produced by reacting an aromatic polyester polyol (a1) containing an aromatic dicarboxylic acid (a1-1) as a raw material monomer, a polyisocyanate (a2), and, if necessary, a chain extender, etc.
  • the urethane resin (A) obtained by this process is dispersed in an aqueous medium (B).
  • the aromatic ring concentration derived from the raw material monomer of the aromatic dicarboxylic acid (a1-1) in the urethane resin (A) is 1 mmol/g or more.
  • the ester bond group concentration in the urethane resin (A) is 1 mmol/g or more.
  • the acid value of the urethane resin (A) is 8 to 45 mgKOH/g.
  • Urethane resin (A) is a general term for polymer compounds having urethane bonds (-NHCOO-), and in the present invention, aromatic polyester polyol (a1) and polyisocyanate (a2) are reacted (crosslinking/curing reaction). It consists of a reactant obtained by Urethane resin (A) may further contain other polyols (a3) in addition to aromatic polyester polyol (a1) and polyisocyanate (a2), and aromatic polyester polyol (a1), polyisocyanate (a2) ), and a reaction product with other polyols (a3).
  • Aromatic polyester polyol (a1) can be produced, for example, by subjecting aromatic dicarboxylic acid (a1-1) and polyol (a1-2) to an esterification reaction.
  • aromatic dicarboxylic acid (a1-1) that can be used in producing the aromatic polyester polyol (a1) include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2, Aromatic dicarboxylic acids such as 5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-P,P'-dicarboxylic acid, and their acid anhydrides or ester-forming derivatives, aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and their ester-forming derivatives, sulfonic acid group-containing aromatic dicarboxylic acids such as 5-sulfoisophthalic acid, and their ester-forming derivatives. It will be done.
  • an aliphatic carboxylic acid or an alicyclic carboxylic acid can be used in combination.
  • aliphatic dicarboxylic acids such as succinic acid, succinic anhydride, adipic acid, suberic acid, azelaic acid, sebacic acid, dimer acid, maleic anhydride, fumaric acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid. , their anhydrides or ester-forming derivatives. These may be used alone or in combination of two or more.
  • polyol (a1-2) examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, and 1,3-butanediol. , 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, Neopentyl glycol and the like can be used.
  • the aromatic dicarboxylic acid (a1-1) and the polyol (a1-2) are heated at normal pressure or in a reaction vessel purged with an inert gas such as nitrogen in the presence of a catalyst if necessary.
  • the reaction can be carried out under reduced pressure.
  • the reaction is preferably carried out at a temperature in the range of 100°C to 300°C.
  • the catalyst for example, acetates of alkali metals or alkaline earth metals, compounds containing zinc, manganese, cobalt, antimony, germanium, titanium, tin, zirconium, etc. can be used. Among these, it is preferable to use tetraalkyl titanates and tin oxalate, which are effective in transesterification reactions, polycondensation reactions, and the like.
  • the same polyol as the above polyol (a1-2) can be used, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol. , dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5 Polyols of relatively low molecular weight such as -hexanediol, 1,6-hexanediol, 1,7-heptanediol, neopentyl glycol, etc. can be used.
  • polyisocyanate (a2) that reacts with the polyol (a1) to form the urethane resin (A)
  • aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate
  • Aliphatic or aliphatic cyclic structure-containing diisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used alone or in combination of two or more.
  • the urethane resin (A) is, for example, in the absence of a solvent or in the presence of an organic solvent, the above aromatic polyester polyol (a1), the above polyisocyanate (a2), and optionally the above polyol (a3), as necessary. It can be produced by reacting with a chain extender as appropriate.
  • the above-mentioned organic solvent it is preferable to remove the above-mentioned organic solvent by a method such as distillation as necessary when dispersing the above-mentioned urethane resin (A) in the aqueous medium (B).
  • organic solvents examples include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile.
  • ketones such as acetone and methyl ethyl ketone
  • ethers such as tetrahydrofuran and dioxane
  • acetate esters such as ethyl acetate and butyl acetate
  • nitriles such as acetonitrile.
  • Dimethylformamide, N-methylpyrrolidone, etc. can be used alone or in combination of two or more.
  • the chain extender that can be used when producing the urethane resin (A) can be used for the purpose of increasing the molecular weight of the urethane resin (A) and improving the durability of the resulting film.
  • the chain extender that can be used in producing the urethane resin (A) polyamines and other active hydrogen atom-containing compounds can be used.
  • polyamines examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl Diamines such as -4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydr
  • active hydrogen-containing compounds include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, neopentyl Glycols such as glycol, sucrose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc. phenols, water, etc. can be used.
  • the chain extender can be used when the aromatic polyester polyol (a1) and the polyisocyanate (a2) are reacted or after the reaction. Furthermore, a chain extender can also be used when dispersing the urethane resin (A) in the aqueous medium (B) to make it aqueous.
  • the aromatic ring concentration derived from the raw material monomer of the aromatic dicarboxylic acid (a1-1) in the urethane resin (A) is 1 mmol/g or more.
  • the aromatic ring concentration is determined by calculating the number of moles of aromatic rings contained in 1 g of urethane resin (A). A specific calculation method will be described later.
  • the aromatic ring concentration is preferably 1.5 mmol/g or more, more preferably 2 mmol/g or more, from the viewpoint of improving the substrate adhesion and deinking property of the resulting primer layer. From the viewpoint of good film-forming properties, etc., it is preferably 6 mmol/g or less, more preferably 5 mmol/g or less.
  • the ester bond group concentration in the urethane resin (A) is 1 mmol/g or more.
  • the concentration of ester bond groups is determined by calculating the number of moles of ester bond groups contained in 1 g of urethane resin (A). A specific calculation method will be described later.
  • the concentration of the ester bond group is preferably 2 mmol/g or more, more preferably 4 mmol/g or more, from the viewpoint of improving the substrate adhesion and deinking property of the resulting primer layer. From the viewpoint of good anti-blocking properties, it is preferably 9 mmol/g or less, more preferably 7 mmol/g or less.
  • the acid value of the urethane resin (A) is 8 to 45 mgKOH/g.
  • the acid value is a value obtained by converting the amount of acid in 1 g of resin, calculated by titrating the acid with an alkali, into mg of potassium hydroxide, and is a value determined according to JIS K0070.
  • the acid value is 8 mgKOH/g or more, water dispersion stability can be improved, and 15 mgKOH/g or more is preferable, and 20 mgKOH/g or more is more preferable.
  • the acid value is 45 mgKOH/g or less, good adhesion to the polyester base material can be ensured, and 40 mgKOH/g or less is preferable, and 30 mgKOH/g or less is more preferable.
  • the value obtained by dividing the mass of the raw material monomer of polyisocyanate (a2) contained in 1 g of urethane resin (A) by the NCO equivalent weight of the raw material monomer of polyisocyanate (a2) is 1.0 to 6.0 mmol/ It is preferable that it is g. If the value is 1.0 mmol/g or more, the substrate adhesion and deinking properties of the resulting primer layer can be improved, and it is more preferably 1.5 mmol/g or more, and 1.8 mmol/g. It is more preferable that it is not less than g. If it is 6.0 mmol/g or less, the film forming properties of the primer layer can be ensured, and it is more preferably 5.0 mmol/g or less, and even more preferably 4.0 mmol/g or less.
  • the weight average molecular weight of the urethane resin (A) is preferably 10,000 to 100,000. From the viewpoints of blocking resistance to the base material, hydrolytic stability of the resin, etc., the weight average molecular weight of the urethane resin (A) is preferably 20,000 or more, more preferably 30,000 or more. Further, from the viewpoint of reducing viscosity during water dispersion, productivity, etc., it is preferably 80,000 or less, more preferably 60,000 or less.
  • the weight average molecular weight indicates a value measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used by connecting them in series. "TSKgelG5000" (7.8mmI.D. x 30cm) x 1 "TSKgelG4000” (7.8mmI.D. x 30cm) x 1 "TSKgelG3000” (7.8mmI.D. x 30cm) x 1 "TSKgelG2000” ” (7.8mm I.D.
  • the glass transition temperature of the urethane resin (A) is preferably 0 to 110°C.
  • aqueous medium (B) serving as a solvent for the urethane resin (A) examples include water, organic solvents miscible with water, and mixtures thereof.
  • organic solvents that are miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; Alkyl ethers; N-methyl-2-pyrrolidone and the like.
  • water alone may be used, a mixture of water and a water-miscible organic solvent may be used, or only a water-miscible organic solvent may be used. From the viewpoint of safety and environmental impact, water alone or a mixture of water and an organic solvent miscible with water is preferred, and water alone is particularly preferred.
  • a machine such as a homogenizer can be used as necessary.
  • the aqueous urethane resin composition of the present invention preferably contains urethane resin (A) in a range of 5% to 50% by mass, and preferably 10% to 25% by mass, based on the total amount of the aqueous urethane resin composition. It is more preferable that the content be within a range. Further, the aqueous medium (B) is preferably contained in a range of 50% by mass to 95% by mass, more preferably in a range of 75% by mass to 90% by mass, based on the total amount of the urethane resin composition. preferable.
  • the aqueous urethane resin composition of the present invention may optionally contain a film-forming aid, a crosslinking agent, a curing accelerator, a plasticizer, an antistatic agent, a wax, a light stabilizer, a fluidity regulator, a dye, a leveling agent, a rheology agent, etc.
  • Various additives such as control agents, ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments, extender pigments, etc. can be used.
  • emulsifiers and leveling agents may cause a decrease in the durability of the obtained film, etc., so if high durability is required for the film, etc., 5% of the total amount of the water-based urethane resin composition is used. It is preferable to use it within a range of % by mass or less.
  • crosslinking agents can be used in combination with the aqueous urethane resin composition of the present invention in order to form a film etc. with excellent durability.
  • the crosslinking agent for example, isocyanate crosslinking agents, epoxy crosslinking agents, amino crosslinking agents, aziridine crosslinking agents, silane coupling agent crosslinking agents, carbodiimide crosslinking agents, oxazolidine crosslinking agents, etc. can be used.
  • the crosslinking agent is preferably used in an amount of 30% by mass or less, and 20% by mass or less, based on the total amount of the urethane resin (A), from the viewpoint of improving adhesion to the substrate and improving deinking performance. It is more preferable to use the range.
  • the crosslinking agent is preferably mixed and used immediately before coating the aqueous urethane resin composition of the present invention.
  • a primer layer can be formed by applying the aqueous urethane resin composition of the present invention onto a substrate. As described below, a printing layer made of a printing ink composition can be formed on the primer layer. The primer layer can be easily removed by treatment with an alkaline solution. Since the primer layer is easily peeled off from the base material, the printed layer formed on the primer layer can also be easily removed from the base material. A detailed explanation of the method for removing the primer layer will be given later.
  • the aqueous urethane resin composition of the present invention can be coated onto a substrate using known printing methods such as gravure printing and flexographic printing.
  • known printing methods include, for example, T-die coater, lip coater, knife coater, curtain, inkjet, bar coater, roll coater, spray coater, comma coater, and reverse roll.
  • Coater direct gravure coater, reverse gravure coater, offset gravure coater, roll kiss coater, reverse kiss coater, kiss gravure coater, reverse kiss gravure coater, air doctor coater, wire bar coater, dip coater, blade coater, brush coater, die slot
  • Any coating method such as a coater, an offset printing machine, a screen printing machine, etc. or a combination of two or more coating methods can be used.
  • water is mixed with an aqueous solution, such as an alcohol-based organic solvent such as ethyl alcohol, isopropyl alcohol, or n-propyl alcohol, to a viscosity and concentration suitable for various printing methods such as gravure printing and flexographic printing. It is diluted with a diluted solvent and supplied to each printing unit either alone or in a mixture.
  • an in-line method in which the aqueous urethane resin composition is applied during the stretching process (for example, biaxial stretching process) of the base material, and then a further stretching process is performed.
  • a coating method or an off-line coating method in which a primer layer is formed by applying an aqueous urethane resin composition and drying it after a step of stretching the base material e.g., a biaxial stretching step.
  • the present invention also provides a laminate having a primer layer formed using the aqueous urethane resin composition of the present invention.
  • the laminate of the present invention has a primer layer coated with the aqueous urethane resin composition of the present invention on a base material, and further has a printing layer formed by printing a printing ink composition on the primer layer. has.
  • Examples of embodiments of the laminate having a primer layer formed using the aqueous urethane resin composition of the present invention include, but are not limited to, the following embodiment (1-A).
  • the laminate of the present invention is not only 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 embodiment (1-A), but also a laminate that is coated on top of the printed layer. Also covered are laminates having a laminate type structure in which membranes (various layers or films) are formed. In other words, in the laminate of the present invention, another base material (for example, base material B) is placed on the surface opposite to the surface on which the base material (for example, base material A) is disposed with respect to the printed layer.
  • the present invention also covers a laminate type structure in which a base material A, a primer layer, a printing layer, and a base material B are laminated.
  • the laminate having a laminate type structure examples include laminates in the following embodiments.
  • the base film 1 corresponds to the base material A in the present invention.
  • each film such as a sealant film, a metal vapor deposited unstretched film, a transparent vapor deposited stretched film, etc. may correspond to the base material A in the present invention.
  • the base film 2 corresponds to the base material B in the present invention.
  • each film such as a sealant film, a metal vapor deposited unstretched film, a transparent vapor deposited stretched film, etc. corresponds to the base material B in the present invention.
  • the base material B refers to a film formed on the surface opposite to the base material A in the laminate, but in some cases, the base material B is not limited to the film disposed on the surface, but may be formed between the layers. In some cases, a plurality of base materials B are provided in the laminate.
  • a primer layer may be coated on both sides of the film located in the intermediate layer.
  • Base film 1/Primer layer/Print layer/Adhesive layer 1/Primer layer/Base film 2/Primer layer/Adhesive layer 2/Sealant film ⁇ (2-6) Base film 1/Primer Layer / Printing layer / Adhesive layer 1 / Primer layer / Metallized stretched film / Primer layer / Adhesive layer 2 / Sealant film (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 (2-9) Base film 1 / Primer layer / Printing layer / Adhesive layer 1 / Primer layer / Base film 2 / Primer layer / Adhesive layer 2 / Metal layer / Adhesive layer 3
  • Base film 1/Primer layer/Print layer/Adhesive layer 1/Primer layer/Sealant film ⁇ (3-2) Base film 1/Primer layer/Print 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) transparent vapor-deposited stretched film/primer layer/printed layer/ Adhesive layer 1 / Primer layer / Sealant film (3-5) Base film 1 / Primer layer / Printing layer / Adhesive layer 1 / Base film 2 / Adhesive layer 2 / Primer layer / Sealant film (3-6) Base film 1/Primer layer/Print layer
  • an embodiment may be adopted in which the primer layer on the side of the printing layer of the vapor-deposited film (transparent/metallic, stretched/unstretched, does not matter) is removed.
  • the vapor deposited layer may be dissolved with an alkaline solution, and the primer layer formed on one side of the vapor deposited film can be removed. Note that in the embodiment (4-3-4) below, since one surface of the vapor-deposited film is located on the surface of the laminate, the primer layer facing the other inner side is omitted.
  • the laminate 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. That is, in the laminate of the present invention, the extruded laminate layer is arranged on the surface opposite to the surface on which the base material (for example, base material A) is disposed with respect to the printing layer, and The invention also covers laminates with a laminate type structure in which a primer layer, a printing layer, and an extrusion laminate layer are laminated. Examples of the laminate having an extrusion laminate type structure include laminates in the following embodiments. In addition, in the following example describing the structure of a laminate type, the base film 1 corresponds to the base material A in the present invention.
  • the extruded laminate layer can be recovered and reused as a resin to which no printed layer is attached.
  • both the base film 1 and the extruded laminate layer can be recovered and reused as a resin to which no printed layer is attached.
  • the “anchor layer for extrusion lamination” is provided on the printed layer, but the “anchor layer for extrusion lamination” is not provided and the “anchor layer for extrusion lamination” is not provided and An “extrusion laminate layer” may be provided directly on the material.
  • other layers such as a sealant layer may be arranged on the surface of the extruded laminate layer opposite to the surface on which the base film 1 is provided. good.
  • the configurations of the other layers are not limited to the following (5-1-1) to (5-1-6), and can be designed as appropriate depending on the required characteristics. The following is an example of a configuration in which another layer is provided in the configuration (5-1) above. A similar configuration is also possible in (5-2) and (5-3) above.
  • the primer layer may be formed by an in-line coating method in which an aqueous urethane resin composition is applied during the film stretching process, and then a further stretching process is performed, or a primer layer may be formed using an aqueous urethane resin composition after the film stretching process.
  • the primer layer may be formed by an off-line coating method in which the primer layer is formed by applying and drying a urethane resin composition.
  • the above-mentioned printed layer is, for example, a printed layer formed using printing ink.
  • the printing layer include a printing layer formed using a printing ink containing a colored pigment or a white pigment as a coloring agent.
  • the printing method for the printing layer is not particularly limited, and the printing layer can be formed by various printing methods such as gravure printing, flexo printing, offset printing, inkjet printing, and screen printing.
  • the printing ink can be an ink suitable for various printing methods, and may be a solvent-based ink or a water-based ink. Further, UV curing type or EB curing type ink may be used.
  • the base film 1 examples include OPP film (polypropylene film, e.g., biaxially oriented polypropylene film), PET film (polyethylene terephthalate film, e.g., biaxially oriented polyethylene terephthalate film), nylon film, and the like.
  • the base film 1 may be coated with a coating for the purpose of improving gas barrier properties and ink receptivity when providing a printing layer.
  • Commercially available coated base films 1 include K-OPP films and K-PET films.
  • the sealant film include CPP film (unstretched polypropylene film), LLDPE film (linear low density polyethylene resin film), and the like.
  • a VM-CPP film in which a metal such as aluminum is vapor-deposited on a CPP film can be used.
  • a metal vapor-deposited stretched film a VM-OPP film in which a metal such as aluminum is vapor-deposited on an OPP film can be used.
  • the transparent vapor-deposited stretched film include OPP film, PET film, nylon film, etc., on which silica or alumina is vapor-deposited.
  • a film coated on the vapor-deposited layer may be used.
  • the metal layer include aluminum foil and the like.
  • the base film 2 include nylon film and the like.
  • a known adhesive for film lamination can be appropriately used.
  • a known anchor coating agent for extrusion lamination can be appropriately used as an adhesion auxiliary agent.
  • a material having gas barrier properties is used as these adhesives or anchor coating agents, a laminate having particularly excellent barrier properties can be obtained.
  • Particularly preferable adhesives with excellent gas barrier properties are those in which the cured coating film of the adhesive applied at 3 g/m 2 (solid content) has an oxygen barrier property of 300 cc/m 2 /day/atm or less, or a water vapor barrier property of 120 g/m 2 /day/atm or less. m 2 /day or less, which satisfies at least one of the conditions.
  • thermoplastic resin examples include polyolefin resins such as polyethylene resins and polypropylene resins, but are not limited to these materials.
  • anchor coating agents can be used as the anchor layer for extrusion lamination. Examples include isocyanate-based and amine polymer-based materials, but are not limited to these materials.
  • anchor layer for extrusion laminate may be formed using the aqueous urethane resin composition of the present invention.
  • anchor layer for extrusion laminate By forming the “anchor layer for extrusion laminate" using the water-based urethane resin composition of the present invention, it is possible to improve the adhesion with the extrusion laminate layer, and also improve the releasability of the extrusion laminate layer during peeling treatment. be able to.
  • the aqueous urethane resin composition of the present invention can be used to print layers of electronic equipment, building materials, textiles/leather, home appliances, vehicles such as cars and airplanes, furniture, office supplies, play equipment, sports equipment, and molded products of their parts. It can be suitably used as a surface treatment agent (primer coating agent) for a base material in a molded product having an overprint layer. Therefore, a laminate having a primer layer formed of the aqueous urethane resin composition of the present invention can be used for electronic equipment, building materials, textiles/leather, home appliances, vehicles such as cars and airplanes, furniture, office supplies, play equipment, and sporting goods.
  • a laminate having a primer layer formed of the aqueous urethane resin composition of the present invention can also be applied to packaging materials (more specifically, multilayer packaging materials).
  • packaging materials can be used as multilayer packaging material.
  • the layer structure may change depending on the contents, usage environment, and usage form.
  • 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 suitably used, for example, as a packaging material for foods, medicines, sanitary products, cosmetics, electronic materials, building materials, industrial materials, and the like.
  • the primer layer formed from the aqueous urethane resin composition of the present invention has good adhesion to the substrate, and the laminate of the present invention has excellent adhesion between the substrate and the printed layer. Further, in the laminate of the present invention, the primer layer can be easily removed by using an alkaline solution, and the base material and the printed layer can be easily peeled off. However, in the laminate of the present invention, the primer layer is not peeled off even when an alkaline solution is applied under normally used temperature conditions. Therefore, under the temperature conditions normally used, even if alkaline solution happens to adhere, it can be used with confidence without worrying about peeling.
  • the laminate having a primer layer formed of the aqueous urethane resin composition of the present invention is applicable not only to the laminate having a surface printing type structure as in the embodiment (1-A) above, but also to the laminate in the above (1-1) to (4-3-2-7) Even for a laminate with a laminate-type structure like the embodiment, the primer layer can be easily removed by applying an alkaline solution, and the base material and the printing layer can be separated. Can be easily peeled off. Furthermore, when the aqueous urethane resin composition of the present invention contains the above-mentioned crosslinking agent, the primer layer formed using the aqueous urethane resin composition containing the crosslinking agent has excellent film strength.
  • the primer layer formed using the aqueous urethane resin composition of the present invention maintains the high peeling performance aimed at by the present invention even if it contains a crosslinking agent. be able to.
  • the laminate of the present invention produced using a crosslinking agent can be excellent in both film formability and removability.
  • the primer layer is detached (removed) from the base material by immersion in an alkaline solution.
  • alkaline aqueous solution used to remove the primer layer in the present invention there are no particular restrictions on the alkaline substances used, including sodium hydroxide (NaOH), potassium hydroxide (KOH), and calcium hydroxide (Ca(OH) 2 ). , ammonia, etc. Preferred is NaOH or KOH.
  • NaOH, KOH, ammonia, etc. may be uniformly dissolved or dispersed in water, and the concentration or pH may be adjusted as appropriate.
  • the conditions for removing the primer layer are 30 minutes of immersion in an alkaline aqueous solution with a pH of 11 or higher or a concentration of 0.5 to 3.0% by mass at a temperature of 10°C or higher and 100°C or lower, followed by washing with water and drying.
  • the pH is preferably 11.0 or higher, more preferably 13.0 or higher.
  • the concentration of the aqueous solution is preferably 0.5 to 3.0% by mass, more preferably 1.0 to 2.5% by mass.
  • the immersion temperature is preferably 100°C or lower, more preferably 90°C or lower, even more preferably 80°C or lower.
  • the immersion temperature is preferably 30°C or higher, more preferably 40°C or higher, and still more preferably 50°C or higher.
  • the immersion time is within 60 minutes, more preferably within 30 minutes, still more preferably within 20 minutes.
  • the removal rate of the primer layer after washing with water and drying is preferably 90% or more, more preferably 95% or more, still more preferably 98% or more.
  • ⁇ Method for removing the primer layer in the case of a laminate type laminate such as the embodiment (1-1) above> In the case of a laminate such as the above embodiment (1-1), the primer layer is sandwiched between plastic films, and it takes a considerable amount of time for the alkaline aqueous solution to reach the primer layer. Therefore, the dipping time is required to be longer than in the embodiment (1-A), but it is more preferable that delamination progresses in a short time.
  • the immersion time is preferably within 24 hours, more preferably within 12 hours, even more preferably within 6 hours.
  • the primer layer can be removed by immersing the laminate in an alkaline solution. That is, according to the present invention, a recycled base material A can be obtained by treating the laminate with an alkaline solution to remove the printing layer together with the primer layer from the base material A. Further, the same applies even if the laminate has a laminate type structure, and according to the present invention, the laminate is treated with an alkaline solution and the printed layer and/or base material B is coated with the primer layer and the base material A.
  • a recycled base material A, a recycled base material A and a recycled base material B, or a sealant film can be obtained by desorption from the base material A.
  • ⁇ Aromatic ring concentration (mmol/g) derived from raw material monomer of aromatic dicarboxylic acid (a1-1)> Calculate the number of moles of aromatic rings contained in 1 g of urethane resin. It can be calculated based on the raw materials used in the synthesis of the aromatic polyester polyol and their blending amounts. It is determined by dividing the mass of the raw material monomer of aromatic dicarboxylic acid (a1-1) contained in 1 g of urethane resin by the molecular weight of the raw material monomer of aromatic dicarboxylic acid (a1-1).
  • ⁇ Ester bonding group concentration (mmol/g)> Calculate the number of moles of ester bond groups contained in 1 g of urethane resin. It can be calculated based on the raw materials used in the synthesis of the aromatic polyester polyol and their blending amounts. First, the concentration of ester bond groups in 1 g of aromatic polyester polyol (a1) is calculated using the following formula (I).
  • the formula (I) is a formula that takes dehydration due to ester formation into consideration.
  • a represents the number of moles of carboxylic acid in 1 g of aromatic polyester polyol (a1).
  • concentration of ester bond groups in 1 g of aromatic polyester polyol (a1) calculates the concentration of ester bond groups in 1 g of aromatic polyester polyol (a1) and the proportion of aromatic polyester polyol (a1) in 1 g of urethane resin. The product of the ratios is determined, and the concentration of ester bond groups in 1 g of urethane resin is calculated.
  • ⁇ Acid value (mgKOH/g)> The COOH group contained in 1 g of urethane resin is determined by the number of mg of KOH required when titrated by the potassium hydroxide method.
  • Weight average molecular weight is determined by gel permeation chromatography (GPC).
  • polyol The compositions and physical properties of polyols 1 to 7 used in Examples and Comparative Examples are shown in Table 1 below.
  • TPA is terephthalic acid
  • IPA is isophthalic acid
  • AA is adipic acid
  • EG is ethylene glycol
  • DEG diethylene glycol
  • 14BG is 1,4-butylene glycol.
  • an aromatic polyester polyol was prepared 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. It is shown that.
  • Urethane resin 1 was synthesized as follows. In a four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 0.74 g of polyol 2, 0.20 g of isophorone diisocyanate, and 0.0 g of 2,2'-dimethylolpropionic acid were added. .06 g of the resin and reacted for 8 hours at 75° C. under a nitrogen stream to obtain urethane resin 1. The composition and physical properties of Urethane Resin 1 are shown in Table 2 below.
  • Urethane resins 2 to 9 were produced in the same manner except that the composition of urethane resin 1 was changed as shown in Table 2 or Table 3 below.
  • the compositions and physical properties of polyurethane resins 2 to 9 are shown in Tables 2 and 3.
  • the aromatic ring concentrations listed in Table 1 were determined as follows. This will be explained using urethane resin 1 as an example. First, the aromatic ring concentration in 1 g of polyol 2 is calculated. - Determine the mass ratio of the raw material monomer of the aromatic dicarboxylic acid (a1-1) containing an aromatic ring/molecular weight of the monomer. When there are multiple raw material monomers for the aromatic dicarboxylic acid (a1-1), the sum is determined.
  • ester bond group concentrations listed in Table 1 were determined as follows. This will be explained using urethane resin 1 as an example. First, the concentration of ester bond groups in 1 g of polyol 2 is calculated. Letting a be the number of moles of carboxylic acid in 1 g of aromatic polyester polyol (a1), a is determined as follows.
  • Laminated body 1 used in Example 1 was produced as follows.
  • As the base film 1 an OPP base film (“FOR 20 ⁇ m” manufactured by Futamura Chemical Co., Ltd.) was used.
  • Urethane Resin 1 was used as the primer layer, and the aqueous urethane resin composition contained a crosslinking agent.
  • a primer layer containing a crosslinking agent was prepared as follows. Using urethane resin 1, 9 parts of "Carbodilite SV-02" manufactured by Nisshinbo Chemical Co., Ltd. was mixed with 100 parts of the urethane resin, and then diluted to a solid content of 10% with isopropyl alcohol (IPA).
  • IPA isopropyl alcohol
  • the aqueous urethane resin composition obtained above was applied onto the base film 1, which had been subjected to corona discharge treatment on one side, using a gravure printing machine (manufactured by DIC Engineering Co., Ltd.) equipped with a gravure plate having a plate depth of 22 ⁇ m. I printed it. Thereafter, it was dried at 100° C. for 10 minutes, and then left at room temperature for one day or more.
  • the ink layer was produced as follows. Laminating ink "Finart (manufactured by DIC)" was diluted with a mixed organic solvent in the same ratio as the ink, and diluted with Zahn Cup No. 3 manufactured by Rigosha to a total of 16 seconds.
  • Laminates 2 to 21 were produced in the same manner except that the configuration of laminate 1 was changed as shown in Table 4, Table 5, or Table 6 below. The configurations of the laminates 2 to 21 are shown in Tables 4 to 6.
  • Comparative laminates 1 to 14 were produced in the same manner except that the configuration of laminate 1 was changed as shown in Table 7 or Table 8 below.
  • the structures of comparative laminates 1 to 14 are shown in Tables 7 to 8.
  • PU resin refers to polyurethane resin.
  • the base film 1 is PET
  • the base film is "E5102 12 ⁇ m” manufactured by Toyobo Co., Ltd.
  • the base film is "FOR 20 ⁇ m” manufactured by Futamura Chemical.
  • the base film is a uniaxially stretched polyethylene film (film thickness 25 ⁇ m, density 0.92 g/m 2 , melting point 125° C.).
  • the crosslinking agent “BU3100” refers to "Bayhydur Ultra 3100” manufactured by Covestro.
  • a primer layer containing a crosslinking agent of "BU3100” was prepared by mixing 3 parts of "Bayhydur Ultra 3100” manufactured by Covestro with 100 parts of a urethane resin, and then diluting the mixture with water to a solid content of 10%.
  • the primer layer did not contain a crosslinking agent, the primer layer was formed using an aqueous urethane resin composition diluted with isopropyl alcohol (IPA) to a solid content of 10%.
  • IPA isopropyl alcohol
  • the method of applying the aqueous urethane resin composition using a gravure printing machine to form a primer layer is as described above in the preparation of the laminate 1.
  • the films used in Comparative Examples 12 to 14 are as follows.
  • the transparent vapor deposited film 1 is an alumina vapor deposited transparent PET film IB-PET-PUB (thickness 12 ⁇ m) manufactured by Dai Nippon Printing Co., Ltd.
  • the transparent vapor deposited film 2 is a silica vapor deposited transparent PET film Tech Barrier TX manufactured by Mitsubishi Chemical Corporation. -R (thickness: 12 ⁇ m)
  • the metal vapor-deposited film was aluminum oxide vapor-deposited transparent PET film GL-ARH (thickness: 12 ⁇ m) manufactured by Toppan Printing Co., Ltd.
  • Laminated body 1' used in Example 1 was produced as follows.
  • the base film an OPP base film (“FOR 20 ⁇ m” manufactured by Futamura Chemical Co., Ltd.) was used.
  • Urethane Resin 1 was used as the primer layer, and the aqueous urethane resin composition contained a crosslinking agent.
  • a primer layer containing a crosslinking agent was prepared as follows. Using urethane resin 1, 9 parts of "Carbodilite SV-02" manufactured by Nisshinbo Chemical Co., Ltd. was mixed with 100 parts of the urethane resin, and then diluted to a solid content of 10% with isopropyl alcohol (IPA).
  • IPA isopropyl alcohol
  • the aqueous urethane resin composition obtained above was applied onto the base film 1, which had been subjected to corona discharge treatment on one side, using a gravure printing machine (manufactured by DIC Engineering Co., Ltd.) equipped with a gravure plate having a plate depth of 22 ⁇ m. I printed it. Thereafter, it was dried at 100° C. for 10 minutes, and then left at room temperature for one day or more.
  • the ink layer was produced as follows. Laminating ink "Finart (manufactured by DIC)" was diluted with a mixed organic solvent in the same ratio as the ink, and diluted with Zahn Cup No. 3 manufactured by Rigosha to a total of 16 seconds.
  • Laminates 2' to 20' were produced in the same manner except that the configuration of laminate 1' was changed as shown in Table 4, Table 5, or Table 6 below.
  • the configurations of the laminates 2' to 20' are shown in Tables 4 to 6.
  • Comparative laminates 1' to 11' were produced in the same manner except that the configuration of laminate 1' was changed as shown in Table 7 or Table 8 below.
  • the structures of comparative laminates 1' to 11' are shown in Tables 7 and 8.
  • PU resin refers to polyurethane resin.
  • the base film 1 is PET
  • the base film is "E5102 12 ⁇ m” manufactured by Toyobo Co., Ltd.
  • the base film is "FOR 20 ⁇ m” manufactured by Futamura Chemical.
  • the base film is a uniaxially stretched polyethylene film (film thickness 25 ⁇ m, density 0.92 g/m 2 , melting point 125° C.).
  • the crosslinking agent “BU3100” refers to "Bayhydur Ultra 3100” manufactured by Covestro.
  • a primer layer containing a crosslinking agent of "BU3100” was prepared by mixing 3 parts of "Bayhydur Ultra 3100” manufactured by Covestro with 100 parts of a urethane resin, and then diluting the mixture with water to a solid content of 10%.
  • the primer layer did not contain a crosslinking agent, the primer layer was formed using an aqueous urethane resin composition diluted with isopropyl alcohol (IPA) to a solid content of 10%.
  • IPA isopropyl alcohol
  • Example 1 The following peelability test was conducted on the laminate 1.
  • delamination is defined as a state in which a specific film in a multilayer body is completely separated. The releasability of the ink coating under the above conditions was evaluated according to the following evaluation criteria.
  • [Evaluation criteria] 4 The base material was delaminated from the multilayer film after stirring for less than 5 hours. 3: The base material was delaminated from the multilayer film after stirring for less than 10 hours. 2: Signs such as lifting of the film could be confirmed after stirring for 10 hours. , the base material was delaminated from the multilayer film after stirring for 24 hours. 1: There was no change in appearance from before treatment after stirring for 10 hours. Regarding the above evaluation results, it is preferable for practical purposes to be 3 or higher, but even in 2. It can be judged that the level is such that it can contribute to recycling.
  • Table 4 shows the peelability evaluation results for the laminate 1 and the delamination evaluation results for the laminate 1'.
  • Examples 2 to 21 and Comparative Examples 1 to 14 The laminates 1 and 1' of Example 1 were changed to laminates 2 to 21, comparative laminates 1 to 14, laminates 2' to 20', or comparative laminates 1' to 11', respectively. Except for this, peelability and delamination tests were conducted in the same manner as in Example 1. The evaluation results are shown in Tables 4 to 8. However, for Comparative Examples 12 (Comparative Laminated Body 12) to Comparative Example 14 (Comparative Laminated Body 14), peeling occurred due to the alkaline solution even under normal temperature conditions, and the objective of the present invention could not be achieved. No delamination test was conducted.
  • a laminate having a primer layer formed of the aqueous urethane resin composition of the present invention can be easily produced by using an alkaline solution under temperature conditions of 85°C and 55°C.
  • the primer layer could be removed.
  • the primer layer was not removed by the alkaline solution.
  • the primer layer could be removed using an alkaline solution.

Abstract

Provided is a material for forming primer layers on common plastic bases, the primer layers being capable of being removed by a simple method to easily remove the printed layers from the plastic bases and being not separated with a strongly alkaline substance under ordinary temperature conditions.　The aqueous urethane resin composition comprises a urethane resin (A) and an aqueous medium (B), wherein the urethane resin (A) comprises a product of reaction between an aromatic polyester polyol (a1) formed from starting-material monomers including an aromatic dicarboxylic acid (a1-1) and a polyisocyanate (a2), the urethane resin (A) has a concentration of aromatic rings derived from the aromatic dicarboxylic acid (a1-1) as a starting-material monomer of 1 mmol/g or higher, the urethane resin (A) has a concentration of ester bond groups of 1 mmol/g or higher, and the urethane resin (A) has an acid value of 8-45 mgKOH/g.

Description

水性ウレタン樹脂組成物Water-based urethane resin composition
　本発明は、基材から脱離可能なプライマー層を形成するための水性ウレタン樹脂組成物に関する。 The present invention relates to an aqueous urethane resin composition for forming a primer layer that is removable from a base material.
　近年海洋に廃棄・投棄されたプラスチックが海水中で分解されて微細化（マイクロプラスチック化）することに起因した海洋プラスチック問題が顕在化している。このマイクロプラスチックは海洋生物の体内に入り込み、濃縮され、食物連鎖を通して海鳥や人間の健康にも影響することが懸念されている。この海洋プラスチック問題を改善する方法の一つがリサイクルである。軟包材やプラスチックボトルなどの資源のリサイクル率を向上させることは、プラスチックが海洋へと混入するのを防ぐことにつながる。しかし、現在のリサイクルでは、プラスチック基材に印刷された印刷層が再生工程において脱離せず、プラスチックに混入することによって色相の悪化や物性の低下を引き起こし、再生プラスチックの価値を低下させているという課題が存在する。リサイクル工程でプラスチック基材から印刷層の脱離を可能としこの課題を解決することができれば、再生プラスチックの価値が向上し、新規リサイクル業者の参入や自治体の分別回収の整備につながる。これにより、リサイクル率が向上することで、海洋プラスチック問題が改善すると考えられる。そのためリサイクル工程において基材から印刷層を脱離できる方法の開発が求められている。
　例えば、基材上に設けられたプライマー層が脱離可能であれば、プライマー層の上に形成された印刷層も取り除くことができる。したがって、基材から脱離可能な脱離用プライマー層の形成材料の開発も求められている。
　ところで、プラスチック基材に対して広く使用される皮膜形成用材料は、作業者の健康や環境に対する影響を考慮し、トルエンフリー、メチルエチルケトン（ＭＥＫ）フリーのものに代替が進んでいるため、上記課題を解決する材料もこのことを考慮して開発を進める必要がある。 In recent years, the problem of marine plastics has become apparent as plastics discarded or dumped into the ocean decompose in seawater and become microplastics (microplastics). There are concerns that this microplastic can enter the bodies of marine organisms and become concentrated, affecting the health of seabirds and humans through the food chain. One way to improve this ocean plastic problem is through recycling. Improving the recycling rate of resources such as flexible packaging and plastic bottles will help prevent plastic from entering the ocean. However, with current recycling, the printed layer printed on the plastic base material does not come off during the recycling process, and when it gets mixed into the plastic, it causes a worsening of the hue and a decline in physical properties, reducing the value of the recycled plastic. Challenges exist. If this problem can be solved by making it possible to separate the printed layer from the plastic base material during the recycling process, the value of recycled plastic will increase, leading to the entry of new recycling companies and the establishment of separate collection systems by local governments. This is expected to improve the ocean plastic problem by increasing recycling rates. Therefore, there is a need to develop a method that can detach the printed layer from the base material during the recycling process.
For example, if the primer layer provided on the base material is removable, the printed layer formed on the primer layer can also be removed. Therefore, there is also a need for the development of a material for forming a release primer layer that can be removed from a base material.
By the way, film-forming materials widely used on plastic substrates are being replaced with toluene-free and methyl ethyl ketone (MEK)-free materials in consideration of the impact on worker health and the environment, so the above-mentioned problems are being replaced. Materials that solve this problem need to be developed with this in mind.
　従来技術では、熱収縮性ＰＥＴフィルムに対して印刷したスチレン－アクリル酸樹脂、フェノール樹脂、スチレン－マレイン酸樹脂をビヒクルとして含む皮膜をアルカリ水で脱離する方法が開示されている（特許文献１）。また同様に熱収縮性ＰＥＴフィルムに対してスチレン－マレイン酸樹脂、ロジン－マレイン酸樹脂、アクリル酸共重合系樹脂を含有したコート層を印刷層の間に配置し、そのコート層をアルカリ水で脱離する方法が開示されている（特許文献２及び特許文献３）。しかしながらこれら技術は特定の基材に対する特性しか担保されておらず、また容易な脱離法の提供という観点からは十分なものとはいえなかった。ポリオレフィンを含む汎用的なプラスチック基材に対して、簡便な方法で皮膜を脱離し、プラスチック基材から印刷層を容易に取り除くことができる、プラスチック基材のリサイクル方法を提供するには、検討の余地があった。
　一方バインダー樹脂として酸価を有するウレタン樹脂を使用したアルカリ水脱離用有機溶剤系印刷インキも開示されている（特許文献４、特許文献５、及び特許文献６）。しかし、皮膜が脱離可能な材料として汎用的に使用するには、検討の余地があった。 In the prior art, a method has been disclosed in which a film printed on a heat-shrinkable PET film containing a styrene-acrylic acid resin, a phenol resin, or a styrene-maleic acid resin as a vehicle is removed with alkaline water (Patent Document 1). ). Similarly, a coat layer containing a styrene-maleic acid resin, a rosin-maleic acid resin, and an acrylic acid copolymer resin is placed between the printing layers on a heat-shrinkable PET film, and the coated layer is soaked with alkaline water. A method for desorption is disclosed (Patent Document 2 and Patent Document 3). However, these techniques only ensure properties for specific base materials, and have not been sufficient from the viewpoint of providing easy desorption methods. In order to provide a recycling method for general-purpose plastic substrates containing polyolefins, in which the film can be detached in a simple manner and the printed layer can be easily removed from the plastic substrate, the following research has been conducted. There was room.
On the other hand, an organic solvent-based printing ink for removing alkaline water using a urethane resin having an acid value as a binder resin has also been disclosed (Patent Document 4, Patent Document 5, and Patent Document 6). However, there is still room for consideration in its general use as a material from which the film can be removed.
　また、脱離可能なプライマー層に水性組成物を用いる方法が開示されている（特許文献７）。しかし、特許文献７では、プライマー層の剥離性は強アルカリかつ低温でも脱離が可能であると記載されており、即ち、特許文献７に記載の水性組成物を用いた場合には、日常生活において洗剤などの強アルカリ性の物質が印刷物に付着するなどの通常使用条件下においてもプライマー層である塗膜が剥離するという問題が生じてしまう。 Additionally, a method using an aqueous composition for a removable primer layer is disclosed (Patent Document 7). However, Patent Document 7 states that the releasability of the primer layer is strong alkali and can be removed even at low temperatures. That is, when the aqueous composition described in Patent Document 7 is used, Even under normal usage conditions, such as when strong alkaline substances such as detergents adhere to printed matter, the problem arises that the paint film, which is the primer layer, peels off.
特許第３８２２７３８号公報Patent No. 3822738 特許第４６５３９１３号公報Patent No. 4653913 特許第４４５１０７１号公報Patent No. 4451071 特許第６６３８８０２号公報Patent No. 6638802 特許第６６３１９６４号公報Patent No. 6631964 特開２０２０－１６９２８０号公報JP2020-169280A 特許第６３８８１３１号公報Patent No. 6388131
　本発明が解決しようとする課題は、上述した海洋プラスチック問題と作業者の健康や環境に対する問題を同時に解決するために、汎用プラスチック基材に対して、簡便な方法でプライマー層を脱離し、プラスチック基材から印刷層を容易に取り除くことができるとともに、通常使用される温度条件下では、強アルカリ性の物質によりプライマー層は剥離されない、プライマー層を形成するための材料を提供することである。 The problem to be solved by the present invention is to remove the primer layer from a general-purpose plastic base material using a simple method, in order to simultaneously solve the above-mentioned marine plastic problem and the problems related to worker health and the environment. It is an object of the present invention to provide a material for forming a primer layer, which allows a printed layer to be easily removed from a substrate and which does not peel off due to strong alkaline substances under normally used temperature conditions.
　発明者らは、上記課題を解決するために研究を重ねた結果、脱離可能なプライマー層を形成する材料として、特定の水性ウレタン樹脂組成物を用いることにより、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of repeated research to solve the above problems, the inventors discovered that the above problems could be solved by using a specific water-based urethane resin composition as a material for forming a removable primer layer. The present invention has now been completed.
　すなわち、本発明は、以下の態様を包含するものである。
[１]　ウレタン樹脂（Ａ）及び水性媒体（Ｂ）を含有する水性ウレタン樹脂組成物であって、
　前記ウレタン樹脂（Ａ）が、芳香族ジカルボン酸（ａ１－１）を原料モノマーとして含む芳香族ポリエステルポリオール（ａ１）とポリイソシアネート（ａ２）との反応物からなり、
　前記ウレタン樹脂（Ａ）における前記芳香族ジカルボン酸（ａ１－１）の原料モノマー由来の芳香環濃度が、１ｍｍｏｌ／ｇ以上であり、
　前記ウレタン樹脂（Ａ）におけるエステル結合基濃度が、１ｍｍｏｌ／ｇ以上であり、
　前記ウレタン樹脂（Ａ）の酸価が８～４５ｍｇＫＯＨ／ｇである、水性ウレタン樹脂組成物。
[２]　前記ポリイソシアネート（ａ２）が、イソホロンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、及びジシクロヘキシルメタンジイソシアネートの群から選ばれる少なくとも１種である、[１]に記載の水性ウレタン樹脂組成物。
[３]　前記ウレタン樹脂（Ａ）の１ｇ中に含有される前記ポリイソシアネート（ａ２）の原料モノマーの質量を、前記ポリイソシアネート（ａ２）の原料モノマーのＮＣＯ当量重量で除した値が、１．０～６．０ｍｍｏｌ／ｇである、[１]又は[２]に記載の水性ウレタン樹脂組成物。
[４]　前記ウレタン樹脂（Ａ）の重量平均分子量が、１０，０００以上である、[１]又は[２]に記載の水性ウレタン樹脂組成物。
[５]　前記ウレタン樹脂（Ａ）のガラス転移温度が、０～１１０℃である、[１]又は[２]に記載の水性ウレタン樹脂組成物。
[６]　基材Ａ上に、[１]～[５]のいずれかに記載の水性ウレタン樹脂組成物が塗工されてなるプライマー層を有し、さらに前記プライマー層上に印刷インキ組成物が印刷されてなる印刷層を有する、積層体。
[７]　前記水性ウレタン樹脂組成物が、架橋剤を含有する、[６]に記載の積層体。
[８]　前記基材Ａ上への前記水性ウレタン樹脂組成物の塗工方法が、前記基材Ａの延伸工程途中に前記水性ウレタン樹脂組成物を塗布し、その後さらに延伸工程を行うインラインコーティング法であるか、又は前記基材の延伸工程の後に、前記水性ウレタン樹脂組成物を塗布し乾燥することで前記プライマー層を形成するオフラインコーティング法である [６]に記載の積層体。
[９]　電子機材、建材、繊維・皮革、家電製品、乗り物、家具、オフィス用品、遊具、スポーツ用品あるいはそれらの部品の成型物として、または包装材料として用いる、[６]に記載の積層体。
[１０]　[６]に記載の積層体に対して、前記印刷層の前記基材Ａが配置されている面とは反対側の面に、基材Ｂを配置し、前記基材Ａと前記プライマー層と前記印刷層と前記基材Ｂとが積層してなる積層体。
[１１]　[６]に記載の積層体に対して、アルカリ溶液で処理することにより前記プライマー層とともに印刷層を基材Ａから脱離して得られるリサイクル基材Ａの製造方法。
[１２]　[１０]に記載の積層体に対して、アルカリ溶液で処理することにより前記プライマー層とともに印刷層及び／又は基材Ｂを基材Ａから脱離して得られるリサイクル基材Ａの製造方法。 That is, the present invention includes the following aspects.
[1] An aqueous urethane resin composition containing a urethane resin (A) and an aqueous medium (B),
The urethane resin (A) is made of a reaction product of an aromatic polyester polyol (a1) containing an aromatic dicarboxylic acid (a1-1) as a raw material monomer and a polyisocyanate (a2),
The aromatic ring concentration derived from the raw material monomer of the aromatic dicarboxylic acid (a1-1) in the urethane resin (A) is 1 mmol/g or more,
The ester bond group concentration in the urethane resin (A) is 1 mmol/g or more,
An aqueous urethane resin composition, wherein the urethane resin (A) has an acid value of 8 to 45 mgKOH/g.
[2] The aqueous urethane resin composition according to [1], wherein the polyisocyanate (a2) is at least one selected from the group of isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.
[3] The value obtained by dividing the mass of the raw material monomer of the polyisocyanate (a2) contained in 1 g of the urethane resin (A) by the NCO equivalent weight of the raw material monomer of the polyisocyanate (a2) is 1. The aqueous urethane resin composition according to [1] or [2], which has a content of 0 to 6.0 mmol/g.
[4] The aqueous urethane resin composition according to [1] or [2], wherein the urethane resin (A) has a weight average molecular weight of 10,000 or more.
[5] The aqueous urethane resin composition according to [1] or [2], wherein the urethane resin (A) has a glass transition temperature of 0 to 110°C.
[6] A primer layer coated with the aqueous urethane resin composition according to any one of [1] to [5] is provided on the base material A, and a printing ink composition is further coated on the primer layer. A laminate having a printed layer.
[7] The laminate according to [6], wherein the aqueous urethane resin composition contains a crosslinking agent.
[8] The method for coating the aqueous urethane resin composition on the base material A is an in-line coating method in which the aqueous urethane resin composition is applied during the stretching process of the base material A, and then a further stretching process is performed. or the laminate according to [6], which is an offline coating method in which the aqueous urethane resin composition is applied and dried to form the primer layer after the step of stretching the base material.
[9] The laminate according to [6], which is used as a molded product for electronic equipment, building materials, textiles/leather, home appliances, vehicles, furniture, office supplies, play equipment, sports equipment, or parts thereof, or as a packaging material.
[10] With respect to the laminate according to [6], a base material B is arranged on the surface of the printing layer opposite to the surface on which the base material A is arranged, and the base material A and the A laminate formed by laminating a primer layer, the printing layer, and the base material B.
[11] A method for producing a recycled base material A, which is obtained by treating the laminate according to [6] with an alkaline solution to remove the printing layer from the base material A together with the primer layer.
[12] Production of recycled base material A obtained by treating the laminate according to [10] with an alkaline solution to remove the printing layer and/or base material B together with the primer layer from base material A. Method.
　本発明により、汎用プラスチック基材に対して、簡便な方法でプライマー層を脱離し、プラスチック基材から印刷層を容易に取り除くことができるとともに、通常使用される温度条件下では、強アルカリ性の物質によりプライマー層は剥離されない、プライマー層を形成するための材料を提供することができる。 According to the present invention, a primer layer can be easily removed from a general-purpose plastic substrate by a simple method, and a printing layer can be easily removed from a plastic substrate. This makes it possible to provide a material for forming the primer layer, which does not cause the primer layer to peel off.
　以下、本発明について詳細に説明する。なお、以下に記載する構成要件の説明は、本発明を説明するための例示であり、本発明はこれらの内容に限定されるものではない。 Hereinafter, the present invention will be explained in detail. Note that the explanation of the constituent elements described below is an illustration for explaining the present invention, and the present invention is not limited to these contents.
（水性ウレタン樹脂組成物）
　本発明の水性ウレタン樹脂組成物は、ウレタン樹脂（Ａ）及び水性媒体（Ｂ）を含有する。
　本発明の水性ウレタン樹脂組成物は、芳香族ジカルボン酸（ａ１－１）を原料モノマーとして含む芳香族ポリエステルポリオール（ａ１）とポリイソシアネート（ａ２）と、必要に応じて鎖伸長剤等とを反応させて得られるウレタン樹脂（Ａ）が、水性媒体（Ｂ）中に分散したものである。
　ウレタン樹脂（Ａ）における芳香族ジカルボン酸（ａ１－１）の原料モノマー由来の芳香環濃度は、１ｍｍｏｌ／ｇ以上である。
　ウレタン樹脂（Ａ）におけるエステル結合基濃度は、１ｍｍｏｌ／ｇ以上である。
　ウレタン樹脂（Ａ）の酸価は、８～４５ｍｇＫＯＨ／ｇである。 (Aqueous urethane resin composition)
The aqueous urethane resin composition of the present invention contains a urethane resin (A) and an aqueous medium (B).
The aqueous urethane resin composition of the present invention is produced by reacting an aromatic polyester polyol (a1) containing an aromatic dicarboxylic acid (a1-1) as a raw material monomer, a polyisocyanate (a2), and, if necessary, a chain extender, etc. The urethane resin (A) obtained by this process is dispersed in an aqueous medium (B).
The aromatic ring concentration derived from the raw material monomer of the aromatic dicarboxylic acid (a1-1) in the urethane resin (A) is 1 mmol/g or more.
The ester bond group concentration in the urethane resin (A) is 1 mmol/g or more.
The acid value of the urethane resin (A) is 8 to 45 mgKOH/g.
＜ウレタン樹脂（Ａ）＞
　ウレタン樹脂（Ａ）は、ウレタン結合（－ＮＨＣＯＯ－）を有する高分子化合物の総称であり、本発明では、芳香族ポリエステルポリオール（ａ１）とポリイソシアネート（ａ２）とを反応（架橋・硬化反応）させて得られる反応物からなる。
　ウレタン樹脂（Ａ）は、芳香族ポリエステルポリオール（ａ１）とポリイソシアネート（ａ２）の他に、さらにその他のポリオール（ａ３）を含有してもよく、芳香族ポリエステルポリオール（ａ１）、ポリイソシアネート（ａ２）、及びその他のポリオール（ａ３）との反応物であってもよい。 <Urethane resin (A)>
Urethane resin (A) is a general term for polymer compounds having urethane bonds (-NHCOO-), and in the present invention, aromatic polyester polyol (a1) and polyisocyanate (a2) are reacted (crosslinking/curing reaction). It consists of a reactant obtained by
Urethane resin (A) may further contain other polyols (a3) in addition to aromatic polyester polyol (a1) and polyisocyanate (a2), and aromatic polyester polyol (a1), polyisocyanate (a2) ), and a reaction product with other polyols (a3).
＜＜芳香族ポリエステルポリオール（ａ１）＞＞
　芳香族ポリエステルポリオール（ａ１）は、例えば、芳香族ジカルボン酸（ａ１－１）と、ポリオール（ａ１－２）とをエステル化反応させることによって製造することができる。 <<Aromatic polyester polyol (a1)>>
Aromatic polyester polyol (a1) can be produced, for example, by subjecting aromatic dicarboxylic acid (a1-1) and polyol (a1-2) to an esterification reaction.
　芳香族ポリエステルポリオール（ａ１）を製造する際に使用することができる芳香族ジカルボン酸（ａ１－１）としては、例えば、テレフタル酸、イソフタル酸、オルソフタル酸、１，４－ナフタレンジカルボン酸、２，５－ナフタレンジカルボン酸、２，６－ナフタレンジカルボン酸、ナフタル酸、ビフェニルジカルボン酸、１，２－ビス（フェノキシ）エタン－Ｐ，Ｐ’－ジカルボン酸等の芳香族ジカルボン酸やそれらの酸無水物又はエステル形成性誘導体、ｐ－ヒドロキシ安息香酸等の芳香族ヒドロキシカルボン酸やそれらのエステル形成性誘導体、５－スルホイソフタル酸等のスルホン酸基含有芳香族ジカルボン酸やそれらのエステル形成性誘導体が挙げられる。 Examples of the aromatic dicarboxylic acid (a1-1) that can be used in producing the aromatic polyester polyol (a1) include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2, Aromatic dicarboxylic acids such as 5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-P,P'-dicarboxylic acid, and their acid anhydrides or ester-forming derivatives, aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and their ester-forming derivatives, sulfonic acid group-containing aromatic dicarboxylic acids such as 5-sulfoisophthalic acid, and their ester-forming derivatives. It will be done.
　また、かかる芳香族ジカルボン酸（ａ１－１）の他に、脂肪族カルボン酸や脂環族カルボン酸を併用することができる。例えばコハク酸、無水コハク酸、アジピン酸、スベリン酸、アゼライン酸、セバシン酸、ダイマー酸、無水マレイン酸、フマル酸等の脂肪族ジカルボン酸、１，４－シクロヘキサンジカルボン酸等の脂環族ジカルボン酸、それらの無水物あるいはエステル形成性誘導体が挙げられる。これらは単独使用でもよく、２種以上を併用してもよい。 In addition to the aromatic dicarboxylic acid (a1-1), an aliphatic carboxylic acid or an alicyclic carboxylic acid can be used in combination. For example, aliphatic dicarboxylic acids such as succinic acid, succinic anhydride, adipic acid, suberic acid, azelaic acid, sebacic acid, dimer acid, maleic anhydride, fumaric acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid. , their anhydrides or ester-forming derivatives. These may be used alone or in combination of two or more.
　ポリオール（ａ１－２）としては、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、ジプロピレングリコール、１，４－ブタンジオール、１，３－ブタンジオール、１，２－ブタンジオール、２，３－ブタンジオール、１，５－ペンタンジオール、１，５－ヘキサンジオール、２，５－ヘキサンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、ネオペンチルグリコール等を使用することができる。 Examples of the polyol (a1-2) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, and 1,3-butanediol. , 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, Neopentyl glycol and the like can be used.
　具体的には、芳香族ジカルボン酸（ａ１－１）と、ポリオール（ａ１－２）とを、必要に応じて触媒の存在下、窒素等の不活性気体で置換した反応容器中で常圧または減圧下で反応することができる。反応は、１００℃～３００℃の範囲で行うことが好ましい。 Specifically, the aromatic dicarboxylic acid (a1-1) and the polyol (a1-2) are heated at normal pressure or in a reaction vessel purged with an inert gas such as nitrogen in the presence of a catalyst if necessary. The reaction can be carried out under reduced pressure. The reaction is preferably carried out at a temperature in the range of 100°C to 300°C.
　触媒としては、例えばアルカリ金属又はアルカリ土類金属の酢酸塩や、亜鉛、マンガン、コバルト、アンチモン、ゲルマニウム、チタン、スズ、ジルコニウム等を含む化合物等を使用することができる。なかでも、エステル交換反応や重縮合反応等に有効なテトラアルキルチタネートや蓚酸スズを使用することが好ましい。 As the catalyst, for example, acetates of alkali metals or alkaline earth metals, compounds containing zinc, manganese, cobalt, antimony, germanium, titanium, tin, zirconium, etc. can be used. Among these, it is preferable to use tetraalkyl titanates and tin oxalate, which are effective in transesterification reactions, polycondensation reactions, and the like.
　ウレタン樹脂（Ａ）を製造する際には、芳香族ポリエステルポリオール（ａ１）と、ポリイソシアネート（ａ２）とともに、その他のポリオール（ａ３）等を組み合わせ使用することもできる。 When producing the urethane resin (A), other polyols (a3) and the like can also be used in combination with the aromatic polyester polyol (a1) and polyisocyanate (a2).
　その他のポリオール（ａ３）としては、上記ポリオール（ａ１－２）と同様なポリオールを使用することができ、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、ジプロピレングリコール、１，４－ブタンジオール、１，３－ブタンジオール、１，２－ブタンジオール、２，３－ブタンジオール、１，５－ペンタンジオール、１，５－ヘキサンジオール、２，５－ヘキサンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、ネオペンチルグリコール等の比較的低分子量のポリオールを使用することができる。 As the other polyol (a3), the same polyol as the above polyol (a1-2) can be used, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol. , dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5 Polyols of relatively low molecular weight such as -hexanediol, 1,6-hexanediol, 1,7-heptanediol, neopentyl glycol, etc. can be used.
＜＜ポリイソシアネート（ａ２）＞＞
　ポリオール（ａ１）と反応しウレタン樹脂（Ａ）を形成するポリイソシアネート（ａ２）としては、例えばフェニレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート等の芳香族ジイソシアネートや、ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の脂肪族または脂肪族環式構造含有ジイソシアネート等を、単独で使用または２種以上を併用して使用することができる。なかでも、イソホロンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、及びジシクロヘキシルメタンジイソシアネートの群から選ばれる１種以上を使用することが、得られるプライマー層の基材密着性および脱墨性向上等の観点からより好ましい。 <<Polyisocyanate (a2)>>
Examples of the polyisocyanate (a2) that reacts with the polyol (a1) to form the urethane resin (A) include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, Aliphatic or aliphatic cyclic structure-containing diisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used alone or in combination of two or more. . Among them, it is recommended to use one or more selected from the group of isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate from the viewpoint of improving the adhesion to the base material and deinking property of the resulting primer layer. More preferred.
　ウレタン樹脂（Ａ）は、例えば無溶剤下または有機溶剤の存在下で、上記芳香族ポリエステルポリオール（ａ１）と、上記ポリイソシアネート（ａ２）と、必要に応じて上記ポリオール（ａ３）と、必要に応じて鎖伸長剤とを反応させることによって製造することができる。上記有機溶剤を使用した場合には、上記ウレタン樹脂（Ａ）を水性媒体（Ｂ）中に分散等する際に、必要に応じて上記有機溶剤を蒸留等の方法で除去することが好ましい。 The urethane resin (A) is, for example, in the absence of a solvent or in the presence of an organic solvent, the above aromatic polyester polyol (a1), the above polyisocyanate (a2), and optionally the above polyol (a3), as necessary. It can be produced by reacting with a chain extender as appropriate. When the above-mentioned organic solvent is used, it is preferable to remove the above-mentioned organic solvent by a method such as distillation as necessary when dispersing the above-mentioned urethane resin (A) in the aqueous medium (B).
　ウレタン樹脂（Ａ）を製造する際に使用可能な有機溶剤としては、例えばアセトン、メチルエチルケトン等のケトン類；テトラヒドロフラン、ジオキサン等のエーテル類；酢酸エチル、酢酸ブチル等の酢酸エステル類；アセトニトリル等のニトリル類；ジメチルホルムアミド、Ｎ－メチルピロリドン等を、単独で使用または２種以上を使用することができる。 Examples of organic solvents that can be used in producing the urethane resin (A) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile. Dimethylformamide, N-methylpyrrolidone, etc. can be used alone or in combination of two or more.
　ウレタン樹脂（Ａ）を製造する際に使用可能な鎖伸長剤は、ウレタン樹脂（Ａ）の分子量を大きくし、得られるフィルム等の耐久性を向上することを目的として使用することができる。
　ウレタン樹脂（Ａ）を製造する際に使用可能な鎖伸長剤としては、ポリアミンや、その他活性水素原子含有化合物等を使用することができる。 The chain extender that can be used when producing the urethane resin (A) can be used for the purpose of increasing the molecular weight of the urethane resin (A) and improving the durability of the resulting film.
As the chain extender that can be used in producing the urethane resin (A), polyamines and other active hydrogen atom-containing compounds can be used.
　ポリアミンとしては、例えば、エチレンジアミン、１，２－プロパンジアミン、１，６－ヘキサメチレンジアミン、ピペラジン、２，５－ジメチルピペラジン、イソホロンジアミン、４，４’－ジシクロヘキシルメタンジアミン、３，３’－ジメチル－４，４’－ジシクロヘキシルメタンジアミン、１，４－シクロヘキサンジアミン等のジアミン類；Ｎ－ヒドロキシメチルアミノエチルアミン、Ｎ－ヒドロキシエチルアミノエチルアミン、Ｎ－ヒドロキシプロピルアミノプロピルアミン、Ｎ－エチルアミノエチルアミン、Ｎ－メチルアミノプロピルアミン；ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン；ヒドラジン、Ｎ，Ｎ’－ジメチルヒドラジン、１，６－ヘキサメチレンビスヒドラジン；コハク酸ジヒドラジッド、アジピン酸ジヒドラジド、グルタル酸ジヒドラジド、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジド；β－セミカルバジドプロピオン酸ヒドラジド、３－セミカルバジッド－プロピル－カルバジン酸エステル、セミカルバジッド－３－セミカルバジドメチル－３，５，５－トリメチルシクロヘキサンを使用することができ、エチレンジアミンを使用することが好ましい。 Examples of polyamines include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl Diamines such as -4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide , isophthalic acid dihydrazide; β-semicarbazidopropionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazidomethyl-3,5,5-trimethylcyclohexane can be used; It is preferable to use
　その他活性水素含有化合物としては、例えば、エチレングリコール、ジエチレンリコール、トリエチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ヘキサメチレングリコール、ネオペンチルグリコール、サッカロース、メチレングリコール、グリセリン、ソルビトール等のグリコール類；ビスフェノールＡ、４，４’－ジヒドロキシジフェニル、４，４’－ジヒドロキシジフェニルエーテル、４，４’－ジヒドロキシジフェニルスルホン、水素添加ビスフェノールＡ、ハイドロキノン等のフェノール類、及び水等を使用することができる。 Other active hydrogen-containing compounds include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, neopentyl Glycols such as glycol, sucrose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc. phenols, water, etc. can be used.
　鎖伸長剤は、上記芳香族ポリエステルポリオール（ａ１）と上記ポリイソシアネート（ａ２）とを反応させる際、または、反応後に使用することができる。また、ウレタン樹脂（Ａ）を水性媒体（Ｂ）中に分散させ水性化する際に、鎖伸長剤を使用することもできる。 The chain extender can be used when the aromatic polyester polyol (a1) and the polyisocyanate (a2) are reacted or after the reaction. Furthermore, a chain extender can also be used when dispersing the urethane resin (A) in the aqueous medium (B) to make it aqueous.
＜＜ウレタン樹脂（Ａ）の特性＞＞
　ウレタン樹脂（Ａ）における芳香族ジカルボン酸（ａ１－１）の原料モノマー由来の芳香環濃度は、１ｍｍｏｌ／ｇ以上である。
　係る芳香環濃度は、ウレタン樹脂（Ａ）１ｇ中に含有されている芳香環のモル数を計算することにより求められる。
　具体的な計算方法は、後述する。
　該芳香環濃度は、得られるプライマー層の基材密着性および脱墨性向上等の観点から、１．５ｍｍｏｌ／ｇ以上であることが好ましく、２ｍｍｏｌ／ｇ以上であることがより好ましく、プライマー層の良好な造膜性等の観点から、６ｍｍｏｌ／ｇ以下であることが好ましく、５ｍｍｏｌ／ｇ以下であることがより好ましい。 <<Characteristics of urethane resin (A)>>
The aromatic ring concentration derived from the raw material monomer of the aromatic dicarboxylic acid (a1-1) in the urethane resin (A) is 1 mmol/g or more.
The aromatic ring concentration is determined by calculating the number of moles of aromatic rings contained in 1 g of urethane resin (A).
A specific calculation method will be described later.
The aromatic ring concentration is preferably 1.5 mmol/g or more, more preferably 2 mmol/g or more, from the viewpoint of improving the substrate adhesion and deinking property of the resulting primer layer. From the viewpoint of good film-forming properties, etc., it is preferably 6 mmol/g or less, more preferably 5 mmol/g or less.
　ウレタン樹脂（Ａ）におけるエステル結合基濃度は、１ｍｍｏｌ／ｇ以上である。
　係るエステル結合基濃度は、ウレタン樹脂（Ａ）１ｇ中に含有されているエステル結合基のモル数を計算することにより求められる。
　具体的な計算方法は、後述する。
　該エステル結合基濃度は、得られるプライマー層の基材密着性および脱墨性向上等の観点から、２ｍｍｏｌ／ｇ以上であることが好ましく、４ｍｍｏｌ／ｇ以上であることがより好ましく、プライマー層の良好な耐ブロッキング性等の観点から、９ｍｍｏｌ／ｇ以下であることが好ましく、７ｍｍｏｌ／ｇ以下であることがより好ましい。 The ester bond group concentration in the urethane resin (A) is 1 mmol/g or more.
The concentration of ester bond groups is determined by calculating the number of moles of ester bond groups contained in 1 g of urethane resin (A).
A specific calculation method will be described later.
The concentration of the ester bond group is preferably 2 mmol/g or more, more preferably 4 mmol/g or more, from the viewpoint of improving the substrate adhesion and deinking property of the resulting primer layer. From the viewpoint of good anti-blocking properties, it is preferably 9 mmol/g or less, more preferably 7 mmol/g or less.
　ウレタン樹脂（Ａ）の酸価は、８～４５ｍｇＫＯＨ／ｇである。
　酸価は、酸をアルカリで滴定して算出した樹脂１ｇ中の酸量を、水酸化カリウムのｍｇ数に換算した値で、ＪＩＳＫ００７０に従って行った値である。
　酸価が８ｍｇＫＯＨ／ｇ以上であれば、水分散安定性を向上することができ、１５ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／以上がより好ましい。酸価が４５ｍｇＫＯＨ／ｇ以下であれば、ポリエステル基材との密着性を良好に担保することができ、４０ｍｇＫＯＨ／ｇ以下が好ましく、３０ｍｇＫＯＨ／以下がより好ましい。 The acid value of the urethane resin (A) is 8 to 45 mgKOH/g.
The acid value is a value obtained by converting the amount of acid in 1 g of resin, calculated by titrating the acid with an alkali, into mg of potassium hydroxide, and is a value determined according to JIS K0070.
When the acid value is 8 mgKOH/g or more, water dispersion stability can be improved, and 15 mgKOH/g or more is preferable, and 20 mgKOH/g or more is more preferable. If the acid value is 45 mgKOH/g or less, good adhesion to the polyester base material can be ensured, and 40 mgKOH/g or less is preferable, and 30 mgKOH/g or less is more preferable.
　ウレタン樹脂（Ａ）の１ｇ中に含有されるポリイソシアネート（ａ２）の原料モノマーの質量を、ポリイソシアネート（ａ２）の原料モノマーのＮＣＯ当量重量で除した値は、１．０～６．０ｍｍｏｌ／ｇであることが好ましい。
　係る値が１．０ｍｍｏｌ／ｇ以上であれば、得られるプライマー層の基材密着性および脱墨性を向上することができ、１．５ｍｍｏｌ／ｇ以上であることがより好ましく、１．８ｍｍｏｌ／ｇ以上であることがより好ましい。６．０ｍｍｏｌ／ｇ以下であれば、プライマー層の造膜性を担保することができ、５．０ｍｍｏｌ／ｇ以下であることがより好ましく、４．０ｍｍｏｌ／ｇ以下であることがより好ましい。 The value obtained by dividing the mass of the raw material monomer of polyisocyanate (a2) contained in 1 g of urethane resin (A) by the NCO equivalent weight of the raw material monomer of polyisocyanate (a2) is 1.0 to 6.0 mmol/ It is preferable that it is g.
If the value is 1.0 mmol/g or more, the substrate adhesion and deinking properties of the resulting primer layer can be improved, and it is more preferably 1.5 mmol/g or more, and 1.8 mmol/g. It is more preferable that it is not less than g. If it is 6.0 mmol/g or less, the film forming properties of the primer layer can be ensured, and it is more preferably 5.0 mmol/g or less, and even more preferably 4.0 mmol/g or less.
　ウレタン樹脂（Ａ）の重量平均分子量は、１０，０００～１００，０００であることが好ましい。基材に対する耐ブロッキング性、樹脂の耐加水分解安定性等の観点から、ウレタン樹脂（Ａ）の重量平均分子量は、２０，０００以上が好ましく、３０，０００以上がより好ましい。また、水分散時の低粘度化、生産性等の観点から、８０，０００以下が好ましく、６０，０００以下がより好ましい。 The weight average molecular weight of the urethane resin (A) is preferably 10,000 to 100,000. From the viewpoints of blocking resistance to the base material, hydrolytic stability of the resin, etc., the weight average molecular weight of the urethane resin (A) is preferably 20,000 or more, more preferably 30,000 or more. Further, from the viewpoint of reducing viscosity during water dispersion, productivity, etc., it is preferably 80,000 or less, more preferably 60,000 or less.
　本発明において、重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した値を示す。
　測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌＧ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌＧ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌＧ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌＧ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成する。 In the present invention, the weight average molecular weight indicates a value measured by gel permeation chromatography (GPC) under the following conditions.
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used by connecting them in series.
"TSKgelG5000" (7.8mmI.D. x 30cm) x 1 "TSKgelG4000" (7.8mmI.D. x 30cm) x 1 "TSKgelG3000" (7.8mmI.D. x 30cm) x 1 "TSKgelG2000" ” (7.8mm I.D. x 30cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40℃
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (Tetrahydrofuran solution with sample concentration 0.4% by mass)
Standard sample: Create a calibration curve using the standard polystyrene shown below.
〔標準ポリスチレン〕
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＡ－５００」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＡ－１０００」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＡ－２５００」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＡ－５０００」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＦ－１」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＦ－２」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＦ－４」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＦ－１０」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＦ－２０」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＦ－４０」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＦ－８０」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＦ－１２８」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＦ－２８８」
東ソー株式会社製「ＴＳＫｇｅｌ標準ポリスチレンＦ－５５０」 [Standard polystyrene]
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
“TSKgel standard polystyrene A-5000” manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
“TSKgel standard polystyrene F-550” manufactured by Tosoh Corporation
　ウレタン樹脂（Ａ）のガラス転移温度は、０～１１０℃であることが好ましい。 The glass transition temperature of the urethane resin (A) is preferably 0 to 110°C.
＜水性媒体（Ｂ）＞
　ウレタン樹脂（Ａ）の溶媒となる水性媒体（Ｂ）としては、水、水と混和する有機溶剤、及び、これらの混合物が挙げられる。
　水と混和する有機溶剤としては、例えば、メタノール、エタノール、ｎ－及びイソプロパノール等のアルコール類；アセトン、メチルエチルケトン等のケトン類；エチレングリコール、ジエチレングリコール、プロピレングリコール等のポリアルキレングリコール類；ポリアルキレングリコールのアルキルエーテル類;Ｎ－メチル－２－ピロリドン等が挙げられる。
　本発明では、水のみを用いてもよく、また水及び水と混和する有機溶剤との混合物を用いてもよく、水と混和する有機溶剤のみを用いてもよい。安全性や環境に対する負荷の点から、水のみ、又は、水及び水と混和する有機溶剤との混合物が好ましく、水のみが特に好ましい。 <Aqueous medium (B)>
Examples of the aqueous medium (B) serving as a solvent for the urethane resin (A) include water, organic solvents miscible with water, and mixtures thereof.
Examples of organic solvents that are miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; Alkyl ethers; N-methyl-2-pyrrolidone and the like.
In the present invention, water alone may be used, a mixture of water and a water-miscible organic solvent may be used, or only a water-miscible organic solvent may be used. From the viewpoint of safety and environmental impact, water alone or a mixture of water and an organic solvent miscible with water is preferred, and water alone is particularly preferred.
　ウレタン樹脂（Ａ）を水性媒体（Ｂ）中に水分散する際に、必要に応じてホモジナイザー等の機械を使用することができる。 When dispersing the urethane resin (A) in the aqueous medium (B), a machine such as a homogenizer can be used as necessary.
　本発明の水性ウレタン樹脂組成物は、水性ウレタン樹脂組成物の全量に対してウレタン樹脂（Ａ）を５質量％～５０質量％の範囲で含有することが好ましく、１０質量％～２５質量％の範囲で含有することがより好ましい。また、水性媒体（Ｂ）は、ウレタン樹脂組成物の全量に対して、５０質量％～９５質量％の範囲で含有することが好ましく、７５質量％～９０質量％の範囲で含有することがより好ましい。 The aqueous urethane resin composition of the present invention preferably contains urethane resin (A) in a range of 5% to 50% by mass, and preferably 10% to 25% by mass, based on the total amount of the aqueous urethane resin composition. It is more preferable that the content be within a range. Further, the aqueous medium (B) is preferably contained in a range of 50% by mass to 95% by mass, more preferably in a range of 75% by mass to 90% by mass, based on the total amount of the urethane resin composition. preferable.
＜その他の添加剤＞
　本発明の水性ウレタン樹脂組成物には、必要に応じて造膜助剤や架橋剤、硬化促進剤、可塑剤、帯電防止剤、ワックス、光安定剤、流動調整剤、染料、レベリング剤、レオロジーコントロール剤、紫外線吸収剤、酸化防止剤、光触媒性化合物、無機顔料、有機顔料、体質顔料、等の各種の添加剤等を使用することができる。 <Other additives>
The aqueous urethane resin composition of the present invention may optionally contain a film-forming aid, a crosslinking agent, a curing accelerator, a plasticizer, an antistatic agent, a wax, a light stabilizer, a fluidity regulator, a dye, a leveling agent, a rheology agent, etc. Various additives such as control agents, ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments, extender pigments, etc. can be used.
　添加剤のうち乳化剤やレベリング剤は、得られるフィルム等の耐久性の低下を引き起こす場合があるため、フィルム等に高耐久性が求められる場合には、水性ウレタン樹脂組成物の全量に対して５質量％以下の範囲で使用することが好ましい。 Among additives, emulsifiers and leveling agents may cause a decrease in the durability of the obtained film, etc., so if high durability is required for the film, etc., 5% of the total amount of the water-based urethane resin composition is used. It is preferable to use it within a range of % by mass or less.
　また、本発明の水性ウレタン樹脂組成物には、耐久性に優れたフィルム等を形成するうえで、各種架橋剤を組み合わせ使用することができる。
　架橋剤としては、例えばイソシアネート系架橋剤やエポキシ系架橋剤、アミノ系架橋剤、アジリジン系架橋剤、シランカップリング剤系架橋剤、カルボジイミド系架橋剤、オキサゾリジン系架橋剤等を使用することができる。
　架橋剤は、ウレタン樹脂（Ａ）の全量に対して、基材への密着性向上、脱墨性向上等の観点から、３０質量％以下の範囲で使用することが好ましく、２０質量％以下の範囲で使用することがより好ましい。また、架橋剤は、本発明の水性ウレタン樹脂組成物を塗工等する直前に混合し、使用することが好ましい。 Moreover, various crosslinking agents can be used in combination with the aqueous urethane resin composition of the present invention in order to form a film etc. with excellent durability.
As the crosslinking agent, for example, isocyanate crosslinking agents, epoxy crosslinking agents, amino crosslinking agents, aziridine crosslinking agents, silane coupling agent crosslinking agents, carbodiimide crosslinking agents, oxazolidine crosslinking agents, etc. can be used. .
The crosslinking agent is preferably used in an amount of 30% by mass or less, and 20% by mass or less, based on the total amount of the urethane resin (A), from the viewpoint of improving adhesion to the substrate and improving deinking performance. It is more preferable to use the range. Further, the crosslinking agent is preferably mixed and used immediately before coating the aqueous urethane resin composition of the present invention.
（プライマー層）
　本発明の水性ウレタン樹脂組成物を用いて、基材上に該水性ウレタン樹脂組成物を塗工することによりプライマー層を形成することができる。
　後述するように、該プライマー層の上には、印刷インキ組成物からなる印刷層を形成することができる。
　該プライマー層は、アルカリ溶液での処理により容易に脱離することができる。
　プライマー層が基材から容易に剥離されることで、プライマー層の上に形成された印刷層も基材から容易に取り除くことができる。尚、プライマー層の脱離方法についての詳しい説明は後述する。 (Primer layer)
A primer layer can be formed by applying the aqueous urethane resin composition of the present invention onto a substrate.
As described below, a printing layer made of a printing ink composition can be formed on the primer layer.
The primer layer can be easily removed by treatment with an alkaline solution.
Since the primer layer is easily peeled off from the base material, the printed layer formed on the primer layer can also be easily removed from the base material. A detailed explanation of the method for removing the primer layer will be given later.
　本発明の水性ウレタン樹脂組成物は、グラビア印刷、フレキソ印刷などの既知の印刷方式を用いて基材上に塗工することができる。既知の印刷方式としては、上述したグラビア印刷、フレキソ印刷の他には、例えば、Ｔ－ダイコーター、リップコーター、ナイフコーター、カーテン、インクジェット、バーコーター、ロールコーター、スプレーコーター、コンマコーター、リバースロールコーター、ダイレクトグラビアコーター、リバースグラビアコーター、オフセットグラビアコーター、ロールキスコーター、リバースキスコーター、キスグラビアコーター、リバースキスグラビアコーター、エアドクターコーター、ワイヤーバーコーター、ディップコーター、ブレードコーター、ブラシコーター、ダイスロットコーター、オフセット印刷機、スクリーン印刷機等のいずれかもしくは二つ以上の塗工方法を組み合わせて用いることができる。
　印刷する際は、グラビア印刷方式、フレキソ印刷方式等の各種の印刷方式に適した粘度及び濃度にまで、水性溶液、例えばエチルアルコール、イソプロピルアルコール、ノルマルプロピルアルコールなどのアルコール系有機溶剤と水を混合した希釈溶剤で希釈され、単独でまたは混合されて各印刷ユニットに供給される。 The aqueous urethane resin composition of the present invention can be coated onto a substrate using known printing methods such as gravure printing and flexographic printing. In addition to the above-mentioned gravure printing and flexographic printing, known printing methods include, for example, T-die coater, lip coater, knife coater, curtain, inkjet, bar coater, roll coater, spray coater, comma coater, and reverse roll. Coater, direct gravure coater, reverse gravure coater, offset gravure coater, roll kiss coater, reverse kiss coater, kiss gravure coater, reverse kiss gravure coater, air doctor coater, wire bar coater, dip coater, blade coater, brush coater, die slot Any coating method such as a coater, an offset printing machine, a screen printing machine, etc. or a combination of two or more coating methods can be used.
When printing, water is mixed with an aqueous solution, such as an alcohol-based organic solvent such as ethyl alcohol, isopropyl alcohol, or n-propyl alcohol, to a viscosity and concentration suitable for various printing methods such as gravure printing and flexographic printing. It is diluted with a diluted solvent and supplied to each printing unit either alone or in a mixture.
　また、基材上への水性ウレタン樹脂組成物の塗工方法としては、基材の延伸工程（例えば、二軸延伸工程）途中に水性ウレタン樹脂組成物を塗布し、その後さらに延伸工程を行うインラインコーティング法であるか、又は基材の延伸工程（例えば、二軸延伸工程）の後に、水性ウレタン樹脂組成物を塗布し乾燥することでプライマー層を形成するオフラインコーティング法を用いることによっても行うことができる。 In addition, as a method for coating the aqueous urethane resin composition on the base material, an in-line method in which the aqueous urethane resin composition is applied during the stretching process (for example, biaxial stretching process) of the base material, and then a further stretching process is performed. A coating method or an off-line coating method in which a primer layer is formed by applying an aqueous urethane resin composition and drying it after a step of stretching the base material (e.g., a biaxial stretching step). Can be done.
（積層体）
　また、本発明は、上記本発明の水性ウレタン樹脂組成物を用いて形成されたプライマー層を有する積層体を提供する。
　本発明の積層体は、基材上に、上記本発明の水性ウレタン樹脂組成物が塗工されてなるプライマー層を有し、さらに該プライマー層上に印刷インキ組成物が印刷されてなる印刷層を有する。 (laminate)
The present invention also provides a laminate having a primer layer formed using the aqueous urethane resin composition of the present invention.
The laminate of the present invention has a primer layer coated with the aqueous urethane resin composition of the present invention on a base material, and further has a printing layer formed by printing a printing ink composition on the primer layer. has.
　本発明の水性ウレタン樹脂組成物を用いて形成されたプライマー層を有する積層体の実施形態としては、限定されるわけではないが、例えば、下記（１－Ａ）態様が好ましく挙げられる。
・（１－Ａ）基材Ａ－プライマー層－印刷層 Examples of embodiments of the laminate having a primer layer formed using the aqueous urethane resin composition of the present invention include, but are not limited to, the following embodiment (1-A).
・(1-A) Base material A-primer layer-printing layer
　また、本発明の積層体は、上記（１－Ａ）態様のように、印刷層が積層体表面に形成された表刷りタイプの構造からなる積層体だけでなく、印刷層の上にさらに塗膜（各種層又はフィルム）が形成されたラミネートタイプの構造からなる積層体も対象とする。
　つまり、本発明の積層体は、印刷層に対して、基材（例えば、基材Ａとする）が配置されている面とは反対側の面に、他の基材（例えば、基材Ｂとする）を配置し、基材Ａとプライマー層と印刷層と基材Ｂとを積層するラミネートタイプの構造の積層体も対象とする。
　ラミネートタイプの構造からなる積層体として、例えば、以下に記載の態様の積層体を挙げることができる。
　尚、下記ラミネートタイプの構造を記載した例示において、基材フィルム１は本発明でいう基材Ａに対応している。ただし、基材フィルム１がない態様の場合、シーラントフィルムや金属蒸着未延伸フィルムや透明蒸着延伸フィルム等の各フィルムが本発明でいう基材Ａに対応する場合がある。また、基材フィルム２は本発明でいう基材Ｂに対応している。基材フィルム２がない態様の場合、シーラントフィルムや金属蒸着未延伸フィルムや透明蒸着延伸フィルム等の各フィルムが本発明でいう基材Ｂに対応する。基材Ｂは、積層体において、基材Ａとは反対面の表面に形成されたフィルムを示す場合が多いが、場合によっては、表面に配されたフィルムに限らず、層間に基材Ｂが存在する場合もあり、また、積層体中に複数の基材Ｂが設けられる場合もある。 In addition, the laminate of the present invention is not only 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 embodiment (1-A), but also a laminate that is coated on top of the printed layer. Also covered are laminates having a laminate type structure in which membranes (various layers or films) are formed.
In other words, in the laminate of the present invention, another base material (for example, base material B) is placed on the surface opposite to the surface on which the base material (for example, base material A) is disposed with respect to the printed layer. The present invention also covers a laminate type structure in which a base material A, a primer layer, a printing layer, and a base material B are laminated.
Examples of the laminate having a laminate type structure include laminates in the following embodiments.
In addition, in the following example describing the structure of a laminate type, the base film 1 corresponds to the base material A in the present invention. However, in the case of an embodiment without the base film 1, each film such as a sealant film, a metal vapor deposited unstretched film, a transparent vapor deposited stretched film, etc. may correspond to the base material A in the present invention. Further, the base film 2 corresponds to the base material B in the present invention. In the case of the embodiment without the base film 2, each film such as a sealant film, a metal vapor deposited unstretched film, a transparent vapor deposited stretched film, etc. corresponds to the base material B in the present invention. In many cases, the base material B refers to a film formed on the surface opposite to the base material A in the laminate, but in some cases, the base material B is not limited to the film disposed on the surface, but may be formed between the layers. In some cases, a plurality of base materials B are provided in the laminate.
　基材Ａに対応するフィルム上にプライマー層を塗工する態様である。
・（１－１）基材フィルム１／プライマー層／印刷層／接着層１／シーラントフィルム
・（１－２）基材フィルム１／プライマー層／印刷層／接着層１／金属蒸着未延伸フィルム
・（１－３）基材フィルム１／プライマー層／印刷層／接着層１／金属蒸着延伸フィルム
・（１－４）透明蒸着延伸フィルム／プライマー層／印刷層／接着層１／シーラントフィルム
・（１－５）基材フィルム１／プライマー層／印刷層／接着層１／基材フィルム２／接着層２／シーラントフィルム
・（１－６）基材フィルム１／プライマー層／印刷層／接着層１／金属蒸着延伸フィルム／接着層２／シーラントフィルム
・（１－７）基材フィルム１／プライマー層／印刷層／接着層１／透明蒸着延伸フィルム／接着層２／シーラントフィルム
・（１－８）基材フィルム１／プライマー層／印刷層／接着層１／金属層／接着層２／シーラントフィルム
・（１－９）基材フィルム１／プライマー層／印刷層／接着層１／基材フィルム２／接着層２／金属層／接着層３／シーラントフィルム
・（１－１０）基材フィルム１／プライマー層／印刷層／接着層１／金属層／接着層２／基材フィルム２／接着層３／シーラントフィルム This is an embodiment in which a primer layer is coated on a film corresponding to base material A.
・(1-1) Base film 1/Primer layer/Print layer/Adhesive layer 1/Sealant film ・(1-2) Base film 1/Primer layer/Print layer/Adhesive layer 1/Metalized unstretched film・(1-3) Base film 1/primer layer/printed layer/adhesive layer 1/metal-deposited stretched film (1-4) transparent vapor-deposited stretched film/primer layer/printed layer/adhesive layer 1/sealant film (1 -5) Base film 1/Primer layer/Print layer/Adhesive layer 1/Base film 2/Adhesive layer 2/Sealant film (1-6) Base film 1/Primer layer/Print layer/Adhesive layer 1/ Metallic vapor-deposited stretched film / adhesive layer 2 / sealant film / (1-7) base film 1 / primer layer / printing layer / adhesive layer 1 / transparent vapor-deposited stretched film / adhesive layer 2 / sealant film / (1-8) base Material film 1 / Primer layer / Printing layer / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Sealant film (1-9) Base film 1 / Primer layer / Printing layer / Adhesive layer 1 / Base film 2 / Adhesion Layer 2 / Metal layer / Adhesive layer 3 / Sealant film (1-10) Base film 1 / Primer layer / Printing layer / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Base film 2 / Adhesive layer 3 / Sealant film
　上記（１－１）～（１－１０）の態様のうち、中間層に位置するフィルムの両面にプライマー層を塗工してもよい。
・（２－５）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／基材フィルム２／プライマー層／接着層２／シーラントフィルム
・（２－６）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／金属蒸着延伸フィルム／プライマー層／接着層２／シーラントフィルム
・（２－７）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／透明蒸着延伸フィルム／プライマー層／接着層２／シーラントフィルム
・（２－９）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／基材フィルム２／プライマー層／接着層２／金属層／接着層３／シーラントフィルム
・（２－１０）基材フィルム１／プライマー層／印刷層／接着層１／金属層／接着層２／プライマー層／基材フィルム２／プライマー層／接着層３／シーラントフィルム Among the embodiments (1-1) to (1-10) above, a primer layer may be coated on both sides of the film located in the intermediate layer.
・(2-5) Base film 1/Primer layer/Print layer/Adhesive layer 1/Primer layer/Base film 2/Primer layer/Adhesive layer 2/Sealant film ・(2-6) Base film 1/Primer Layer / Printing layer / Adhesive layer 1 / Primer layer / Metallized stretched film / Primer layer / Adhesive layer 2 / Sealant film (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 (2-9) Base film 1 / Primer layer / Printing layer / Adhesive layer 1 / Primer layer / Base film 2 / Primer layer / Adhesive layer 2 / Metal layer / Adhesive layer 3 / Sealant film (2-10) Base film 1 / Primer layer / Printing layer / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Primer layer / Base film 2 / Primer layer / Adhesive layer 3/Sealant film
　上記（１－１）～（１－１０）、（２－５）～（２－７）、及び（２－９）～（２－１０）の態様に対して、基材Ｂに対応するフィルム（基材Ａとは反対面の表面に位置するフィルム）にプライマー層を塗工してもよい。
・（３－１）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／シーラントフィルム
・（３－２）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／金属蒸着未延伸フィルム
・（３－３）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／金属蒸着延伸フィルム
・（３－４）透明蒸着延伸フィルム／プライマー層／印刷層／接着層１／プライマー層／シーラントフィルム
・（３－５）基材フィルム１／プライマー層／印刷層／接着層１／基材フィルム２／接着層２／プライマー層／シーラントフィルム
・（３－６）基材フィルム１／プライマー層／印刷層／接着層１／金属蒸着延伸フィルム／接着層２／プライマー層／シーラントフィルム
・（３－７）基材フィルム１／プライマー層／印刷層／接着層１／透明蒸着延伸フィルム／接着層２／プライマー層／シーラントフィルム
・（３－８）基材フィルム１／プライマー層／印刷層／接着層１／金属層／接着層２／プライマー層／シーラントフィルム
・（３－９）基材フィルム１／プライマー層／印刷層／接着層１／基材フィルム２／接着層２／金属層／接着層３／プライマー層／シーラントフィルム
・（３－１０）基材フィルム１／プライマー層／印刷層／接着層１／金属層／接着層２／基材フィルム２／接着層３／プライマー層／シーラントフィルム
・（３－２－５）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／基材フィルム２／プライマー層／接着層２／プライマー層／シーラントフィルム
・（３－２－６）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／金属蒸着延伸フィルム／プライマー層／接着層２／プライマー層／シーラントフィルム
・（３－２－７）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／透明蒸着延伸フィルム／プライマー層／接着層２／プライマー層／シーラントフィルム
・（３－２－９）基材フィルム１／プライマー層／印刷層／接着層１／プライマー層／基材フィルム２／プライマー層／接着層２／金属層／接着層３／プライマー層／シーラントフィルム
・（３－２－１０）基材フィルム１／プライマー層／印刷層／接着層１／金属層／接着層２／プライマー層／基材フィルム２／プライマー層／接着層３／プライマー層／シーラントフィルム A film corresponding to the base material B for the embodiments (1-1) to (1-10), (2-5) to (2-7), and (2-9) to (2-10) above. (The film located on the surface opposite to the substrate A) may be coated with a primer layer.
・(3-1) Base film 1/Primer layer/Print layer/Adhesive layer 1/Primer layer/Sealant film ・(3-2) Base film 1/Primer layer/Print 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) transparent vapor-deposited stretched film/primer layer/printed layer/ Adhesive layer 1 / Primer layer / Sealant film (3-5) Base film 1 / Primer layer / Printing layer / Adhesive layer 1 / Base film 2 / Adhesive layer 2 / Primer layer / Sealant film (3-6) Base film 1/Primer layer/Print layer/Adhesive layer 1/Metal-deposited stretched film/Adhesive layer 2/Primer layer/Sealant film (3-7) Base film 1/Primer layer/Print layer/Adhesive layer 1/ Transparent vapor-deposited stretched film/adhesive layer 2/primer layer/sealant film (3-8) Base film 1/primer layer/printing layer/adhesive layer 1/metal layer/adhesive layer 2/primer layer/sealant film (3 -9) Base film 1/Primer layer/Printing layer/Adhesive layer 1/Base film 2/Adhesive layer 2/Metal layer/Adhesive layer 3/Primer layer/Sealant film (3-10) Base film 1/ Primer layer / Printing layer / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Base film 2 / Adhesive layer 3 / Primer layer / Sealant film (3-2-5) Base film 1 / Primer layer / Printing layer / Adhesive layer 1 / Primer layer / Base film 2 / Primer layer / Adhesive layer 2 / Primer layer / Sealant film (3-2-6) Base film 1 / Primer layer / Printing layer / Adhesive layer 1 / Primer layer / Metallic vapor-deposited stretched film/primer layer/adhesive layer 2/primer layer/sealant film (3-2-7) Base film 1/primer layer/printing layer/adhesive layer 1/primer layer/transparent vapor-deposited stretched film/primer layer /Adhesive layer 2/Primer layer/Sealant film・(3-2-9) Base film 1/Primer layer/Printing layer/Adhesive layer 1/Primer layer/Base film 2/Primer layer/Adhesive layer 2/Metal layer /Adhesive layer 3/Primer layer/Sealant film・(3-2-10) Base film 1/Primer layer/Printing layer/Adhesive layer 1/Metal layer/Adhesive layer 2/Primer layer/Base film 2/Primer layer /Adhesive layer 3/Primer layer/Sealant film
　上記態様のうち、蒸着フィルム（透明/金属、延伸/未延伸は問わない）の印刷層側に面のプライマー層を削除した態様であってもよい。蒸着層はアルカリ溶液で溶解する場合もあり、蒸着フィルムの片方の面に形成されたプライマー層を削除することができる。尚、下記（４－３－４）の態様については、蒸着フィルムの一方の面は積層体の表面に位置しているため、他方の内側に面したプライマー層を削除している。
・（４－２－６）基材フィルム１／プライマー層／印刷層／接着層１／金属蒸着延伸フィルム／プライマー層／接着層２／シーラントフィルム
・（４－２－７）基材フィルム１／プライマー層／印刷層／接着層１／透明蒸着延伸フィルム／プライマー層／接着層２／シーラントフィルム
・（４－３－４）透明蒸着延伸フィルム／印刷層／接着層１／プライマー層／シーラントフィルム
・（４－３－２－６）基材フィルム１／プライマー層／印刷層／接着層１／金属蒸着延伸フィルム／プライマー層／接着層２／プライマー層／シーラントフィルム
・（４－３－２－７）基材フィルム１／プライマー層／印刷層／接着層１／透明蒸着延伸フィルム／プライマー層／接着層２／プライマー層／シーラントフィルム Among the above embodiments, an embodiment may be adopted in which the primer layer on the side of the printing layer of the vapor-deposited film (transparent/metallic, stretched/unstretched, does not matter) is removed. The vapor deposited layer may be dissolved with an alkaline solution, and the primer layer formed on one side of the vapor deposited film can be removed. Note that in the embodiment (4-3-4) below, since one surface of the vapor-deposited film is located on the surface of the laminate, the primer layer facing the other inner side is omitted.
・(4-2-6) Base film 1/Primer layer/Print layer/Adhesive layer 1/Metal-deposited stretched film/Primer layer/Adhesive layer 2/Sealant film・(4-2-7) Base film 1/ Primer layer / Printing layer / Adhesive layer 1 / Transparent vapor-deposited stretched film / Primer layer / Adhesive layer 2 / Sealant film (4-3-4) Transparent vapor-deposited stretched film / Printing layer / Adhesive layer 1 / Primer layer / Sealant film (4-3-2-6) Base film 1/primer layer/printing layer/adhesive layer 1/metal-deposited stretched film/primer layer/adhesive layer 2/primer layer/sealant film・(4-3-2-7 ) Base film 1/primer layer/printing layer/adhesive layer 1/transparent vapor-deposited stretched film/primer layer/adhesive layer 2/primer layer/sealant film
　ラミネートタイプの構造からなる積層体として、押出ラミネートにより、印刷層の上にさらに塗膜（各種層又はフィルム）が形成されたラミネートタイプの構造としてもよい。
　つまり、本発明の積層体は、印刷層に対して、基材（例えば、基材Ａとする）が配置されている面とは反対側の面に、押出ラミネート層を配置し、基材Ａとプライマー層と印刷層と押出ラミネート層とを積層するラミネートタイプの構造の積層体も対象とする。
　押出ラミネートタイプの構造からなる積層体として、例えば、以下に記載の態様の積層体を挙げることができる。
　尚、下記ラミネートタイプの構造を記載した例示において、基材フィルム１は本発明でいう基材Ａに対応している。 The laminate 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.
That is, in the laminate of the present invention, the extruded laminate layer is arranged on the surface opposite to the surface on which the base material (for example, base material A) is disposed with respect to the printing layer, and The invention also covers laminates with a laminate type structure in which a primer layer, a printing layer, and an extrusion laminate layer are laminated.
Examples of the laminate having an extrusion laminate type structure include laminates in the following embodiments.
In addition, in the following example describing the structure of a laminate type, the base film 1 corresponds to the base material A in the present invention.
・（５－１）基材フィルム１／プライマー層／印刷層／押出ラミネート用アンカー層／押出ラミネート層
・（５－２）基材フィルム１／印刷層／プライマー層／押出ラミナート用アンカー層／押出ラミネート層
・（５－３）基材フィルム１／プライマー層／印刷層／プライマー層／押出ラミナート用アンカー層／押出ラミネート層 ・(5-1) Base film 1/Primer layer/Print layer/Anchor layer for extrusion laminate/Extrusion laminate layer ・(5-2) Base film 1/Print layer/Primer layer/Anchor layer for extrusion laminate/Extrusion Laminate layer/(5-3) Base film 1/Primer layer/Printing layer/Primer layer/Anchor layer for extruded laminate/Extruded laminate layer
　上記（５－２）及び（５－３）の態様の場合、押出ラミネート層を回収し、印刷層が付着していない樹脂として再利用可能である。（５－３）の態様は、基材フィルム１及び押出ラミネート層の両方を回収し、印刷層が付着していない樹脂として再利用可能である。
　上記（５－１）～（５－３）は、印刷層の上に「押出ラミネート用アンカー層」を設ける構成としたが、「押出ラミネート用アンカー層」を設けずに「印刷層」の上に直接「押出ラミネート層」を設けてもよい。 In the case of the above embodiments (5-2) and (5-3), the extruded laminate layer can be recovered and reused as a resin to which no printed layer is attached. In the embodiment (5-3), both the base film 1 and the extruded laminate layer can be recovered and reused as a resin to which no printed layer is attached.
In (5-1) to (5-3) above, the "anchor layer for extrusion lamination" is provided on the printed layer, but the "anchor layer for extrusion lamination" is not provided and the "anchor layer for extrusion lamination" is not provided and An "extrusion laminate layer" may be provided directly on the material.
　上記（５－１）～（５－３）の構成の他に、押出ラミネート層の基材フィルム１が設けられる面とは反対側の面に、シーラント層等の他の層を配置してもよい。他の層の構成は、下記（５－１－1）～（５－１－６）に限定されるものではなく、必要とされる特性に応じて適宜設計可能である。
　以下は、上記（５－１）の構成において他の層を設けた構成の例である。上記（５－２）、（５－３）においても同様の構成が可能である。
・（５－１－１）基材フィルム１／プライマー層／印刷層／押出ラミネートアンカー層／押出ラミネート層／接着層１／シーラントフィルム
・（５－１－２）基材フィルム１／プライマー層／印刷層／押出ラミネートアンカー層／押出ラミネート層／接着層１／金属層／接着層２／シーラントフィルム
・（５－１－３）基材フィルム１／プライマー層／印刷層／押出ラミネートアンカー層／押出ラミネート層／プライマー層／接着層１／シーラントフィルム
・（５－１－４）基材フィルム１／プライマー層／印刷層／押出ラミネートアンカー層／押出ラミネート層／プライマー層／接着層１／金属層／接着層２／シーラントフィルム
・（５－１－５）基材フィルム１／プライマー層／印刷層／押出ラミネートアンカー層／押出ラミネート層／プライマー層／接着層１／プライマー層／シーラントフィルム
・（５－１－６）基材フィルム１／プライマー層／印刷層／押出ラミネートアンカー層／押出ラミネート層／プライマー層／接着層１／金属層／接着層２／プライマー層／シーラントフィルム In addition to the configurations (5-1) to (5-3) above, other layers such as a sealant layer may be arranged on the surface of the extruded laminate layer opposite to the surface on which the base film 1 is provided. good. The configurations of the other layers are not limited to the following (5-1-1) to (5-1-6), and can be designed as appropriate depending on the required characteristics.
The following is an example of a configuration in which another layer is provided in the configuration (5-1) above. A similar configuration is also possible in (5-2) and (5-3) above.
・(5-1-1) Base film 1/Primer layer/Print layer/Extrusion laminate anchor layer/Extrusion laminate layer/Adhesive layer 1/Sealant film ・(5-1-2) Base film 1/Primer layer/ Printing 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/printing layer/extrusion laminate anchor layer/extrusion Laminate layer / Primer layer / Adhesive layer 1 / Sealant film / (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 / Extruded laminate anchor layer / Extruded laminate layer / Primer layer / Adhesive layer 1 / Primer layer / Sealant film (5- 1-6) Base film 1/primer layer/printing layer/extruded laminate anchor layer/extruded laminate layer/primer layer/adhesive layer 1/metal layer/adhesive layer 2/primer layer/sealant film
　上記各態様の積層体を製造するにあたり、基材フィルム１、基材フィルム２、金属蒸着延伸フィルム、及び透明蒸着延伸フィルムの各フィルム上にプライマー層を形成する場合には、上記（プライマー層）の欄でも説明した通り、フィルムの延伸工程途中に水性ウレタン樹脂組成物を塗布し、その後さらに延伸工程を行うインラインコーティング法によりプライマー層を形成してもよいし、フィルムの延伸工程の後に、水性ウレタン樹脂組成物を塗布し乾燥することでプライマー層を形成するオフラインコーティング法によりプライマー層を形成してもよい。 In producing the laminate of each of the above embodiments, when forming a primer layer on each of the base film 1, base film 2, metal vapor deposited stretched film, and transparent vapor deposited stretched film, the above (primer layer) As explained in the section above, the primer layer may be formed by an in-line coating method in which an aqueous urethane resin composition is applied during the film stretching process, and then a further stretching process is performed, or a primer layer may be formed using an aqueous urethane resin composition after the film stretching process. The primer layer may be formed by an off-line coating method in which the primer layer is formed by applying and drying a urethane resin composition.
　積層体の構造として、上記各態様を挙げたが、これに限定されない。
　上記印刷層としては、例えば、印刷インキにより形成された印刷層をいう。印刷層としては、例えば、着色剤として有色顔料あるいは白色顔料を用い、該着色剤を含有する印刷インキにより形成された印刷層が挙げられる。
　印刷層の印刷方式は特に限定されず、グラビア印刷、フレキソ印刷、オフセット印刷、インクジェット印刷、スクリーン印刷等の各種の印刷方式により印刷層を形成可能である。印刷インキは各種印刷方式に応じたインキを用いることができ、溶剤系のインキであっても水性インキであってもよい。また、ＵＶ硬化型やＥＢ硬化型のインキを用いてもよい。 Although the above-mentioned embodiments have been described as the structure of the laminate, the present invention is not limited thereto.
The above-mentioned printed layer is, for example, a printed layer formed using printing ink. Examples of the printing layer include a printing layer formed using a printing ink containing a colored pigment or a white pigment as a coloring agent.
The printing method for the printing layer is not particularly limited, and the printing layer can be formed by various printing methods such as gravure printing, flexo printing, offset printing, inkjet printing, and screen printing. The printing ink can be an ink suitable for various printing methods, and may be a solvent-based ink or a water-based ink. Further, UV curing type or EB curing type ink may be used.
　上記基材フィルム１としては、ＯＰＰフィルム（ポリプロピレンフィルム、例えば二軸延伸ポリプロピレンフィルム）、ＰＥＴフィルム（ポリエチレンテレフタレートフィルム、例えば二軸延伸ポリエチレンテレフタレートフィルム）、ナイロンフィルム等が挙げられる。基材フィルム１としてガスバリア性や、印刷層を設ける際のインキ受容性の向上等を目的としたコーティングが施されたものを用いてもよい。コーティングが施された基材フィルム１の市販品としては、Ｋ－ＯＰＰフィルムやＫ－ＰＥＴフィルム等が挙げられる。
　上記シーラントフィルムとしては、ＣＰＰフィルム（無延伸ポリプロピレンフィルム）、ＬＬＤＰＥフィルム（直鎖状低密度ポリエチレン樹脂フィルム）等が挙げられる。
　上記金属蒸着未延伸フィルムとしては、ＣＰＰフィルムにアルミニウム等の金属蒸着を施したＶＭ－ＣＰＰフィルムを用いることができる。
　上記金属蒸着延伸フィルムとしては、ＯＰＰフィルムにアルミニウム等の金属蒸着を施したＶＭ－ＯＰＰフィルムを用いることができる。
　上記透明蒸着延伸フィルムとしては、ＯＰＰフィルム、ＰＥＴフィルム、ナイロンフィルム等にシリカやアルミナ蒸着を施したフィルムが挙げられる。シリカやアルミナの無機蒸着層の保護等を目的として、蒸着層上にコーティングが施されたフィルムを用いてもよい。
　上記金属層としては、アルミニウム箔等が挙げられる。
　基材フィルム２としては、ナイロンフィルム等が挙げられる。 Examples of the base film 1 include OPP film (polypropylene film, e.g., biaxially oriented polypropylene film), PET film (polyethylene terephthalate film, e.g., biaxially oriented polyethylene terephthalate film), nylon film, and the like. The base film 1 may be coated with a coating for the purpose of improving gas barrier properties and ink receptivity when providing a printing layer. Commercially available coated base films 1 include K-OPP films and K-PET films.
Examples of the sealant film include CPP film (unstretched polypropylene film), LLDPE film (linear low density polyethylene resin film), and the like.
As the metal vapor-deposited unstretched film, a VM-CPP film in which a metal such as aluminum is vapor-deposited on a CPP film can be used.
As the metal vapor-deposited stretched film, a VM-OPP film in which a metal such as aluminum is vapor-deposited on an OPP film can be used.
Examples of the transparent vapor-deposited stretched film include OPP film, PET film, nylon film, etc., on which silica or alumina is vapor-deposited. For the purpose of protecting the inorganic vapor-deposited layer of silica or alumina, a film coated on the vapor-deposited layer may be used.
Examples of the metal layer include aluminum foil and the like.
Examples of the base film 2 include nylon film and the like.
　上記接着層は、公知のフィルムラミネート用の接着剤を適宜使用することができる。また、押出しラミネーションにより積層する場合は、公知の押出しラミネーション用のアンカーコート剤を接着補助剤として適宜使用することができる。これらの接着剤やアンカーコート剤としてガスバリア性を有する材料を使用すると、特にバリア性に優れる積層体を得ることができる。
　ガスバリア性に優れる接着剤として特に好ましくは、３ｇ／ｍ２（固形分）で塗布した接着剤の硬化塗膜の酸素バリア性が３００ｃｃ／ｍ２／ｄａｙ／ａｔｍ以下、または水蒸気バリア性が１２０ｇ／ｍ２／ｄａｙ以下の、少なくとも一方の条件を満足するものをいう。市販品としてはＤＩＣ株式会社製のＰＡＳＬＩＭ　ＶＭ００１やＰＡＳＬＩＭ　Ｊ３５０Ｘ等の「ＰＡＳＬＩＭ」シリーズや、三菱ガス化学社製の「マクシーブ」が挙げられる。
　上記押出ラミネート層としては、公知の熱可塑性樹脂を使用することができる。熱可塑性樹脂としては、ポリエチレン系樹脂やポリプロピレン系樹脂のポリオレフィン系樹脂が挙げられるが、これらの材料に限定されるものではない。
　上記押出ラミネート用アンカー層としては、各種の公知のアンカーコート剤が用いられる。例えば、イソシアネート系やアミン重合体系の材料が挙げられるが、これらの材料に限定されるものではない。また、「押出ラミネート用アンカー層」を、本発明の水性ウレタン樹脂組成物を用いて形成してもよい。本発明の水性ウレタン樹脂組成物を用いて「押出ラミネート用アンカー層」を形成することにより、押出ラミネート層との密着性を向上させると共に、剥離処理の際は押出ラミネート層の剥離性を向上させることができる。 For the adhesive layer, a known adhesive for film lamination can be appropriately used. Moreover, when laminating by extrusion lamination, a known anchor coating agent for extrusion lamination can be appropriately used as an adhesion auxiliary agent. When a material having gas barrier properties is used as these adhesives or anchor coating agents, a laminate having particularly excellent barrier properties can be obtained.
Particularly preferable adhesives with excellent gas barrier properties are those in which the cured coating film of the adhesive applied at 3 g/m 2 (solid content) has an oxygen barrier property of 300 cc/m 2 /day/atm or less, or a water vapor barrier property of 120 g/m 2 /day/atm or less. m 2 /day or less, which satisfies at least one of the conditions. Commercially available products include the "PASLIM" series such as PASLIM VM001 and PASLIM J350X manufactured by DIC Corporation, and "Maxive" manufactured by Mitsubishi Gas Chemical Company.
As the extrusion laminate layer, a known thermoplastic resin can be used. Examples of thermoplastic resins include polyolefin resins such as polyethylene resins and polypropylene resins, but are not limited to these materials.
Various known anchor coating agents can be used as the anchor layer for extrusion lamination. Examples include isocyanate-based and amine polymer-based materials, but are not limited to these materials. Furthermore, the "anchor layer for extrusion laminate" may be formed using the aqueous urethane resin composition of the present invention. By forming the "anchor layer for extrusion laminate" using the water-based urethane resin composition of the present invention, it is possible to improve the adhesion with the extrusion laminate layer, and also improve the releasability of the extrusion laminate layer during peeling treatment. be able to.
＜積層体の用途＞
　本発明の水性ウレタン樹脂組成物は、電子機材、建材、繊維・皮革、家電製品、車や飛行機等の乗り物、家具、オフィス用品、遊具、スポーツ用品あるいはそれらの部品の成型物等の印刷層を含む上刷層を持つ成型物における基材の表面処理剤（プライマーコート剤）として好適に使用することができる。
　従って、本発明の水性ウレタン樹脂組成物で形成されたプライマー層を有する積層体は、電子機材、建材、繊維・皮革、家電製品、車や飛行機等の乗り物、家具、オフィス用品、遊具、スポーツ用品あるいはそれらの部品の成型物等の各成型物に適用することができる。
　また、本発明の水性ウレタン樹脂組成物で形成されたプライマー層を有する積層体は、包装材料（より具体的には、多層包装材料）に適用することもできる。
　多層包装材料として使用することができる。多層包装材料として使用する場合には、内容物や使用環境、使用形態に応じてその層構成は変化し得る。
　包装材料として使用する場合、例えば、その開口部から内容物を充填した後、開口部をヒートシールして、本発明の積層体から形成される包装材料を使用した製品が製造される。包装材料の用途は特に限定されないが、例えば、食品、医薬品、サニタリー、コスメ、電子材料、建築材料、工業材料等の包装材料として好適に使用できる。 <Applications of laminate>
The aqueous urethane resin composition of the present invention can be used to print layers of electronic equipment, building materials, textiles/leather, home appliances, vehicles such as cars and airplanes, furniture, office supplies, play equipment, sports equipment, and molded products of their parts. It can be suitably used as a surface treatment agent (primer coating agent) for a base material in a molded product having an overprint layer.
Therefore, a laminate having a primer layer formed of the aqueous urethane resin composition of the present invention can be used for electronic equipment, building materials, textiles/leather, home appliances, vehicles such as cars and airplanes, furniture, office supplies, play equipment, and sporting goods. Alternatively, it can be applied to each molded product such as a molded product of those parts.
Further, a laminate having a primer layer formed of the aqueous urethane resin composition of the present invention can also be applied to packaging materials (more specifically, multilayer packaging materials).
Can be used as multilayer packaging material. When used as a multilayer packaging material, the layer structure may change depending on the contents, usage environment, and usage form.
When used as a packaging material, for example, after filling the contents through the opening, 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 suitably used, for example, as a packaging material for foods, medicines, sanitary products, cosmetics, electronic materials, building materials, industrial materials, and the like.
＜積層体の特性＞
　本発明の水性ウレタン樹脂組成物で形成されたプライマー層は、基材との密着性も良好であり、本発明の積層体は、基材と印刷層との密着性に優れている。
　また、本発明の積層体は、アルカリ溶液を用いることにより簡便な方法でプライマー層を脱離することができ、基材と印刷層とを容易に剥離することができる。ただし、本発明の積層体は、通常使用される温度条件下では、アルカリ溶液を適用してもプライマー層は剥離されない。したがって、通常使用される温度条件下では、たとえたまたまアルカリ溶液が付着することがあっても、剥離を気にせず安心して使用することができる。
　本発明の水性ウレタン樹脂組成物で形成されたプライマー層を有する積層体は、上記（１－Ａ）態様のような表刷りタイプの構造からなる積層体だけでなく、上記（１－１）～（４－３－２－７）態様のようなラミネートタイプの構造からなる積層体に対しても、アルカリ溶液の適用によりプライマー層を容易に脱離することができ、基材と印刷層とを容易に剥離することができる。
　また、本発明の水性ウレタン樹脂組成物が上述したような架橋剤を含有している場合、架橋剤を含有する水性ウレタン樹脂組成物を用いて形成されたプライマー層は、膜強度に優れており良好な成膜性を示すが、一方、本発明の水性ウレタン樹脂組成物を用いて形成されたプライマー層は、架橋剤を含有していても、本発明の目的とする高い剥離性能を維持することができる。つまり、架橋剤を用いて製造された本発明の積層体は、成膜性、及び脱離性の両面で優れたものとすることができる。 <Characteristics of laminate>
The primer layer formed from the aqueous urethane resin composition of the present invention has good adhesion to the substrate, and the laminate of the present invention has excellent adhesion between the substrate and the printed layer.
Further, in the laminate of the present invention, the primer layer can be easily removed by using an alkaline solution, and the base material and the printed layer can be easily peeled off. However, in the laminate of the present invention, the primer layer is not peeled off even when an alkaline solution is applied under normally used temperature conditions. Therefore, under the temperature conditions normally used, even if alkaline solution happens to adhere, it can be used with confidence without worrying about peeling.
The laminate having a primer layer formed of the aqueous urethane resin composition of the present invention is applicable not only to the laminate having a surface printing type structure as in the embodiment (1-A) above, but also to the laminate in the above (1-1) to (4-3-2-7) Even for a laminate with a laminate-type structure like the embodiment, the primer layer can be easily removed by applying an alkaline solution, and the base material and the printing layer can be separated. Can be easily peeled off.
Furthermore, when the aqueous urethane resin composition of the present invention contains the above-mentioned crosslinking agent, the primer layer formed using the aqueous urethane resin composition containing the crosslinking agent has excellent film strength. On the other hand, the primer layer formed using the aqueous urethane resin composition of the present invention maintains the high peeling performance aimed at by the present invention even if it contains a crosslinking agent. be able to. In other words, the laminate of the present invention produced using a crosslinking agent can be excellent in both film formability and removability.
（基材Ａからのプライマー層の脱離方法）
　基材からプライマー層を脱離（除去）するには、アルカリ溶液中に浸漬して行う。本発明におけるプライマー層を除去するために使用するアルカリ水溶液では、使用するアルカリ性物質は特に制限は無く、水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（ＫＯＨ）、水酸化カルシウム（Ｃａ（ＯＨ）２）、アンモニア等が挙げられる。
　好ましくはＮａＯＨあるいはＫＯＨである。アルカリ水溶液の製造方法としては、ＮａＯＨ、ＫＯＨ、アンモニア等を水に均一に溶解または分散させ、指定の濃度あるいはｐＨに適宜調整すればよい。 (Method for removing primer layer from base material A)
The primer layer is detached (removed) from the base material by immersion in an alkaline solution. In the alkaline aqueous solution used to remove the primer layer in the present invention, there are no particular restrictions on the alkaline substances used, including sodium hydroxide (NaOH), potassium hydroxide (KOH), and calcium hydroxide (Ca(OH) 2 ). , ammonia, etc.
Preferred is NaOH or KOH. As a method for producing an alkaline aqueous solution, NaOH, KOH, ammonia, etc. may be uniformly dissolved or dispersed in water, and the concentration or pH may be adjusted as appropriate.
＜上記（１－Ａ）態様の積層体の場合のプライマー層の脱離方法＞
　通常、プライマー層の除去条件としては、１０℃以上１００℃以下で、ｐＨ１１以上あるいは濃度０．５～３．０質量％のアルカリ水溶液に、３０分浸漬し、水洗・乾燥したときにプライマー層の９０％以上を除去する方法が挙げられる。ｐＨとして好ましくは１１．０以上、より好ましくは１３．０以上である。濃度では０．５～３．０質量％水溶液のものが好ましく、より好ましくは１．０～２．５質量％水溶液である。浸漬温度は１００℃以下が好ましく、より好ましくは９０℃以下、更に好ましくは８０℃以下である。一方で、意図せずにアルカリ性物質が積層体に付着した際に、プライマー層の脱離、ひいては印刷層の除去が引き起こされないためには、低温においてはプライマーが脱離されないことが必要である。そのため、浸漬温度は、３０℃以上が好ましく、より好ましくは４０℃以上、更に好ましくは５０℃以上である。浸漬時間としては６０分以内、より好ましくは３０分以内、更に好ましくは２０分以内である。その後水洗・乾燥したときのプライマー層の除去率は好ましくは９０％以上、より好ましくは９５％以上、更に好ましくは９８％以上である。 <Method for removing the primer layer in the case of the laminate of the above (1-A) aspect>
Normally, the conditions for removing the primer layer are 30 minutes of immersion in an alkaline aqueous solution with a pH of 11 or higher or a concentration of 0.5 to 3.0% by mass at a temperature of 10°C or higher and 100°C or lower, followed by washing with water and drying. One example is a method that removes 90% or more. The pH is preferably 11.0 or higher, more preferably 13.0 or higher. The concentration of the aqueous solution is preferably 0.5 to 3.0% by mass, more preferably 1.0 to 2.5% by mass. The immersion temperature is preferably 100°C or lower, more preferably 90°C or lower, even more preferably 80°C or lower. On the other hand, in order to prevent the removal of the primer layer and even the removal of the printing layer when an alkaline substance unintentionally adheres to the laminate, it is necessary that the primer not be removed at low temperatures. . Therefore, the immersion temperature is preferably 30°C or higher, more preferably 40°C or higher, and still more preferably 50°C or higher. The immersion time is within 60 minutes, more preferably within 30 minutes, still more preferably within 20 minutes. The removal rate of the primer layer after washing with water and drying is preferably 90% or more, more preferably 95% or more, still more preferably 98% or more.
＜上記（１－１）態様等のラミネートタイプの積層体の場合のプライマー層の脱離方法＞
　上記（１－１）態様等の積層体の場合、プライマー層はプラスチックフィルムに挟まれており、アルカリ水溶液がプライマー層に到達するために相当時間を要する。したがって、浸漬時間は（１－Ａ）態様より長く必要となるが、短時間で脱ラミネーションが進行するものがより好ましい。浸漬時間としては、２４時間以内が好ましく、より好ましくは１２時間以内、更に好ましくは６時間以内である。 <Method for removing the primer layer in the case of a laminate type laminate such as the embodiment (1-1) above>
In the case of a laminate such as the above embodiment (1-1), the primer layer is sandwiched between plastic films, and it takes a considerable amount of time for the alkaline aqueous solution to reach the primer layer. Therefore, the dipping time is required to be longer than in the embodiment (1-A), but it is more preferable that delamination progresses in a short time. The immersion time is preferably within 24 hours, more preferably within 12 hours, even more preferably within 6 hours.
　上述したように、積層体をアルカリ溶液に浸漬することにより、プライマー層を脱離することができる。
　つまり、本発明により、積層体に対してアルカリ溶液で処理しプライマー層とともに印刷層を基材Ａから脱離して、リサイクルされた基材Ａを得ることができる。
　また、積層体がラミネートタイプの構造からなる積層体であっても同様であり、本発明により、積層体に対してアルカリ溶液で処理しプライマー層とともに印刷層及び／又は基材Ｂを基材Ａから脱離して、リサイクルされた基材Ａ、あるいは、リサイクルされた基材Ａ及びリサイクルされた基材Ｂやシーラントフィルムを得ることができる。 As described above, the primer layer can be removed by immersing the laminate in an alkaline solution.
That is, according to the present invention, a recycled base material A can be obtained by treating the laminate with an alkaline solution to remove the printing layer together with the primer layer from the base material A.
Further, the same applies even if the laminate has a laminate type structure, and according to the present invention, the laminate is treated with an alkaline solution and the printed layer and/or base material B is coated with the primer layer and the base material A. A recycled base material A, a recycled base material A and a recycled base material B, or a sealant film can be obtained by desorption from the base material A.
　以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例の組成物における「％」は「質量％」を意味する。 Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Moreover, "%" in the compositions of the following examples means "mass %".
＜芳香族ジカルボン酸（ａ１－１）の原料モノマー由来の芳香環濃度（ｍｍｏｌ／ｇ）＞
　ウレタン樹脂１ｇ中に含有する芳香環のモル数を計算する。芳香族ポリエステルポリオールの合成に用いた原料及びその配合量に基づいて算出することができる。
　ウレタン樹脂１ｇ中に含有する芳香族ジカルボン酸（ａ１－１）の原料モノマーの質量を、芳香族ジカルボン酸（ａ１－１）の原料モノマーの分子量で除することで求める。 <Aromatic ring concentration (mmol/g) derived from raw material monomer of aromatic dicarboxylic acid (a1-1)>
Calculate the number of moles of aromatic rings contained in 1 g of urethane resin. It can be calculated based on the raw materials used in the synthesis of the aromatic polyester polyol and their blending amounts.
It is determined by dividing the mass of the raw material monomer of aromatic dicarboxylic acid (a1-1) contained in 1 g of urethane resin by the molecular weight of the raw material monomer of aromatic dicarboxylic acid (a1-1).
＜エステル結合基濃度（ｍｍｏｌ／ｇ）＞
　ウレタン樹脂１ｇ中に含有するエステル結合基のモル数を計算する。芳香族ポリエステルポリオールの合成に用いた原料及びその配合量に基づいて算出することができる。
　まず、芳香族ポリエステルポリオール（ａ１）１ｇ中のエステル結合基濃度を、下式（Ｉ）により算出する。係る式（Ｉ）は、エステル形成による脱水を考慮した式である。 <Ester bonding group concentration (mmol/g)>
Calculate the number of moles of ester bond groups contained in 1 g of urethane resin. It can be calculated based on the raw materials used in the synthesis of the aromatic polyester polyol and their blending amounts.
First, the concentration of ester bond groups in 1 g of aromatic polyester polyol (a1) is calculated using the following formula (I). The formula (I) is a formula that takes dehydration due to ester formation into consideration.
　式（Ｉ）中、ａは、芳香族ポリエステルポリオール（ａ１）１ｇ中のカルボン酸のモル数を表す。
　芳香族ポリエステルポリオール（ａ１）１ｇ中のエステル結合基濃度を求めたら、次に、芳香族ポリエステルポリオール（ａ１）１ｇ中のエステル結合基濃度とウレタン樹脂１ｇ中に占める芳香族ポリエステルポリオール（ａ１）の割合の積を求め、ウレタン樹脂１ｇ中のエステル結合基濃度を算出する。 In formula (I), a represents the number of moles of carboxylic acid in 1 g of aromatic polyester polyol (a1).
After determining the concentration of ester bond groups in 1 g of aromatic polyester polyol (a1), next, calculate the concentration of ester bond groups in 1 g of aromatic polyester polyol (a1) and the proportion of aromatic polyester polyol (a1) in 1 g of urethane resin. The product of the ratios is determined, and the concentration of ester bond groups in 1 g of urethane resin is calculated.
＜酸価（ｍｇＫＯＨ／ｇ）＞
　ウレタン樹脂１ｇ中に含有するＣＯＯＨ基を、水酸化カリウム法により滴定した場合に要するＫＯＨのｍｇ数で求める。 <Acid value (mgKOH/g)>
The COOH group contained in 1 g of urethane resin is determined by the number of mg of KOH required when titrated by the potassium hydroxide method.
＜ウレタン＋ウレア官能基濃度（ｍｍｏｌ／ｇ）＞
　ウレタン樹脂１ｇ中に含有されるポリイソシアネート（ａ２）の原料モノマーの質量を、ポリイソシアネート（ａ２）の原料モノマーのＮＣＯ当量重量で除し求める。 <Urethane + urea functional group concentration (mmol/g)>
It is determined by dividing the mass of the raw material monomer of polyisocyanate (a2) contained in 1 g of urethane resin by the NCO equivalent weight of the raw material monomer of polyisocyanate (a2).
＜重量平均分子量＞
　ゲル浸透クロマトグラフィー（ＧＰＣ）により、重量平均分子量を測定する。 <Weight average molecular weight>
Weight average molecular weight is determined by gel permeation chromatography (GPC).
＜ガラス転移温度（℃）＞
　示差走査熱量計により、ガラス転移温度を測定する。 <Glass transition temperature (℃)>
Measure the glass transition temperature using a differential scanning calorimeter.
＜ポリオール　水酸基価＞
　ＪＩＳＫ１５５７－１に記載の方法に準拠し測定する。 <Polyol hydroxyl value>
Measured according to the method described in JIS K1557-1.
（ポリオール）
　実施例及び比較例で使用したポリオール１～７の組成及び物性を下記表１に示す。
　表１において、
ＴＰＡはテレフタル酸、ＩＰＡはイソフタル酸、ＡＡはアジピン酸、ＥＧはエチレングリコール、ＤＥＧはジエチレングリコール、１４ＢＧは１，４－ブチレングリコールを示す。
　例えば、表１のポリオール２は、テレフタル酸を０．３２ｇ、イソフタル酸を０．３２ｇ、エチレングリコールを０．１３ｇ、ジエチレングリコールを０．２３ｇの割合で混合し反応させて芳香族ポリエステルポリオールを作製したことを示している。 (polyol)
The compositions and physical properties of polyols 1 to 7 used in Examples and Comparative Examples are shown in Table 1 below.
In Table 1,
TPA is terephthalic acid, IPA is isophthalic acid, AA is adipic acid, EG is ethylene glycol, DEG is diethylene glycol, and 14BG is 1,4-butylene glycol.
For example, for polyol 2 in Table 1, an aromatic polyester polyol was prepared 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. It is shown that.
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
（ウレタン樹脂）
　ウレタン樹脂１は、次のようにして合成した。
　撹拌機、温度計、環流冷却器および窒素ガス導入管を備えた４つ口フラスコに、ポリオール２を０．７４ｇと、イソホロンジイソシアネートを０．２０ｇと、２，２’－ジメチロールプロピオン酸を０．０６ｇとの割合で仕込み、窒素気流下に７５℃で８時間反応させ、ウレタン樹脂１を得た。
　ウレタン樹脂１の組成及び物性を下記表２に示す。 (Urethane resin)
Urethane resin 1 was synthesized as follows.
In a four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 0.74 g of polyol 2, 0.20 g of isophorone diisocyanate, and 0.0 g of 2,2'-dimethylolpropionic acid were added. .06 g of the resin and reacted for 8 hours at 75° C. under a nitrogen stream to obtain urethane resin 1.
The composition and physical properties of Urethane Resin 1 are shown in Table 2 below.
　ウレタン樹脂１の組成を下記表２又は下記表３に示すように変えた他は同様の方法により、ウレタン樹脂２～９を作製した。
　ポリウレタン樹脂２～９の組成及び物性を表２及び表３に示す。 Urethane resins 2 to 9 were produced in the same manner except that the composition of urethane resin 1 was changed as shown in Table 2 or Table 3 below.
The compositions and physical properties of polyurethane resins 2 to 9 are shown in Tables 2 and 3.
Figure JPOXMLDOC01-appb-T000003
  
Figure JPOXMLDOC01-appb-T000003
  
Figure JPOXMLDOC01-appb-T000004
  
Figure JPOXMLDOC01-appb-T000004
  
　表１に記載の芳香環濃度は、以下の様にして求めた。
　ウレタン樹脂１を例に説明する。
　まず、ポリオール２の１ｇ中における芳香環濃度を算出する。
　・芳香環を含有する芳香族ジカルボン酸（ａ１－１）の原料モノマーの質量比率／そのモノマーの分子量、を求める。
　芳香族ジカルボン酸（ａ１－１）の原料モノマーが複数ある場合は、その和を求める。
　・｛０．３２（ポリオール２のテレフタル酸含有率）／１６６（テレフタル酸の分子量）＋０．３２（ポリオール２のイソフタル酸含有率）／１６６（イソフタル酸の分子量)｝×１０００＝３．８ｍｍｏｌ／ｇ The aromatic ring concentrations listed in Table 1 were determined as follows.
This will be explained using urethane resin 1 as an example.
First, the aromatic ring concentration in 1 g of polyol 2 is calculated.
- Determine the mass ratio of the raw material monomer of the aromatic dicarboxylic acid (a1-1) containing an aromatic ring/molecular weight of the monomer.
When there are multiple raw material monomers for the aromatic dicarboxylic acid (a1-1), the sum is determined.
・{0.32 (terephthalic acid content of polyol 2) / 166 (molecular weight of terephthalic acid) + 0.32 (isophthalic acid content of polyol 2) / 166 (molecular weight of isophthalic acid)} × 1000 = 3.8 mmol / g
　次に、芳香族ポリエステルポリオール（ａ１）１ｇ中の芳香環濃度とウレタン樹脂１ｇ中に占める芳香族ポリエステルポリオール（ａ１）の割合の積を求め、ウレタン樹脂１ｇ中の芳香環濃度を算出する。
　・３．８４（ポリオール２の芳香環濃度）×０．７４（ウレタン樹脂１のポリオール２の含有量）＝２．８ｍｍｏｌ／ｇ Next, the product of the aromatic ring concentration in 1 g of aromatic polyester polyol (a1) and the proportion of aromatic polyester polyol (a1) in 1 g of urethane resin is calculated to calculate the aromatic ring concentration in 1 g of urethane resin.
・3.84 (aromatic ring concentration of polyol 2) x 0.74 (content of polyol 2 in urethane resin 1) = 2.8 mmol/g
　表１に記載のエステル結合基濃度は、以下の様にして求めた。
　ウレタン樹脂１を例に説明する。
　まず、ポリオール２の１ｇ中におけるエステル結合基濃度を算出する。
　芳香族ポリエステルポリオール（ａ１）１ｇ中のカルボン酸のモル数をａとすると、ａは、以下の様にして求められる。
　・ａ＝｛０．３２（ポリオール２のテレフタル酸含有率）／１６６（テレフタル酸の分子量）＋０．３２（ポリオール２のイソフタル酸含有率）／１６６（イソフタル酸の分子量）｝×２（芳香族ジカルボン酸（ａ１－１）の原料モノマー中カルボン酸は２つ含まれている）＝０．００７７１
　次に、求めたａを上記式（Ｉ）に代入する。
　・{ａ／（１－ａ×１８（脱水する水の量））}×１０００＝８．９ｍｍｏｌ／ｇ The ester bond group concentrations listed in Table 1 were determined as follows.
This will be explained using urethane resin 1 as an example.
First, the concentration of ester bond groups in 1 g of polyol 2 is calculated.
Letting a be the number of moles of carboxylic acid in 1 g of aromatic polyester polyol (a1), a is determined as follows.
・a = {0.32 (terephthalic acid content of polyol 2) / 166 (molecular weight of terephthalic acid) + 0.32 (isophthalic acid content of polyol 2) / 166 (molecular weight of isophthalic acid)} x 2 (aromatic Two carboxylic acids are included in the raw material monomer of dicarboxylic acid (a1-1)) = 0.00771
Next, the obtained a is substituted into the above formula (I).
・{a/(1-a×18 (amount of water to be dehydrated))}×1000=8.9 mmol/g
　次に、芳香族ポリエステルポリオール（ａ１）１ｇ中のエステル結合基濃度とウレタン樹脂１ｇ中に占める芳香族ポリエステルポリオール（ａ１）の割合の積を求め、ウレタン樹脂１ｇ中のエステル結合基濃度を算出する。
　・８．９（ポリオール２のエステル結合基濃度）×０．７４（ウレタン樹脂１のポリオール２の含有量）＝６．６ｍｍｏｌ／ｇ Next, find the product of the ester bond group concentration in 1 g of aromatic polyester polyol (a1) and the proportion of aromatic polyester polyol (a1) in 1 g of urethane resin, and calculate the ester bond group concentration in 1 g of urethane resin. .
・8.9 (ester bond group concentration of polyol 2) x 0.74 (content of polyol 2 in urethane resin 1) = 6.6 mmol/g
　表１に記載のウレタン＋ウレア官能基濃度は、以下の様にして求めた。
　ウレタン樹脂１を例に説明する。
　・０．２（ウレタン樹脂１中のイソホロンジイソシアネートの含有量）÷１１１．１５（イソホロンジイソシアネートのＮＣＯ当量重量）＝１．８ｍｍｏｌ／ｇ
　　ここで、イソホロンジイソシアネートのＮＣＯ当量重量は、イソホロンジイソシアネートの分子量÷２で求められ、２２２．３÷２＝１１１．１５である。 The urethane+urea functional group concentrations listed in Table 1 were determined as follows.
This will be explained using urethane resin 1 as an example.
・0.2 (content of isophorone diisocyanate in urethane resin 1) ÷ 111.15 (NCO equivalent weight of isophorone diisocyanate) = 1.8 mmol/g
Here, the NCO equivalent weight of isophorone diisocyanate is determined by the molecular weight of isophorone diisocyanate/2, and is 222.3/2=111.15.
（（１－Ａ）タイプの積層体）
　下記に記載の表刷りタイプの構造からなる積層体を作製した。
　・（１－Ａ）基材Ａ－プライマー層－印刷層 ((1-A) type laminate)
A laminate having a surface printing type structure described below was produced.
・(1-A) Base material A-primer layer-printing layer
　実施例１で使用した積層体１は以下のようにして作製した。
　基材フィルム１として、ＯＰＰ基材フィルム（フタムラ化学株式会社製「ＦＯＲ　２０μｍ」）を使用した。
　プライマー層として、ウレタン樹脂１を使用し、水性ウレタン樹脂組成物には、架橋剤を含有させた。
　架橋剤を含むプライマー層は、次のように作製した。ウレタン樹脂１を用い、該ウレタン樹脂１００部に対し、日清紡ケミカル株式会社製「カルボジライトＳＶ－０２」を９部混合し、その後イソプロピルアルコール（ＩＰＡ）で固形分１０％に希釈した。
　上記で得られた水性ウレタン樹脂組成物を、版深度２２μｍを有するグラビア版を取り付けたグラビア印刷機（ＤＩＣエンジニアリング株式会社製）を用いて、片面にコロナ放電処理を施した基材フィルム１上に印刷を行った。その後、１００℃で１０分間、乾燥させ、その後、室温で１日以上放置した。
　インキ層は、次のように作製した。ラミネート用インキ「フィナート（ＤＩＣ社製）」をインキと同一比率の混合有機溶剤で希釈し、離合社製ザーンカップＮｏ３で１６秒になるように希釈した。それを、版深度２２μｍを有するグラビア版を取り付けたグラビア印刷機（ＤＩＣエンジニアリング株式会社製）を用いて、印刷を行った。
　得られた積層体１を４０℃で５日間エージングした。
　積層体１の構成を下記表４に示す。 Laminated body 1 used in Example 1 was produced as follows.
As the base film 1, an OPP base film (“FOR 20 μm” manufactured by Futamura Chemical Co., Ltd.) was used.
Urethane Resin 1 was used as the primer layer, and the aqueous urethane resin composition contained a crosslinking agent.
A primer layer containing a crosslinking agent was prepared as follows. Using urethane resin 1, 9 parts of "Carbodilite SV-02" manufactured by Nisshinbo Chemical Co., Ltd. was mixed with 100 parts of the urethane resin, and then diluted to a solid content of 10% with isopropyl alcohol (IPA).
The aqueous urethane resin composition obtained above was applied onto the base film 1, which had been subjected to corona discharge treatment on one side, using a gravure printing machine (manufactured by DIC Engineering Co., Ltd.) equipped with a gravure plate having a plate depth of 22 μm. I printed it. Thereafter, it was dried at 100° C. for 10 minutes, and then left at room temperature for one day or more.
The ink layer was produced as follows. Laminating ink "Finart (manufactured by DIC)" was diluted with a mixed organic solvent in the same ratio as the ink, and diluted with Zahn Cup No. 3 manufactured by Rigosha to a total of 16 seconds. It was printed using a gravure printing machine (manufactured by DIC Engineering Co., Ltd.) equipped with a gravure plate having a plate depth of 22 μm.
The obtained laminate 1 was aged at 40° C. for 5 days.
The structure of the laminate 1 is shown in Table 4 below.
　積層体１の構成を下記表４、下記表５、又は下記表６に示すように変えた他は同様の方法により、積層体２～２１を作製した。
　積層体２～２１の構成を表４～表６に示す。 Laminates 2 to 21 were produced in the same manner except that the configuration of laminate 1 was changed as shown in Table 4, Table 5, or Table 6 below.
The configurations of the laminates 2 to 21 are shown in Tables 4 to 6.
　積層体１の構成を下記表７、又は下記表８に示すように変えた他は同様の方法により、比較積層体１～１４を作製した。
　比較積層体１～１４の構成を表７～表８に示す。 Comparative laminates 1 to 14 were produced in the same manner except that the configuration of laminate 1 was changed as shown in Table 7 or Table 8 below.
The structures of comparative laminates 1 to 14 are shown in Tables 7 to 8.
　表４～８において、ＰＵ樹脂とは、ポリウレタン樹脂を示す。基材フィルム１が、ＰＥＴである場合は、該基材フィルムは、東洋紡株式会社製「Ｅ５１０２　１２μｍ」を示す。ＰＰ（ポリプロピレン）である場合は、該基材フィルムは、フタムラ化学製「ＦＯＲ　２０μｍ」を示す。
　ＯＰＥである場合は、該基材フィルムは、一軸延伸ポリエチレンフィルム（膜厚２５μｍ、密度０．９２ｇ／ｍ２、融点１２５℃）を示す。
　架橋剤が「ＢＵ３１００」とは、Ｃｏｖｅｓｔｒｏ社製の「Ｂａｙｈｙｄｕｒ　Ｕｌｔｒａ　３１００」を示す。
　「ＢＵ３１００」の架橋剤を含むプライマー層は、ウレタン樹脂１００部に対し、Ｃｏｖｅｓｔｒｏ社製「Ｂａｙｈｙｄｕｒ　Ｕｌｔｒａ　３１００」を３部混合し、その後、水で固形分１０％に希釈した。
　プライマー層が架橋剤を含まない場合、該プライマー層は、ウレタン樹脂に対し、イソプロピルアルコール（ＩＰＡ）で固形分１０％に希釈した水性ウレタン樹脂組成物を用いて形成した。該水性ウレタン樹脂組成物をグラビア印刷機を用いて塗布し、プライマー層を形成する方法は、積層体１の作製で上述したとおりである。
　比較例１２～１４で使用した各フィルムは、それぞれ次のとおりである。透明蒸着フィルム１は、大日本印刷株式会社製のアルミナ蒸着透明ＰＥＴフィルムＩＢ－ＰＥＴ－ＰＵＢ（厚み１２μｍ）であり、透明蒸着フィルム２は、三菱ケミカル株式会社製のシリカ蒸着透明ＰＥＴフィルム　テックバリア　ＴＸ－Ｒ（厚み１２μｍ）であり、金属蒸着フィルムは、凸版印刷株式会社製の酸化アルミニウム蒸着透明ＰＥＴフィルム　ＧＬ－ＡＲＨ（厚み１２μｍ）であった。 In Tables 4 to 8, PU resin refers to polyurethane resin. When the base film 1 is PET, the base film is "E5102 12 μm" manufactured by Toyobo Co., Ltd. In the case of PP (polypropylene), the base film is "FOR 20 μm" manufactured by Futamura Chemical.
In the case of OPE, the base film is a uniaxially stretched polyethylene film (film thickness 25 μm, density 0.92 g/m 2 , melting point 125° C.).
The crosslinking agent "BU3100" refers to "Bayhydur Ultra 3100" manufactured by Covestro.
A primer layer containing a crosslinking agent of "BU3100" was prepared by mixing 3 parts of "Bayhydur Ultra 3100" manufactured by Covestro with 100 parts of a urethane resin, and then diluting the mixture with water to a solid content of 10%.
When the primer layer did not contain a crosslinking agent, the primer layer was formed using an aqueous urethane resin composition diluted with isopropyl alcohol (IPA) to a solid content of 10%. The method of applying the aqueous urethane resin composition using a gravure printing machine to form a primer layer is as described above in the preparation of the laminate 1.
The films used in Comparative Examples 12 to 14 are as follows. The transparent vapor deposited film 1 is an alumina vapor deposited transparent PET film IB-PET-PUB (thickness 12 μm) manufactured by Dai Nippon Printing Co., Ltd., and the transparent vapor deposited film 2 is a silica vapor deposited transparent PET film Tech Barrier TX manufactured by Mitsubishi Chemical Corporation. -R (thickness: 12 μm), and the metal vapor-deposited film was aluminum oxide vapor-deposited transparent PET film GL-ARH (thickness: 12 μm) manufactured by Toppan Printing Co., Ltd.
（（１－１）タイプの積層体）
　下記に記載のラミネート構造を有する積層体を作製した。
　・（１－１）基材フィルム１／プライマー層／印刷層／接着層／シーラントフィルム ((1-1) type laminate)
A laminate having the laminate structure described below was produced.
・(1-1) Base film 1/primer layer/printing layer/adhesive layer/sealant film
　実施例１で使用した積層体１’は以下のようにして作製した。
　基材フィルム１として、ＯＰＰ基材フィルム（フタムラ化学株式会社製「ＦＯＲ　２０μｍ」）を使用した。
　プライマー層として、ウレタン樹脂１を使用し、水性ウレタン樹脂組成物には、架橋剤を含有させた。
　架橋剤を含むプライマー層は、次のように作製した。ウレタン樹脂１を用い、該ウレタン樹脂１００部に対し、日清紡ケミカル株式会社製「カルボジライトＳＶ－０２」を９部混合し、その後イソプロピルアルコール（ＩＰＡ）で固形分１０％に希釈した。
　上記で得られた水性ウレタン樹脂組成物を、版深度２２μｍを有するグラビア版を取り付けたグラビア印刷機（ＤＩＣエンジニアリング株式会社製）を用いて、片面にコロナ放電処理を施した基材フィルム１上に印刷を行った。その後、１００℃で１０分間、乾燥させ、その後、室温で１日以上放置した。
　インキ層は、次のように作製した。ラミネート用インキ「フィナート（ＤＩＣ社製）」をインキと同一比率の混合有機溶剤で希釈し、離合社製ザーンカップＮｏ３で１６秒になるように希釈した。それを、版深度２２μｍを有するグラビア版を取り付けたグラビア印刷機（ＤＩＣエンジニアリング株式会社製）を用いて、印刷を行った。
　上記のようにして得られた基材フィルム１、プライマー層、及び印刷層が積層された印刷物に対し、エーテル系接着剤のドライラミネート接着剤「ディックドライＬＸ－７６０Ａ／ＫＰ－７０（ＤＩＣ製）」を使用し、ドライラミネート機（ＤＩＣエンジニアリング製）によってシーラントフィルムを積層させ、実施例１の積層体１’を得た。
　ここで、シーラントフィルムは、東洋紡株式会社製「パイレンフィルムＣＴ　Ｐ１１２８　３０μｍ」を使用した。
　得られた積層体１’を４０℃で５日間エージングした。
　積層体１’の構成を下記表４に示す。 Laminated body 1' used in Example 1 was produced as follows.
As the base film 1, an OPP base film (“FOR 20 μm” manufactured by Futamura Chemical Co., Ltd.) was used.
Urethane Resin 1 was used as the primer layer, and the aqueous urethane resin composition contained a crosslinking agent.
A primer layer containing a crosslinking agent was prepared as follows. Using urethane resin 1, 9 parts of "Carbodilite SV-02" manufactured by Nisshinbo Chemical Co., Ltd. was mixed with 100 parts of the urethane resin, and then diluted to a solid content of 10% with isopropyl alcohol (IPA).
The aqueous urethane resin composition obtained above was applied onto the base film 1, which had been subjected to corona discharge treatment on one side, using a gravure printing machine (manufactured by DIC Engineering Co., Ltd.) equipped with a gravure plate having a plate depth of 22 μm. I printed it. Thereafter, it was dried at 100° C. for 10 minutes, and then left at room temperature for one day or more.
The ink layer was produced as follows. Laminating ink "Finart (manufactured by DIC)" was diluted with a mixed organic solvent in the same ratio as the ink, and diluted with Zahn Cup No. 3 manufactured by Rigosha to a total of 16 seconds. It was printed using a gravure printing machine (manufactured by DIC Engineering Co., Ltd.) equipped with a gravure plate having a plate depth of 22 μm.
The printed matter in which the base film 1, primer layer, and printing layer obtained as above were laminated was coated with an ether-based dry laminating adhesive "Dick Dry LX-760A/KP-70 (manufactured by DIC)". A sealant film was laminated using a dry laminating machine (manufactured by DIC Engineering) to obtain a laminate 1' of Example 1.
Here, as the sealant film, "Pyren Film CT P1128 30 μm" manufactured by Toyobo Co., Ltd. was used.
The obtained laminate 1' was aged at 40° C. for 5 days.
The structure of the laminate 1' is shown in Table 4 below.
　積層体１’の構成を下記表４、下記表５、又は下記表６に示すように変えた他は同様の方法により、積層体２’～２０’を作製した。
　積層体２’～２０’の構成を表４～表６に示す。 Laminates 2' to 20' were produced in the same manner except that the configuration of laminate 1' was changed as shown in Table 4, Table 5, or Table 6 below.
The configurations of the laminates 2' to 20' are shown in Tables 4 to 6.
　積層体１’の構成を下記表７、又は下記表８に示すように変えた他は同様の方法により、比較積層体１’～１１’を作製した。
　比較積層体１’～１１’の構成を表７～表８に示す。 Comparative laminates 1' to 11' were produced in the same manner except that the configuration of laminate 1' was changed as shown in Table 7 or Table 8 below.
The structures of comparative laminates 1' to 11' are shown in Tables 7 and 8.
　表４～８において、ＰＵ樹脂とは、ポリウレタン樹脂を示す。基材フィルム１が、ＰＥＴである場合は、該基材フィルムは、東洋紡株式会社製「Ｅ５１０２　１２μｍ」を示す。ＰＰ（ポリプロピレン）である場合は、該基材フィルムは、フタムラ化学製「ＦＯＲ　２０μｍ」を示す。
　ＯＰＥである場合は、該基材フィルムは、一軸延伸ポリエチレンフィルム（膜厚２５μｍ、密度０．９２ｇ／ｍ２、融点１２５℃）を示す。
　架橋剤が「ＢＵ３１００」とは、Ｃｏｖｅｓｔｒｏ社製の「Ｂａｙｈｙｄｕｒ　Ｕｌｔｒａ　３１００」を示す。
　「ＢＵ３１００」の架橋剤を含むプライマー層は、ウレタン樹脂１００部に対し、Ｃｏｖｅｓｔｒｏ社製「Ｂａｙｈｙｄｕｒ　Ｕｌｔｒａ　３１００」を３部混合し、その後、水で固形分１０％に希釈した。
　プライマー層が架橋剤を含まない場合、該プライマー層は、ウレタン樹脂に対し、イソプロピルアルコール（ＩＰＡ）で固形分１０％に希釈した水性ウレタン樹脂組成物を用いて形成した。該水性ウレタン樹脂組成物をグラビア印刷機を用いて塗布し、プライマー層を形成する方法は、積層体１’の作製で上述したとおりである。 In Tables 4 to 8, PU resin refers to polyurethane resin. When the base film 1 is PET, the base film is "E5102 12 μm" manufactured by Toyobo Co., Ltd. In the case of PP (polypropylene), the base film is "FOR 20 μm" manufactured by Futamura Chemical.
In the case of OPE, the base film is a uniaxially stretched polyethylene film (film thickness 25 μm, density 0.92 g/m 2 , melting point 125° C.).
The crosslinking agent "BU3100" refers to "Bayhydur Ultra 3100" manufactured by Covestro.
A primer layer containing a crosslinking agent of "BU3100" was prepared by mixing 3 parts of "Bayhydur Ultra 3100" manufactured by Covestro with 100 parts of a urethane resin, and then diluting the mixture with water to a solid content of 10%.
When the primer layer did not contain a crosslinking agent, the primer layer was formed using an aqueous urethane resin composition diluted with isopropyl alcohol (IPA) to a solid content of 10%. The method of applying the aqueous urethane resin composition using a gravure printing machine to form a primer layer is as described above in the preparation of the laminate 1'.
（実施例１）
　積層体１に対して、以下に示す剥離性の試験を行った。 (Example 1)
The following peelability test was conducted on the laminate 1.
＜剥離性の評価＞
＜＜アルカリ溶液＞＞
　下記各条件で剥離試験を実施し、各条件下における剥離のしやすさを比較した。
　　・水酸化ナトリウム１質量％、界面活性剤なし
　液温は試験条件に合わせて、各８５℃、５５℃、２５℃に設定した。 <Evaluation of peelability>
<<Alkaline solution>>
A peel test was conducted under the following conditions, and the ease of peeling under each condition was compared.
- 1% by mass of sodium hydroxide, no surfactant The liquid temperature was set at 85°C, 55°C, and 25°C, respectively, according to the test conditions.
＜＜剥離試験条件＞＞
　印刷物を２０ｍｍ×２０ｍｍのサイズにカットした試験片を溶液に浸漬してスターラーで撹拌した。
　撹拌後に剥離状態を確認した後、指で印刷物を擦り、擦ることで塗膜が剥離するかも確認した。
　上記の条件におけるインキ塗膜の剥離性を下記評価基準に従い評価した。 <<Peeling test conditions>>
A test piece obtained by cutting a printed matter into a size of 20 mm x 20 mm was immersed in the solution and stirred with a stirrer.
After checking the peeling state after stirring, the printed matter was rubbed with a finger to check whether the coating film peeled off by rubbing.
The releasability of the ink coating under the above conditions was evaluated according to the following evaluation criteria.
［評価基準］
　　５：　５分以内の撹拌でインキ塗膜の剥離を確認。擦ると完全に脱離
　　４：　１５分の撹拌でインキ塗膜の剥離を確認。擦ると完全に脱離
　　３：　１５分の撹拌でインキ塗膜の剥離を未確認。擦ると完全に脱離
　　２：　６０分の撹拌でインキ塗膜の剥離を未確認。擦ると部分的に脱離
　　１：　６０分の撹拌でインキ塗膜の剥離を未確認。擦っても脱離を未確認
　尚、上記評価結果については、実用上４以上の水準であることが好ましいが、３においてもリサイクルに貢献可能な水準であるため、３以上の水準を合格水準であると判断することができる。 [Evaluation criteria]
5: Peeling of the ink coating was confirmed within 5 minutes of stirring. Completely removed when rubbed 4: Peeling of the ink coating was confirmed after 15 minutes of stirring. Completely removed when rubbed 3: No peeling of the ink coating was observed after 15 minutes of stirring. Completely removed when rubbed 2: No peeling of the ink coating was observed after 60 minutes of stirring. Partial detachment when rubbed 1: No peeling of the ink film was confirmed after 60 minutes of stirring. Desorption has not been confirmed even when rubbed.For the above evaluation results, a level of 4 or higher is preferable for practical purposes, but even a level of 3 is a level that can contribute to recycling, so a level of 3 or higher is considered a passing level. It can be determined that
　積層体１’に対して、以下に示す脱ラミネーション性の試験を行った。 The following delamination test was conducted on the laminate 1'.
＜脱ラミネーション性の評価＞
＜＜アルカリ溶液＞＞
　下記各条件で剥離試験を実施し、各条件下における剥離のしやすさを比較した。
　　・水酸化ナトリウム１質量％、界面活性剤なし
　液温は８５℃に設定した。 <Evaluation of delamination performance>
<<Alkaline solution>>
A peel test was conducted under the following conditions, and the ease of peeling under each condition was compared.
・Sodium hydroxide 1% by mass, no surfactant The liquid temperature was set at 85°C.
＜＜脱ラミネーション試験条件＞＞
　ラミネーション物（複層フィルム）を１０ｍｍ×１０ｍｍのサイズにカットした試験片を溶液に浸漬してスターラーで撹拌した。
　複層フィルムから基材が脱ラミネーションしているかを確認した。
　ここで脱ラミネーションとは複層体のうち、特定のフィルムが完全に分離されている状態と定義する。
　上記の条件におけるインキ塗膜の剥離性を下記評価基準に従い評価した。 <<Delamination test conditions>>
A test piece obtained by cutting a laminated product (multilayer film) into a size of 10 mm x 10 mm was immersed in the solution and stirred with a stirrer.
It was confirmed whether the base material was delaminated from the multilayer film.
Here, delamination is defined as a state in which a specific film in a multilayer body is completely separated.
The releasability of the ink coating under the above conditions was evaluated according to the following evaluation criteria.
［評価基準］
　　４：　５時間未満の撹拌で複層フィルムから基材が脱ラミネーション
　　３：　１０時間以内の撹拌で複層フィルムから基材が脱ラミネーション
　　２：　１０時間の撹拌でフィルムが浮き上がる等の兆候が確認でき、２４時間の撹拌で複層フィルムから基材が脱ラミネーション
　　１：　１０時間の撹拌で処理前と外観変化なし
　尚、上記評価結果については、実用上３以上であることが好ましいが、２においてもリサイクルに貢献可能な水準であると判断することができる。 [Evaluation criteria]
4: The base material was delaminated from the multilayer film after stirring for less than 5 hours. 3: The base material was delaminated from the multilayer film after stirring for less than 10 hours. 2: Signs such as lifting of the film could be confirmed after stirring for 10 hours. , the base material was delaminated from the multilayer film after stirring for 24 hours. 1: There was no change in appearance from before treatment after stirring for 10 hours. Regarding the above evaluation results, it is preferable for practical purposes to be 3 or higher, but even in 2. It can be judged that the level is such that it can contribute to recycling.
　積層体１に対する剥離性の評価結果、及び積層体１’に対する脱ラミネーション性の評価結果を、表４に示す。 Table 4 shows the peelability evaluation results for the laminate 1 and the delamination evaluation results for the laminate 1'.
（実施例２～２１、及び比較例１～１４）
　実施例１の積層体１及び積層体１’を、それぞれ積層体２～２１、もしくは比較積層体１～１４、又は積層体２’～２０’、もしくは比較積層体１’～１１’に変更した以外は、実施例１と同様にして、剥離性、及び脱ラミネーション性の試験を行った。
　評価結果を表４～表８に示す。但し、比較例１２（比較積層体１２）～比較例１４（比較積層体１４）については、通常の温度条件下でもアルカリ溶液による剥離が生じ、本発明の目的を達成することができなかったため、脱ラミネーション性の試験は行わなかった。 (Examples 2 to 21 and Comparative Examples 1 to 14)
The laminates 1 and 1' of Example 1 were changed to laminates 2 to 21, comparative laminates 1 to 14, laminates 2' to 20', or comparative laminates 1' to 11', respectively. Except for this, peelability and delamination tests were conducted in the same manner as in Example 1.
The evaluation results are shown in Tables 4 to 8. However, for Comparative Examples 12 (Comparative Laminated Body 12) to Comparative Example 14 (Comparative Laminated Body 14), peeling occurred due to the alkaline solution even under normal temperature conditions, and the objective of the present invention could not be achieved. No delamination test was conducted.
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000006
  
Figure JPOXMLDOC01-appb-T000006
  
Figure JPOXMLDOC01-appb-T000007
  
Figure JPOXMLDOC01-appb-T000007
  
Figure JPOXMLDOC01-appb-T000008
  
Figure JPOXMLDOC01-appb-T000008
  
Figure JPOXMLDOC01-appb-T000009
  
Figure JPOXMLDOC01-appb-T000009
  
　上記実施例の結果から明らかなように、本発明の水性ウレタン樹脂組成物で形成されたプライマー層を有する積層体は、８５℃及び５５℃の温度条件下で、アルカリ溶液を用いることにより容易にプライマー層を脱離することができた。一方、２５℃の温度条件下では、アルカリ溶液によりプライマー層は脱離されなかった。
　また、本発明の積層体は、複数の層が積層されてなるラミネートタイプの構造を有していても、アルカリ溶液によりプライマー層を脱離することができた。

  As is clear from the results of the above examples, a laminate having a primer layer formed of the aqueous urethane resin composition of the present invention can be easily produced by using an alkaline solution under temperature conditions of 85°C and 55°C. The primer layer could be removed. On the other hand, under the temperature condition of 25° C., the primer layer was not removed by the alkaline solution.
Furthermore, even if the laminate of the present invention had a laminate type structure in which a plurality of layers were laminated, the primer layer could be removed using an alkaline solution.

Claims (12)

  1. 　ウレタン樹脂（Ａ）及び水性媒体（Ｂ）を含有する水性ウレタン樹脂組成物であって、
    　前記ウレタン樹脂（Ａ）が、芳香族ジカルボン酸（ａ１－１）を原料モノマーとして含む芳香族ポリエステルポリオール（ａ１）とポリイソシアネート（ａ２）との反応物からなり、
    　前記ウレタン樹脂（Ａ）における前記芳香族ジカルボン酸（ａ１－１）の原料モノマー由来の芳香環濃度が、１ｍｍｏｌ／ｇ以上であり、
    　前記ウレタン樹脂（Ａ）におけるエステル結合基濃度が、１ｍｍｏｌ／ｇ以上であり、
    　前記ウレタン樹脂（Ａ）の酸価が８～４５ｍｇＫＯＨ／ｇである、水性ウレタン樹脂組成物。     An aqueous urethane resin composition containing a urethane resin (A) and an aqueous medium (B),
    The urethane resin (A) is made of a reaction product of an aromatic polyester polyol (a1) containing an aromatic dicarboxylic acid (a1-1) as a raw material monomer and a polyisocyanate (a2),
    The aromatic ring concentration derived from the raw material monomer of the aromatic dicarboxylic acid (a1-1) in the urethane resin (A) is 1 mmol/g or more,
    The ester bond group concentration in the urethane resin (A) is 1 mmol/g or more,
    An aqueous urethane resin composition, wherein the urethane resin (A) has an acid value of 8 to 45 mgKOH/g.
  2. 　前記ポリイソシアネート（ａ２）が、イソホロンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、及びジシクロヘキシルメタンジイソシアネートの群から選ばれる少なくとも１種である、請求項１に記載の水性ウレタン樹脂組成物。 The aqueous urethane resin composition according to claim 1, wherein the polyisocyanate (a2) is at least one selected from the group of isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.
  3. 　前記ウレタン樹脂（Ａ）の１ｇ中に含有される前記ポリイソシアネート（ａ２）の原料モノマーの質量を、前記ポリイソシアネート（ａ２）の原料モノマーのＮＣＯ当量重量で除した値が、１．０～６．０ｍｍｏｌ／ｇである、請求項１に記載の水性ウレタン樹脂組成物。 The value obtained by dividing the mass of the raw material monomer of the polyisocyanate (a2) contained in 1 g of the urethane resin (A) by the NCO equivalent weight of the raw material monomer of the polyisocyanate (a2) is 1.0 to 6. The aqueous urethane resin composition according to claim 1, which has a content of .0 mmol/g.
  4. 　前記ウレタン樹脂（Ａ）の重量平均分子量が、１０，０００以上である、請求項１に記載の水性ウレタン樹脂組成物。 The aqueous urethane resin composition according to claim 1, wherein the urethane resin (A) has a weight average molecular weight of 10,000 or more.
  5. 　前記ウレタン樹脂（Ａ）のガラス転移温度が、０～１１０℃である、請求項１に記載の水性ウレタン樹脂組成物。 The aqueous urethane resin composition according to claim 1, wherein the urethane resin (A) has a glass transition temperature of 0 to 110°C.
  6. 　基材Ａ上に、請求項１～５のいずれかに記載の水性ウレタン樹脂組成物が塗工されてなるプライマー層を有し、さらに前記プライマー層上に印刷インキ組成物が印刷されてなる印刷層を有する、積層体。 Printing comprising a primer layer coated with the aqueous urethane resin composition according to any one of claims 1 to 5 on the base material A, and further printing with a printing ink composition on the primer layer. A laminate having layers.
  7. 　前記水性ウレタン樹脂組成物が、架橋剤を含有する、請求項６に記載の積層体。 The laminate according to claim 6, wherein the aqueous urethane resin composition contains a crosslinking agent.
  8. 　前記基材Ａ上への前記水性ウレタン樹脂組成物の塗工方法が、前記基材Ａの延伸工程途中に前記水性ウレタン樹脂組成物を塗布し、その後さらに延伸工程を行うインラインコーティング法であるか、又は前記基材の延伸工程の後に、前記水性ウレタン樹脂組成物を塗布し乾燥することで前記プライマー層を形成するオフラインコーティング法である、請求項６に記載の積層体。 The method for applying the aqueous urethane resin composition onto the base material A is an in-line coating method in which the aqueous urethane resin composition is applied during the stretching process of the base material A, and then a further stretching process is performed. 7. The laminate according to claim 6, which is an offline coating method in which the aqueous urethane resin composition is applied and dried to form the primer layer after the step of stretching the base material.
  9. 　電子機材、建材、繊維・皮革、家電製品、乗り物、家具、オフィス用品、遊具、スポーツ用品あるいはその部品の成型物として、または包装材料として用いる、請求項６に記載の積層体。 The laminate according to claim 6, which is used as a molded product for electronic equipment, building materials, textiles/leather, home appliances, vehicles, furniture, office supplies, play equipment, sports equipment, or parts thereof, or as a packaging material.
  10. 　請求項６に記載の積層体に対して、前記印刷層の前記基材Ａが配置されている面とは反対側の面に、基材Ｂを配置し、前記基材Ａと前記プライマー層と前記印刷層と前記基材Ｂとが積層してなる積層体。 In the laminate according to claim 6, a base material B is disposed on a surface of the printing layer opposite to the surface on which the base material A is disposed, and the base material A and the primer layer are disposed. A laminate formed by laminating the printing layer and the base material B.
  11. 　請求項６に記載の積層体に対して、アルカリ溶液で処理することにより前記プライマー層とともに印刷層を基材Ａから脱離して得られるリサイクル基材Ａの製造方法。 A method for producing a recycled base material A, which is obtained by treating the laminate according to claim 6 with an alkaline solution to remove the printing layer from the base material A together with the primer layer.
  12. 　請求項１０に記載の積層体に対して、アルカリ溶液で処理することにより前記プライマー層とともに印刷層及び／又は基材Ｂを基材Ａから脱離して得られるリサイクル基材Ａの製造方法。

          A method for producing a recycled substrate A, which is obtained by treating the laminate according to claim 10 with an alkaline solution to remove the printing layer and/or the substrate B together with the primer layer from the substrate A.
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Citations (5)

* Cited by examiner, † Cited by third party
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US20150284598A1 (en) * 2014-04-07 2015-10-08 Avery Dennison Corporation Compositions for Removable Labels
JP2015218191A (en) * 2014-05-14 2015-12-07 Dic株式会社 Aqueous pigment composition, printing ink, printing method, and inkjet printing method
JP2017014307A (en) * 2015-06-26 2017-01-19 Dic株式会社 Aqueous resin composition, and laminate and article using the same
JP2017115018A (en) * 2015-12-24 2017-06-29 Dic株式会社 Aqueous resin composition, laminate and article using the same
JP2018104535A (en) * 2016-12-26 2018-07-05 Dic株式会社 Aqueous resin composition, coating agent and article

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150284598A1 (en) * 2014-04-07 2015-10-08 Avery Dennison Corporation Compositions for Removable Labels
JP2015218191A (en) * 2014-05-14 2015-12-07 Dic株式会社 Aqueous pigment composition, printing ink, printing method, and inkjet printing method
JP2017014307A (en) * 2015-06-26 2017-01-19 Dic株式会社 Aqueous resin composition, and laminate and article using the same
JP2017115018A (en) * 2015-12-24 2017-06-29 Dic株式会社 Aqueous resin composition, laminate and article using the same
JP2018104535A (en) * 2016-12-26 2018-07-05 Dic株式会社 Aqueous resin composition, coating agent and article

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