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.

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