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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • 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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • 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
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• • 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
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
• • 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
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
• • 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
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
  • C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/06—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
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/08—Polyurethanes from polyethers
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric coating
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/28—Multiple coating on one surface
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/748—Releasability
• • 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
  • B32B2553/00—Packaging equipment or accessories not otherwise provided for
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard

Definitions

• the present invention relates to an adhesive, a laminate obtained using the adhesive, and a packaging material.
• Laminates used for various packaging materials, labels, etc. are given design, functionality, storage stability, convenience, and transportability by laminating a wide variety of base materials such as plastic films, metal foils, and paper.
• packages formed by molding the laminate into bags are used as packages for foods, medicines, detergents, and the like.
• laminates used for packaging are produced by applying an adhesive dissolved in a volatile organic solvent (sometimes referred to as a solvent-based lamination adhesive) to a base material, and then passing through an oven.
• a volatile organic solvent sometimes referred to as a solvent-based lamination adhesive
• reaction lamination methods that do not contain volatile organic solvents have been used.
• Demand for a two-liquid type lamination adhesive (hereinafter referred to as a non-solvent adhesive) is increasing (Patent Document 1).
• Solvent-free adhesives do not require a drying process and do not emit solvents. They are energy-saving and have good running costs. It has many merits, such as the fact that there is no concern that the solvent will remain in the laminate after being combined. On the other hand, there is a problem that air bubbles caught in the adhesive when it is mixed and applied to the base material tend to remain in the cured coating film of the adhesive, and the air bubbles tend to aggregate during the aging process, resulting in a poor appearance.
• a printed layer is generally provided with printing ink on the back side of the base material that is the outermost layer (viewed from the content), and the printed layer and other base materials are connected via an adhesive. are pasted together.
• the components used in solvent-free adhesives must be designed to have a low molecular weight so that they can be applied when heated to about 40°C to 100°C. It is easy to dissolve the layer again, and there is a possibility that the printed layer may have black spots and other appearance defects.
• the present invention has been made in view of such circumstances, and provides a solvent-free adhesive that is unlikely to cause poor appearance due to air bubbles or dissolution of a printed layer, a laminate obtained using the adhesive, and a packaging material. for the purpose.
• the present invention provides a polyisocyanate composition (A) containing a urethane prepolymer (A1) which is a reaction product of a polyester polyol (a1), a polyether polyol (a2), and a polyisocyanate compound (a3); and a polyol composition (B) containing a polyester polyol (B1) which is a reaction product of a monomer composition containing a carboxylic acid (b1-1) and a polyol (b1-2), and a polyester polyol (a1 ) is a reaction product of a monomer composition containing a polyhydric carboxylic acid (a1-1) and a polyhydric alcohol (a1-2), and the polyhydric alcohol (a1-2) contains 80% by mass or more of diethylene glycol.
• the amount of the polyester polyol (a1) in the total amount of the polyester polyol (a1) and the polyether polyol (a2) is 50% by mass or more and 90% by mass or less, and the polyhydric alcohol (b1-2) contains 80% diethylene glycol. It relates to a two-liquid curable adhesive containing more than mass %.
• the present invention includes a first base material, a second base material, and an adhesive layer that bonds the first base material and the second base material, and the adhesive layer is the above-described two-liquid curing type
• the present invention relates to a laminate that is a cured coating film of an adhesive, and a packaging material comprising the laminate.
• the adhesive of the present invention it is possible to provide a laminate and a packaging material in which defects in the appearance of the laminate due to air bubbles and redissolution of ink are suppressed.
• the adhesive of the present invention is a two-liquid curing adhesive comprising a polyisocyanate composition (A) and a polyol composition (B).
• A polyisocyanate composition
• B polyol composition
• the polyisocyanate composition (A) used in the adhesive of the present invention is a urethane prepolymer (A1 )including.
• the polyester polyol (a1) is a reaction product of a monomer composition containing a polyhydric carboxylic acid (a1-1) and a polyhydric alcohol (a1-2), and contains 80% by mass or more of the polyhydric alcohol (a1-2). is diethylene glycol.
• Examples of the polyvalent carboxylic acid (a1-1) used in the synthesis of the polyester polyol (a1) include orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, and 2,5-naphthalenedicarboxylic acid.
• Aliphatic polybasic acids such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, and itaconic acid; Aliphatic polybasic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate Alkyl ester of;
• the polyvalent carboxylic acid (a1-1) preferably contains adipic acid because it is excellent in reducing the viscosity of the urethane prepolymer (A1) and improving the coatability at low temperatures.
• the blending amount of adipic acid can be appropriately adjusted according to the temperature at the time of coating, etc., but it is preferably 80% by mass or more, more preferably 90% by mass or more, of the polyvalent carboxylic acid (a1-1). preferable.
• the total amount of polycarboxylic acid (a1-1) may be adipic acid.
• the polyhydric alcohol (a1-2) that can be used in combination with diethylene glycol is not particularly limited.
• bifunctional alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3 - propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl 1,5-pentanediol, neopentyl glycol, Aliphatic diols such as 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2,4-trimethyl-1,3-pentanediol;
• Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol; Modified poly(s) obtained by ring-opening polymerization of aliphatic diols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether.
• ether diol
• Lactone-based polyester polyols obtained by polycondensation reaction of aliphatic diols with various lactones such as lactanoids and ⁇ -caprolactone; Bisphenols such as bisphenol A and bisphenol F; Alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F can be mentioned.
• Tri- or higher functional polyols include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol; Modified polyols obtained by ring-opening polymerization of aliphatic polyols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether.
• ether polyols examples include lactone-based polyester polyols obtained by polycondensation reaction of aliphatic polyols with various lactones such as ⁇ -caprolactone.
• the proportion of diethylene glycol in the polyhydric alcohol (a1-2) is preferably 90% by mass or more, more preferably 95% by mass or more, because the ink is difficult to re-dissolve when the adhesive is applied onto the printed layer. is more preferred. All of the polyhydric alcohol (a1-2) may be diethylene glycol.
• the number average molecular weight of the polyester polyol (a1) is not particularly limited, it is, for example, 400 or more and 10,000 or less, more preferably 500 or more and 2,000 or less.
• the number average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) under the following conditions.
• HLC-8320GPC manufactured by Tosoh Corporation Column
• TSKgel 4000HXL TSKgel 3000HXL
• TSKgel 2000HXL TSKgel 1000HXL manufactured by Tosoh Corporation Detector
• RI differential refractometer
• Multi-station GPC-8020modelII manufactured by Tosoh Corporation Measurement conditions
• Monodisperse polystyrene Sample 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 ⁇ l)
• polyether polyol (a2) oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran are polymerized using a low molecular weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane and glycerin as an initiator. Those obtained can be mentioned, and one type or two or more types can be used in combination.
• the number of functional groups of the polyether polyol (a2) is not particularly limited, and in addition to bifunctional ones, trifunctional or higher functional groups can also be used. It is preferred to use bifunctional or trifunctional polypropylene glycol.
• the number average molecular weight of the polyether polyol (a2) is not particularly limited, it is, for example, 200 or more and 10,000 or less, more preferably 400 or more and 2,000 or less.
• the blending amount of the polyester polyol (a1) in the total amount of the polyester polyol (a1) and the polyether polyol (a2) is 50% by mass or more and 90% by mass or less.
• the polyisocyanate compound (a3) is not particularly limited, and includes aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and burettes, nurates, adducts, allophanates, and carbodiimide modifications of these diisocyanates. , uretdione-modified products, urethane prepolymers obtained by reacting these polyisocyanates with polyols, and the like, and these can be used alone or in combination.
• aromatic diisocyanates examples include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (also referred to as polymeric MDI or crude MDI).
• Araliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, m- or p-xylylene diisocyanate (also known as XDI), ⁇ , ⁇ , ⁇ ', ⁇ '-tetra Methyl xylylene diisocyanate (another name: TMXDI) and the like can be mentioned, but not limited to these.
• Aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodecamethylene. Examples include, but are not limited to, diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.
• Alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4′-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, etc., and these is not limited to
• Polyols used for synthesis of urethane prepolymers include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Alkylene glycols such as 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol;
• Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F; dimer diall; bishydroxyethoxybenzene;
• Polyalkylene glycols such as diethylene glycol, triethylene glycol, other polyethylene glycols, polypropylene glycol, polybutylene glycol; Urethane bond-containing polyether polyol obtained by further polymerizing polyalkylene glycol with aromatic or aliphatic polyisocyanate;
• polyester polyol Obtained by reacting with at least one aromatic polyvalent carboxylic acid such as aliphatic dicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid having a carbon atom number in the range of 2 to 13 a polyester polyol; Polyester obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, glycol, glycerin, trimethylolpropane, pentaerythritol, etc. and a polyester polyol which is a reaction product with a polyhydric alcohol.
• aromatic polyvalent carboxylic acid such as aliphatic dicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid having a carbon atom
• aromatic diisocyanate and/or its derivatives From the viewpoint of initial cohesion and shortening of aging time, it is preferable to use aromatic diisocyanate and/or its derivatives.
• the urethane prepolymer (A1) is obtained by reacting the polyester polyol (a1), the polyether polyol (a2), and the polyisocyanate compound (a3) described above under conditions of excess isocyanate groups.
• the ratio [NCO]/[OH] between the number of moles [NCO] of isocyanate groups and the number of moles [OH] of hydroxyl groups used for the reaction is preferably 1.0 or more and 3.0 or less. It is more preferably 1.5 to 2.0.
• the polyisocyanate composition (A) may contain an isocyanate compound (A2) other than the urethane prepolymer.
• an isocyanate compound (A2) the same polyisocyanate compound (a3) as described above can be used.
• the viscosity of the polyisocyanate composition (A) is adjusted within a range suitable for the non-solvent lamination method.
• the viscosity at 40° C. is adjusted to be in the range of 500-5000 mPas, more preferably 500-3000 mPas.
• the viscosity of the polyisocyanate composition (A) can be adjusted by, for example, the blending amount of the urethane prepolymer (A1) and the blending amount of the isocyanate compound (A2).
• the polyol composition (B) used in the adhesive of the present invention contains a polyester polyol (B1) which is a reaction product of a polyhydric carboxylic acid (b1-1) and a polyhydric alcohol (b1-2). Also, the polyhydric alcohol (b1-2) contains 80% by mass or more of diethylene glycol.
• the same polycarboxylic acid (a1-1) can be used.
• the amount of adipic acid to be blended can be appropriately adjusted depending on the coating conditions and the like, but as an example, it is preferably 10% by mass or more and 50% by mass or less of the polyvalent carboxylic acid (b1-1).
• Acid (b1-1) preferably comprises isophthalic acid.
• the content of isophthalic acid is preferably 50% by mass or more and 70% by mass or less of the polyvalent carboxylic acid (b1-1).
• the total amount of adipic acid and isophthalic acid in the polycarboxylic acid (b-1) is preferably 90% by mass or more.
• the same polyhydric alcohol (a1-2) can be used.
• the content of diethylene glycol in the polyhydric alcohol (b1-2) is more preferably 90% by mass or more, more preferably 95% by mass or more, because of its excellent effect of suppressing redissolution of the ink. All of the polyhydric alcohol (b1-2) may be diethylene glycol.
• the number average molecular weight of the polyester polyol (B1) is not particularly limited, it is preferably 500 or more and 3,000 or less as an example.
• the blending amount of the polyester polyol (B1) is preferably 50% by mass or more of the polyol composition (B). This increases the cohesive force of the adhesive, suppresses the aggregation and growth of air bubbles, and improves the appearance of the laminate.
• the polyol composition (B) preferably contains a monool compound (B2).
• a monool compound (B2) does not have a hydroxyl group at one end, so that the viscosity of the polyol composition (B) is easily reduced, and entrainment of air bubbles is suppressed when the adhesive is applied. is doing.
• the monool compound (B2) the crosslink density of the adhesive layer is reduced and the flexibility is improved, thereby improving the adhesion of the metal or metal oxide to the deposited layer. Effects such as improved coatability and low-temperature workability can also be obtained.
• the main chain of the monool compound (B2) is not particularly limited, and vinyl resins having one hydroxyl group, acrylic resins, polyesters, epoxy resins, urethane resins and the like can be mentioned. Aliphatic alcohols, alkyl alkylene glycols, and the like can also be used.
• the main chain of the monool compound (B2) may be linear or branched.
• the bonding position of the hydroxyl group is also not particularly limited, but it is preferably present at the end of the molecular chain.
• Such monool compounds (B2) include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, hepta aliphatic monools such as decanol, stearyl alcohol, nonadecanol, other alkanols (C20-50), oleyl alcohol, and isomers thereof;
• Aromatic aliphatic monools such as benzyl alcohol,
• Examples include polyoxyalkylene monools obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using an alkyl compound containing one active hydrogen as an initiator.
• alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using an alkyl compound containing one active hydrogen as an initiator.
• polyoxyalkylene monool it is preferable to use polyoxyalkylene monool, and it is preferable to use polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, and polypropylene monobutyl ether.
• the amount of the monool compound (B2) to be blended can be appropriately adjusted depending on the intended physical properties, but since the above-mentioned effects are likely to be obtained, as an example, it should be 1% by mass or more of the total amount with the polyester polyol (B1). is preferred. It is more preferably 3% by mass or more, still more preferably 5% by mass or more of the polyol composition (X). Moreover, in order to maintain the cohesive strength of the adhesive, it is preferably 30% by mass or less of the total amount with the polyester polyol (B1).
• the polyol composition (B) may contain a polyol (B3) other than the polyester polyol (B1) and the monool compound (B2).
• polyols (B3) include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexane Glycols such as diols, 1,4-cyclohexanedimethanol, triethylene glycol;
• trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diol; Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of polymerization initiators such as the aforementioned glycols and trifunctional or tetrafunctional aliphatic alcohols. ; A polyether urethane polyol obtained by further increasing the molecular weight of a polyether polyol with the aromatic or aliphatic polyisocyanate;
• Polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, and the aforementioned glycols, glycerin, trimethylolpropane, pentaerythritol, etc.
• polyester polyol (1) which is a reaction product with a polyhydric alcohol
• Polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a polyvalent carboxylic acid
• Polyester polyol (3) obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid
• a polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid
• polyester polyols (5) which are polymers of hydroxyl acids such as dimethylolpropionic acid and castor oil fatty acids;
• Polyester polyether polyols obtained by reacting polyester polyols (1) to (5) with the above polyether polyols and aromatic or aliphatic polyisocyanates; Polyester polyurethane polyols obtained by polymerizing polyester polyols (1) to (5) with aromatic or aliphatic polyisocyanates; Castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated castor oil, castor oil-based polyols such as adducts of 5 to 50 moles of alkylene oxide of castor oil, and mixtures thereof.
• Examples of the polyvalent carboxylic acid used for preparing the polyester polyol (2) include those exemplified as the raw material for the polyester polyol (B1).
• the blending amount of the polyol (B3) is not particularly limited, but it is preferable to limit it to 50% by mass or less of the total amount with the polyester polyol (B1).
• the viscosity of the polyol composition (B) is adjusted within a range suitable for the non-solvent lamination method.
• the viscosity at 40° C. is adjusted to be in the range of 100-5000 mPas, more preferably 100-3000 mPas.
• the viscosity of the polyol composition (B) can be adjusted, for example, by the skeleton of the polyester polyol (B1) and the plasticizer (C5) described later.
• the adhesive of the present invention may contain components other than those mentioned above.
• the other component (C) may be contained in either or both of the polyisocyanate composition (A) and the polyol composition (B), or may be prepared separately from these and applied to the adhesive. It may be mixed with the polyisocyanate composition (A) and the polyol composition (B) immediately before use. Each component will be described below.
• Catalyst (C1) examples include metal-based catalysts, amine-based catalysts, and aliphatic cyclic amide compounds.
• Metal-based catalysts (C1) include metal complex-based, inorganic metal-based, and organic metal-based catalysts.
• the metal complex catalyst a group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), Co (cobalt) Examples include acetylacetonate salts of metals selected from the above, such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate and the like.
• inorganic metal-based catalysts examples include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.
• Organometallic catalysts include organozinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; , dioctyltin dilaurate, dibutyltin oxide, dibutyltin dichloride and other organic tin compounds, nickel octylate, nickel naphthenate and other organic nickel compounds, cobalt octylate, cobalt naphthenate and other organic cobalt compounds, bismuth octylate, neodecanoic acid At least one of organic bismuth compounds such as bismuth and bismuth naphthenate, tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and alcohols having 2 to 10 carbon atoms.
• Amine catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl Propylenediamine, N,N,N',N',N''-pentamethyldiethylenetriamine, N,N,N',N'',N'-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N', N′′,N′′-pentamethyldipropylenetriamine, N,N,N′,N′-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol , N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl
• Aliphatic cyclic amide compounds include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthollactam, ⁇ -capryllactam, ⁇ -propiolactam and the like. Among these, ⁇ -caprolactam is more effective in accelerating hardening.
• the acid anhydride (C2) includes cyclic aliphatic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, and the like, and can be used alone or in combination of two or more.
• phthalic anhydride trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic acid Anhydride, poly(ethyloctadecanedioic anhydride), poly(phenylhexadecanedioic anhydride), tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , methylhimic acid anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, het acid anhydride, ethylene glyco
• the above-described compound modified with glycol may be used.
• Glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol.
• alkylene glycols such as ethylene glycol, propylene glycol and neopentyl glycol
• polyether glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol.
• two or more of these glycols and/or copolymerized polyether glycols of polyether glycols can also be used.
• Coupleling agent (C3) examples include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like.
• Silane coupling agents include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -amino Aminosilanes such as propyltrimethyldimethoxysilane and N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxy epoxysilanes such as propyltriethoxysilane; vinylsilanes such as vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxypropyl
• Titanate-based coupling agents include, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. are mentioned.
• aluminum-based coupling agents examples include acetoalkoxyaluminum diisopropylate.
• the pigment (C4) is not particularly limited, and includes extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, and pigments described in the 1970 edition of Handbook of Paint Materials (edited by the Japan Paint Manufacturers Association).
• Organic pigments and inorganic pigments such as blue pigments, metal powder pigments, luminescent pigments and pearlescent pigments, and plastic pigments can be used.
• Extender pigments include, for example, precipitated barium sulfate, rice flour, precipitated calcium carbonate, calcium bicarbonate, Kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.
• organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10; various (copper) pigments such as phthalocyanine blue and phthalocyanine green.
• insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R
• soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10
• various (copper) pigments such as phthalocyanine blue and phthalocyanine green.
• Phthalocyanine pigments various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant pigments such as quinoline lake and fast sky blue; various pigments such as anthraquinone pigments, thioindigo pigments and perinone pigments vat dye-based pigments; various quinacridone-based pigments such as Cincasia Red B; various dioxazine-based pigments such as dioxazine violet; various condensed azo pigments such as chromophtal;
• inorganic pigments include various chromates such as yellow lead, zinc chromate, molybdate orange; various ferrocyanic compounds such as Prussian blue; Various metal oxides such as zirconium oxide; various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types of silicon such as calcium silicate and ultramarine blue.
• chromates such as yellow lead, zinc chromate, molybdate orange
• ferrocyanic compounds such as Prussian blue
• metal oxides such as zirconium oxide
• various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide
• various sulfates such as barium sulfate and lead sulfate
• silicon such as calcium silicate and ultramarine blue.
• various acid salts such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder; These metal flake pigments and mica flake pigments; metallic pigments and pearl pigments such as mica-like iron oxide pigments and mica-like iron oxide pigments coated with metal oxides; graphite, carbon black and the like.
• plastic pigments examples include "Grandol PP-1000" and “PP-2000S” manufactured by DIC Corporation.
• the pigment (C4) to be used may be appropriately selected depending on the purpose.
• inorganic oxides such as titanium oxide and zinc oxide may be used as white pigments because they are excellent in durability, weather resistance, and design.
• Carbon black is preferably used as the black pigment.
• the amount of the pigment (C4) is, for example, 1 to 400 parts by mass with respect to 100 parts by mass of the total solid content of the polyisocyanate composition (A) and the polyol composition (B). It is more preferable to use 10 to 300 parts by mass for better results.
• plasticizer examples include phthalic acid-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphoric acid-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and carbonate-based plasticizers. plasticizers, and the like.
• phthalic plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate, octyldecyl phthalate, dimethyl isophthalate, Phthalic ester plasticizers such as di-(2-ethylhexyl) isophthalate and diisooc
• fatty acid-based plasticizers include adipic acids such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate.
• adipic acids such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate.
• azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, diisooctyl azelate, di-n-butyl sebacate, di-(2- ethylhexyl) sebacate, diisononyl sebacate and other sebacic acid plasticizers, e.g.
• di-n-butyl fumarate, di-(2-ethylhexyl) fumarate and other fumaric acid plasticizers such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Itaconic acid plasticizers such as di-(2-ethylhexyl) itaconate, stearic acid plasticizers such as n-butyl stearate, glycerin monostearate, diethylene glycol distearate, butyl oleate, glyceryl monooleate, Oleic acid plasticizers such as diethylene glycol monooleate, citric acid such as triethyl citrate, tri-n-butyl citrate, acetyltriethyl citrate, acetyltributyl citrate, acetyl tri-(2-ethylhexyl) citrate ric acid
• aromatic polycarboxylic acid-based plasticizers include tri-n-hexyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, and triisononyl. trimellitate, tridecyl trimellitate, triisodecyl trimellitate and other trimellitic acid plasticizers, e.g., tetra-(2-ethylhexyl) pyromellitate, tetra-n-octyl pyromellitate and other pyromellitic acid plasticizers plasticizers and the like.
• Phosphate plasticizers include, for example, triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyldiphenyl phosphate, cresyldiphenyl phosphate, cresylphenyl phosphate, trichlé Zyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, tris(isopropylphenyl) phosphate and the like.
• polyol plasticizers examples include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate ), glycol-based plasticizers such as dibutylmethylene bisthioglycolate, and glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.
• glycol-based plasticizers such as dibutylmethylene bisthioglycolate
• glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.
• epoxy plasticizers include epoxidized soybean oil, epoxybutyl stearate, di-2-ethylhexyl epoxyhexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate. etc.
• polyester-based plasticizers examples include adipic acid-based polyesters, sebacic acid-based polyesters, and phthalic acid-based polyesters.
• Propylene carbonate and ethylene carbonate are examples of carbonate-based plasticizers.
• plasticizers include partially hydrogenated terphenyl, adhesive plasticizers, diallyl phthalate, polymerizable plasticizers such as acrylic monomers and oligomers, and the like. These plasticizers can be used alone or in combination of two or more.
• Phosphoric acid compounds (C6) include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, and isododecyl acid.
• the adhesive of the present invention is used in solventless form.
• the "solvent-free" adhesive means that the polyisocyanate composition (A) and the polyol composition (B) are esters such as ethyl acetate, butyl acetate and cellosolve acetate, acetone, methyl ethyl ketone and isobutyl ketone.
• ketones such as cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, soluble hydrocarbons such as dimethylsulfoxide and dimethylsulfamide.
• a method that substantially does not contain expensive organic solvents, especially ethyl acetate or methyl ethyl ketone, and after applying an adhesive to a base material, attaches it to another base material without going through the process of heating in an oven or the like to volatilize the solvent. refers to the form of the adhesive used in the so-called non-solvent lamination method.
• the constituent components of the polyisocyanate composition (A) or the polyol composition (B) and the organic solvent used as the reaction medium during the production of the raw materials cannot be completely removed, resulting in the polyisocyanate composition (A) or the polyol composition ( If a small amount of organic solvent remains in B), it is understood that the organic solvent is not substantially contained.
• the polyol composition (B) contains a low-molecular-weight alcohol
• the low-molecular-weight alcohol reacts with the polyisocyanate composition (A) and becomes part of the coating film, so it is not necessary to volatilize after coating.
• Such forms are therefore also treated as solventless adhesives and low molecular weight alcohols are not considered organic solvents.
• the adhesive of the present invention has a ratio [NCO]/[ OH] is preferably 1.0 to 3.0. Thereby, appropriate curability can be obtained without depending on the environmental humidity at the time of coating.
• the adhesive of the present invention is excellent in suppressing appearance defects due to air bubbles and in suppressing appearance defects due to re-dissolving of ink is presumed as follows. Microscopic air bubbles caught in the adhesive during coating are not visible to the human eye if they remain as they are, so they do not cause appearance defects. become defective. In general, poor appearance due to air bubbles is less likely to occur when the compounds contained in the polyisocyanate composition (A) and the polyol composition (B) have a polyester skeleton, and tends to occur when they have a polyether skeleton. This is presumably because the adhesive itself has a high cohesive force when it has a polyester skeleton, preventing the cohesion of air bubbles.
• the printed layer will have areas densely filled with pigment and relatively sparse areas.
• the difference between the pigment dense and sparse areas becomes more visible, and the printed layer can be observed from the surface of the laminate. Then it looks black.
• the adhesive of the present invention can highly suppress poor appearance due to re-dissolution of ink, and can provide a laminate having a good appearance even when the adhesive is applied in a small amount.
• polyhydric alcohol (a1-2) diethylene glycol is selected as a compound contained in polyhydric alcohol (b1-2), and polyester polyol occupying the total amount of polyester polyol (a1) and polyester polyol (a2)
• the amount of diethylene glycol in the polyhydric alcohol (b1-2) is 80% by mass or more
• the amount of the polyether polyol (a2) in the total amount of the polyester polyol (a1) and the polyether polyol (a2) is 10% by mass. Re-dissolution of the ink can also be suppressed by setting the amount to 50% by mass or less.
• the adhesive of the present invention is excellent in suppressing appearance defects due to air bubbles even when barrier films are laminated to each other, although this is particularly likely to occur in some cases.
• solvent-free adhesives have a relatively low molecular weight compared to solvent-based adhesives, so curing shrinkage is large.
• the adhesive of the present invention is also excellent in adhesive strength when using such substrates. This is probably because the adhesive has a high proportion of ester bonds, which interact with the vapor deposited metal layer and the vapor deposited metal oxide layer to maintain the adhesive strength.
• the laminate of the present invention is obtained by laminating a plurality of substrates (films or papers) using the adhesive of the present invention by a non-solvent lamination method.
• the film to be used is not particularly limited, and a suitable film can be selected according to the application.
• PET polyethylene terephthalate
• polystyrene film polyamide film
• polyacrylonitrile film polyethylene film
• LLDPE low density polyethylene film
• HDPE high density polyethylene film
• CPP unstretched Polyolefin films such as polypropylene film, OPP (biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like.
• the film may be stretched.
• a stretching treatment method it is common to melt-extrude a resin into a sheet by an extrusion film-forming method or the like, and then subject the sheet to simultaneous biaxial stretching or sequential biaxial stretching.
• sequential biaxial stretching it is common to first perform longitudinal stretching and then laterally stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and lateral stretching using a tenter is often used.
• Various surface treatments such as flame treatment and corona discharge treatment may be applied to the film surface as necessary so that an adhesive layer without defects such as film breakage and repellency is formed.
• a barrier film containing a vapor-deposited layer of a metal such as aluminum, a metal oxide such as silica or alumina, or a gas barrier layer of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used. good.
• a laminate having barrier properties against water vapor, oxygen, alcohol, inert gas, volatile organic matter (fragrance) and the like can be obtained.
• a known paper base material can be used without any particular limitation. Specifically, it is produced by a known paper machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified.
• natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as Manila hemp pulp, sisal pulp and flax pulp, and pulp obtained by chemically modifying these pulps.
• the types of pulp that can be used include chemical pulp, ground pulp, chemi-grand pulp, thermomechanical pulp, and the like prepared by sulfate cooking, acid/neutral/alkaline sulfite cooking, soda salt cooking, and the like.
• various types of commercially available fine paper, coated paper, lined paper, impregnated paper, cardboard, paperboard, etc. can also be used.
• the adhesive of the present invention can suppress the occurrence of poor appearance due to air bubbles, it has a nylon film, a polyester film, a film having a vapor deposition layer of a metal such as aluminum or a metal oxide such as silica and alumina (transparent vapor deposition film).
• a metal such as aluminum or a metal oxide such as silica and alumina
• transparent vapor deposition film transparent vapor deposition film.
• Specific examples of such a configuration include PET film/adhesive layer/aluminum-deposited OPP film, PET film/adhesive layer/aluminum-deposited CP film, PET film/adhesive layer/aluminum-deposited PET film, PET film/adhesive layer/aluminum.
• the adhesive layer is a cured coating film of the adhesive of the present invention.
• a printed layer may be provided between the adhesive layer and the substrate (usually the substrate that is the outermost layer for the content).
• the printing layer is formed by a general printing method conventionally used for printing on films using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink.
• the adhesive of the present invention preheated to about 40° C. to 100° C. to a film or paper material as a base material using a roll such as a gravure roll, the other base material is immediately attached.
• a laminate of the present invention is obtained. It is preferable to perform an aging treatment after lamination.
• the aging temperature is preferably room temperature to 70° C., and the aging time is preferably 6 to 240 hours.
• the amount of the adhesive to be applied is appropriately adjusted depending on the appearance of the laminate (whether there is any defect due to re-dissolution of the ink), adhesive physical properties, and the like, and is, for example, 1 g/m 2 or more and 5 g/m 2 or less. If the coating amount of the adhesive is large, it may become easy to roll off, and from the viewpoint of workability, the coating amount is preferably 1 g/m 2 or more and 3 g/m 2 or less.
• the lamination speed (adhesive coating speed) can be appropriately adjusted in consideration of the appearance of the laminate (whether there are defects due to air bubbles or re-dissolution of the ink) and productivity. 150-200.
• the higher the lamination speed the more easily air bubbles are involved when the adhesive is applied, and the appearance defects due to the air bubbles are more likely to occur. Poor appearance due to air bubbles can be suppressed, and a laminate with good appearance can be provided.
• the laminate of the present invention is obtained by bonding two base materials together with the adhesive of the present invention, but may contain other base materials as necessary.
• known methods such as dry lamination, non-solvent lamination, heat lamination, heat sealing, and extrusion lamination may be used.
• the adhesive used at this time may or may not be that of the present invention.
• another base material the same base material as described above can be used.
• the packaging material of the present invention is formed by molding the laminate into a bag shape and heat-sealing the bag.
• Packaging materials include three-side seal bags, four-side seal bags, gusset packaging bags, pillow packaging bags, gobel-top type bottomed containers, tetraclassics, Bruck types, tube containers, paper cups, lids, and the like.
• the packaging material of the present invention may be appropriately provided with an easy-opening treatment or resealing means.
• the packaging material of the present invention can be used industrially as a packaging material mainly filled with foods, detergents, and medicines. Specific uses include detergents and chemicals such as liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and pharmaceutical tablets. It can also be used as a secondary packaging material for packaging the container described above.
• ⁇ Polyisocyanate composition (A)> Synthesis of polyester polyol (a1)-1) 7 parts of ethylene glycol and 35 parts of diethylene glycol are charged into a flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectifying tube, a water separator, etc., and heated to 80°C while stirring under a nitrogen gas stream. did. Further, while stirring, 36 parts of adipic acid and 22 parts of isophthalic acid were introduced into the reaction vessel, and gradually heated so that the temperature at the top of the rectification tube did not exceed 100°C, and the internal temperature was maintained at 250°C to initiate the esterification reaction. gone.
• polyester polyol having hydroxyl groups was obtained. This polyester polyol is designated as (a1)-1.
• polyester polyol (a1)-1 and 23 parts of polypropylene glycol having a number average molecular weight of 1000 (hereinafter abbreviated as "PPG-1000") are added dropwise in several portions and further heated to an internal temperature of 70°C. for 4 hours to carry out a urethanization reaction to obtain a urethane prepolymer having an NCO group content of 14.7% and having isocyanate groups at both ends.
• This urethane prepolymer is designated as (A)-1.
• ⁇ Polyol composition (B)> Synthesis of polyester polyol (B1)-1) 9 parts of ethylene glycol and 39 parts of diethylene glycol are charged into a flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectifying tube, a water separator, etc., and heated to 80°C while stirring under a nitrogen gas stream. did. Further, while stirring, 52 parts of adipic acid was introduced into the reaction vessel, and the mixture was gradually heated so that the temperature at the top of the rectifying tube did not exceed 100°C, and the internal temperature was maintained at 250°C to carry out an esterification reaction.
• polyester polyol having hydroxyl groups was obtained. This polyester polyol is designated as (B1)-1.
• Polyol compositions (B)-1 to (B)-10 were prepared according to the formulations shown in Tables 5 and 6.
• the prepared adhesive was applied to the surface of the printed layer printed on the PET film at a coating amount of 2.0 g/m 2 and coating speeds of 250 m/min, 200 m/min, and 150 m/min. 100 m/min, respectively, and the vapor-deposited surface of an aluminum vapor-deposited unstretched polypropylene film (hereinafter referred to as VMCPP; thickness: 25 ⁇ m) was overlaid on the coated surface. Then, aging was performed in an environment of 40° C. and 50% RH for 24 hours to cure the adhesive, and a laminate having a configuration of PET/printing layer/adhesive layer/VMCPP was produced to obtain sample 1 for evaluation. rice field.
• VMCPP aluminum vapor-deposited unstretched polypropylene film
• the prepared adhesive was applied to the surface of the printed layer printed on the PET film at a coating speed of 200 m/min, and the coating amount was 1.8 g/m 2 , 2.1 g/m 2 , 2.1 g/m 2 , They were coated at 2.3 g/m 2 and 2.5 g/m 2 , respectively, and the VMCPP vapor-deposited surface was laminated on the coated surface.
• aging was performed in an environment of 40° C. and 50% RH for 24 hours to cure the adhesive, and a laminate having a configuration of PET/printing layer/adhesive layer/VMCPP was produced to obtain sample 2 for evaluation. rice field.
• the prepared adhesive is applied to the surface of the printed layer printed on the PET film at a coating speed of 200 m / min and a coating amount of 2.0 g, and the coated surface is the vapor deposition surface of VMCPP. were pasted together. Then, aging was performed in an environment of 40° C. and 50% RH for 48 hours to cure the adhesive, and a laminate having a configuration of PET/printing layer/adhesive layer/VMCPP was produced to obtain sample 3 for evaluation. rice field.
• a sample 3 for evaluation was cut into a length of 300 mm and a width of 15 mm to obtain a test piece.
• the T-peel strength (N) between PET/VMCPP was measured at a width of 15 mm by pulling at a peel speed of 300 mm/min under an environment of 25°C. This test was performed 5 times, and the average value was obtained and evaluated according to the following criteria.

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• Chemical & Material Sciences (AREA)
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• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 2022
  • 2022-01-27 CN CN202280009641.6A patent/CN116723932B/zh active Active
  • 2022-01-27 EP EP22752589.6A patent/EP4293091A4/en not_active Withdrawn
  • 2022-01-27 US US18/273,393 patent/US20240117229A1/en active Pending
  • 2022-01-27 JP JP2022563974A patent/JP7231127B2/ja active Active
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