Classifications

• • 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
  • 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
• • 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
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
  • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
• • 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
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/285—Nitrogen containing compounds
  • C08G18/2855—Lactams
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/302—Water
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
  • C08G18/348—Hydroxycarboxylic acids
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/36—Hydroxylated esters of higher fatty acids
• • 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
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
  • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from 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
  • C08G18/4825—Polyethers containing two hydroxy 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
  • C08G18/28—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
  • C08G18/50—Polyethers having heteroatoms other than oxygen
  • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
  • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
  • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
  • C08G18/7825—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing ureum 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
• • 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

Definitions

• the present invention relates to two-component curing adhesives, laminates, and packaging materials.
• Laminates used for various packaging materials, labels, etc. are given design, functionality, preservability, convenience, transportation resistance, etc. by laminating a wide variety of base materials such as plastic films, metal foils, and paper. be done.
• a packaging material obtained by molding the laminate into a bag shape is used as a packaging material in various fields including foods, medicines, detergents, and the like.
• urethane reactive two-liquid type adhesives (hereinafter sometimes referred to as two-liquid curing adhesives or reactive adhesives) have been used as adhesives for laminating laminates used in such packaging materials. ) has been widely used.
• urethane-reactive two-component curing adhesives use isocyanate prepolymer as a curing component, so isocyanate monomers remaining in the adhesive layer have become a problem.
• the handling conditions will be strengthened by the REACH regulation by the European Commission, regardless of the type of isocyanate monomer, and it is required to reduce the amount of isocyanate monomer remaining in the adhesive layer as much as possible. .
• Patent Document 1 100 parts by weight of a urethane prepolymer and 10 to 40 parts by weight of a fluidity imparting agent or a softening agent made of a low molecular weight polar polymer having no active hydrogen and a number average molecular weight of 300 to 10000, Polyurethane adhesives are disclosed characterized by an amount of isocyanate monomer in the adhesive of 0.01 to 4% by weight.
• Patent Document 2 (a) a polyol selected from the group consisting of polyether polyols, polyester polyols, polyester polyether polyols, acrylic polyols, glycols and mixtures thereof is reacted with an isocyanate monomer; forming a reaction mixture comprising a prepolymer having an NCO content of 5 to 11.5% by weight and having an average NCO functionality in the range of 2.0 to 3.0; A method of forming a low residual isocyanate isocyanate-functional prepolymer is disclosed comprising passing the reaction mixture containing (See Patent Document 2, for example).
• Patent Document 1 a composition substantially using diphenylmethane diisocyanate (hereinafter sometimes referred to as MDI) is stirred for 20 minutes in an environment reduced to 960 Pa for defoaming. Only residual concentrations and viscosities of MDI remaining in the cooled adhesive composition are disclosed.
• MDI diphenylmethane diisocyanate
• Patent Document 2 substantially, a prepolymer obtained by reacting a polyol and toluene diisocyanate (hereinafter sometimes referred to as TDI) is passed through a short-path evaporator, and the amount is less than 0.15% by weight. Only specific embodiments for removing the reactive isocyanate are disclosed.
• the present invention maintains an adhesive function that is comparable to the currently distributed urethane reaction type two-component curing adhesive, and reduces the isocyanate monomer to a level that is judged to have no effect on the human body or the environment.
• An object of the present invention is to provide a polyisocyanate composition and a two-component curing adhesive using the same.
• the present inventors have found that a polyisocyanate composition containing a specific amount of a specific low-molecular-weight isocyanate monomer and a two-component curing adhesive using the same can solve the above problems.
• the low-molecular-weight isocyanate monomer contributes to the crosslinked structure of the cured film, but the degree of contribution is presumed to be different from that of the high-molecular-weight urethane prepolymer.
• high-molecular-weight urethane prepolymers have a relatively large distance between cross-linking points after cross-linking, and the cross-linking point density is slightly low because the structure after cross-linking is close to the network structure of a linear polymer, resulting in a cured film. is known to be flexible but somewhat inferior in strength.
• low-molecular-weight isocyanate monomers are known to have a high cross-linking point density because the distance between cross-linking points after cross-linking is short, and the resulting cured film is poor in flexibility but excellent in strength.
• the present inventors have found that a compound (A1) having one or more isocyanate groups with a number average molecular weight exceeding 280 and an isocyanate monomer (A2) having a number average molecular weight of 140 to 280 are included.
• the polyisocyanate composition is a polyisocyanate composition in which the amount of the isocyanate monomer (A2) is 0.001% by mass or more and 0.1% by mass or less with respect to the solid content of the polyisocyanate composition, the crosslink point density is well balanced. A cured film can be obtained, and it maintains adhesive functions comparable to those of the urethane reaction type two-component curing type adhesives currently in circulation. It was found that a two-component curing adhesive can be obtained.
• the present invention contains a compound (A1) having one or more isocyanate groups having a number average molecular weight exceeding 280 and an isocyanate monomer (A2) having a number average molecular weight of 140 to 280, and the amount of the isocyanate monomer (A2) is 0.001% by mass or more and 0.1% by mass or less based on the solid content of the polyisocyanate composition.
• the present invention contains a compound (A1) having one or more isocyanate groups having a number average molecular weight exceeding 280 and an isocyanate monomer (A2) having a number average molecular weight of 140 to 280, and the amount of the isocyanate monomer (A2). is 0.001% by mass or more and 0.1% by mass or less based on the solid content, and a composition (Y) containing a compound having a group capable of reacting with an isocyanate group.
• a two-component curing adhesive is provided.
• the present invention has 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 adhesive layer.
• a laminate that is a cured coating film of a two-part curable adhesive.
• the present invention also provides a packaging material comprising the laminate described above.
• the polyisocyanate composition of the present invention maintains an adhesive function comparable to that of currently distributed urethane reaction type two-component curing adhesives, and isocyanate monomers up to a level that is judged to have no effect on the human body or the environment. is reduced, it is possible to provide an adhesive that is safe and has functions comparable to those of the urethane reaction type two-liquid curing adhesive currently in circulation.
• the two-component curing adhesive of the present invention is safe and has functions comparable to those of urethane reaction-type two-component curing adhesives currently in circulation, so it can be used in various fields such as foods, pharmaceuticals, and detergents.
• a laminate that can be applied to packaging materials can be provided.
• the number average molecular weight and weight average molecular weight are values 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)
• the polyisocyanate composition of the present invention (hereinafter sometimes referred to as polyisocyanate composition (X)) includes a compound (A1) having one or more isocyanate groups with a number average molecular weight exceeding 280, and a number average molecular weight of 140 to 280.
• An isocyanate monomer (A2) is contained, and the blending amount of the isocyanate monomer (A2) is 0.001% by mass or more and 0.1% by mass or less based on the solid content of the polyisocyanate composition.
• the compound (A1) having one or more isocyanate groups with a number average molecular weight exceeding 280 (hereinafter sometimes referred to as isocyanate compound (A1)) used in the present invention is not particularly limited, and has a number average molecular weight exceeding 280.
• a compound having one or more isocyanates may be used, but it should be a urethane prepolymer (A1-1), or a urea-modified polyisocyanate, or an isocyanate polymer (A1-2), which is preferably used in the field of adhesives. is preferred.
• the urethane prepolymer (A1-1) used in the present invention is not particularly limited, and any urethane prepolymer used in the field of adhesive technology can be used.
• the isocyanate composition (i) and the polyol composition (ii) are mixed so that the isocyanate groups contained in the isocyanate group (i) are excessive with respect to the active hydrogen groups contained in the polyol composition (ii).
• a urethane prepolymer obtained by reacting under the following conditions is used.
• the isocyanate composition (i) used in the present invention contains an isocyanate compound.
• the isocyanate compound is not particularly limited, and those commonly used for synthesizing urethane prepolymers can be appropriately used.
• examples thereof include re
• aromatic diisocyanates examples include 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (also known as MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI, or crude MDI (also called : TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, tolidine diisocyanate (alias: TODI), dianisidine diisocyanate, naphthalene diisocyanate (alias: NDI ), 4,4′-diphenyl ether diisocyanate, 4,4′,4′′-triphenylmethane triisocyanate, and the like, but are not limited thereto.
• MDI polymethylene polyphenyl polyisocyanate
• the 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 (also known as PDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Examples include butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate (also known as LDI), and the like, but are not limited to these.
• 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-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebiscyclohexyl isocyanate (also known as hydrogenated MDI or HMDI), 1,3-bis(isocyanatomethyl)cyclohexane ( Alias: hydrogenated XDI or HXDI), norbornane diisocyanate (alias: NBDI), etc., but not limited to these.
• IPDI isophorone diisocyanate
• 1,3-cyclopentane diisocyanate 1,3-
• the polyol composition (ii) used for synthesizing the urethane prepolymer contains a polyol compound.
• the polyol compound is not particularly limited, and those commonly used for synthesizing urethane prepolymers can be appropriately used.
• ethylene glycol 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5 - pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4 - glycols such as cyclohexanediol, 1,4-cyclohexanedimethanol;
• 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 glycols and trifunctional or tetrafunctional aliphatic alcohols. ; Polyether urethane polyol obtained by further increasing the molecular weight of polyether polyol with an isocyanate compound;
• 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;
• Polyvalent carboxylic acids used in the synthesis of polyester polyols (2) to (4) include orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy ) aromatic polybasic acids such as ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride
• 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;
• isocyanate compounds used in the synthesis of polyurethane polyols the same non-aromatic isocyanates as those usable in the isocyanate composition (i) can be used.
• aromatic diisocyanates include 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (also known as MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI, or crude MDI (also called : TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, tolidine diisocyanate (alias: TODI), dianisidine diisocyanate, naphthalene diisocyanate (alias: NDI ), 4,4′-diphenyl ether diisocyanate
• the polyol compound preferably contains at least one polyether polyol or polyester polyol.
• the urethane prepolymer (A1-1) contains the isocyanate composition (i) and the polyol composition (ii) in the isocyanate group (i) with respect to the active hydrogen group contained in the polyol composition (ii). It is obtained by reacting under conditions in which the isocyanate groups contained are excessive.
• the equivalent ratio [NCO]/[active hydrogen group] of the isocyanate group to the active hydrogen group contained in the polyol composition (ii) can be appropriately adjusted depending on the purpose. be.
• the urethane prepolymer (A1-1) preferably has a molecular weight of more than 280 and an upper limit of 50,000 in terms of number average molecular weight. More preferably, it exceeds the lower limit of 300 and the upper limit is 30,000 or less.
• urea-modified polyisocyanate or isocyanate polymer (A1-2) As the urea-modified polyisocyanate or isocyanate polymer (A1-2), specifically, an isocyanate monomer is bonded via a structure selected from a urea structure, a biuret structure, an uretdione bond, a nurate structure, a carbodiimide structure, and the like. is a compound.
• the isocyanate monomer used in the urethane prepolymer (A1-1) can be used.
• araliphatic diisocyanates such as m- or p-xylylene diisocyanate (alias: XDI), ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate (alias: TMXDI),
• trimethylene diisocyanate trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate (also known as PDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate , 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate (alias: LDI) and other aliphatic diisocyanates,
• IPDI isophorone diisocyanate
• 1,3-cyclopentane diisocyanate 1,3-cycl
• Urea-modified polyisocyanates include polyisocyanates having a biuret structure or a urea structure. Their number average molecular weight is more than 280, and the upper limit is preferably 2000 or less. More preferably, it exceeds the lower limit of 300, and more preferably exceeds 350. The upper limit is preferably 1,800 or less, and is 1,500 or less.
• isocyanate polymers include polyisocyanates having a uretdione structure or a nurate structure. Their number average molecular weight is more than 280, and the upper limit is preferably 2000 or less. More preferably, it exceeds the lower limit of 300, and more preferably exceeds 350. The upper limit is preferably 1,800 or less, and is 1,500 or less.
• a polyisocyanate having a uretdione structure or a urea structure it is particularly preferred to contain a polyisocyanate having a uretdione structure or a urea structure.
• compounds represented by general formula (1) and satisfying (1) and (2) are preferred.
• R 1 is a residue excluding one isocyanate group of a diisocyanate compound selected from the group consisting of aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates, and R 2 represents a uretdione group or a urea group.
• the number average molecular weight of the compound represented by formula (1) is in the range of more than 280 and within 600. (2) It contains 0.001% by mass or more and 30% by mass or less of the compound represented by the general formula (1) based on the solid content of the polyisocyanate composition.
• the compound represented by the general formula (1) has a slightly low compatibility with the isocyanate compound (A1) other than the compound represented by the general formula (1), and if the content is large, the polyisocyanate composition Turbidity may occur.
• the compound represented by the general formula (1) is preferably contained in the range of 0.005% by mass or more and 20% by mass or less, based on the solid content of the polyisocyanate composition, and 0.01% by mass or more and 10% by mass. % or less, more preferably 0.01 mass % or more and 3 mass % or less.
• the molecular weight of these urea-modified polyisocyanates or isocyanate polymers (A1-2) is preferably more than 280, with an upper limit of 2000 or less in terms of number average molecular weight. More preferably, it exceeds the lower limit of 300, and more preferably exceeds 350.
• the upper limit is preferably 1,800 or less, and is 1,500 or less.
• the isocyanate compound (A1) may be polymeric diphenylmethane diisocyanate, polyisocyanate having an allophanate structure, or the like.
• the isocyanate compound (A1) can be used by combining a plurality of compounds corresponding to the isocyanate compound (A1) depending on the application. Examples of specific embodiments are listed below, but the present invention is not limited to these and can be used in various combinations.
• (I) Contains one or more compounds corresponding to urethane prepolymer (A1-1).
• (II) Contains one or more compounds corresponding to urea-modified polyisocyanate or isocyanate polymer (A1-2).
• (III) Contains one or more compounds corresponding to urethane prepolymer (A1-1), and one or more compounds corresponding to urea-modified polyisocyanate or isocyanate polymer (A1-2).
• (IV) Contains one or more compounds corresponding to the urethane prepolymer (A1-1) and a compound represented by general formula (1) which is a polyisocyanate having a uretdione structure or a urea structure.
• a polyisocyanate containing one or more compounds corresponding to urea-modified polyisocyanate or isocyanate polymer (A1-2) and having a uretdione structure or a urea structure represented by the general formula (1) Contains compounds.
• (VI) contains one or more compounds corresponding to urethane prepolymer (A1-1), and one or more compounds corresponding to urea-modified polyisocyanate or isocyanate polymer (A1-2), and , a compound represented by the general formula (1), which is a polyisocyanate having a uretdione structure or a urea structure.
• the compound corresponding to the urethane prepolymer (A1-1) of (III) is used alone or in plurality, and the compound corresponding to the urea-modified polyisocyanate or the isocyanate polymer (A1-2) is used alone or A combination containing a plurality of compounds and a combination containing a compound represented by the general formula (1), which is a polyisocyanate having a uretdione structure or a urea structure (IV) to (VI), is a urea-modified polyisocyanate or an isocyanate
• Various effects can be expected depending on the added amount of the polymer (A1-2) and the added amount of the compound represented by the general formula (1), which is a polyisocyanate having a uretdione structure or a urea structure.
• the polyisocyanate composition of the present invention is a composition of a compound having an isocyanate group.
• the isocyanate group is highly reactive and reacts even with moisture in the air. It may cause the time to be shortened.
• the compound represented by the general formula (1) which is more reactive with water than the urethane prepolymer (A1-1)
• the effect of selectively reacting with water and suppressing the increase in viscosity can be expected.
• Such a moisture catcher effect can be exhibited even with a very small amount of the compound represented by the general formula (1). It may be 0.001% by mass or more, more preferably 0.01% by mass or more, based on the solid content of the isocyanate composition of the present invention.
• the isocyanate compound used for synthesizing the compound represented by the general formula (1) preferably has reactivity equal to or higher than that of the isocyanate compound used for synthesizing the urethane prepolymer (A1-1). Specifically, when the isocyanate compound used to synthesize the urethane prepolymer (A1-1) is an aromatic diisocyanate, the isocyanate compound used to synthesize the compound represented by the general formula (1) is also an aromatic diisocyanate.
• the isocyanate compound used to synthesize the urethane prepolymer (A1-1) is an araliphatic diisocyanate
• the isocyanate compound used to synthesize the compound represented by the general formula (1) is an aromatic diisocyanate and an araliphatic It is preferably selected from diisocyanates.
• the isocyanate compound used to synthesize the urethane prepolymer (A1-1) is an aliphatic diisocyanate
• the isocyanate compound used to synthesize the compound represented by the general formula (1) is an aromatic diisocyanate or an araliphatic diisocyanate. , aliphatic diisocyanates.
• the isocyanate compound used to synthesize the urethane prepolymer (A1-1) is an alicyclic diisocyanate
• the isocyanate compound used to synthesize the compound represented by the general formula (1) is an aromatic diisocyanate, an araliphatic It may be selected from diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates.
• the isocyanate compound used for synthesizing the compound represented by the general formula (1) preferably has a reactivity comparable to or higher than that of the isocyanate compound used for synthesizing the isocyanate polymer.
• the isocyanate compound used to synthesize the isocyanate polymer is an aromatic diisocyanate
• the isocyanate compound used to synthesize the compound represented by the general formula (1) is also preferably an aromatic diisocyanate. .
• the isocyanate compound used to synthesize the isocyanate polymer is an araliphatic diisocyanate
• the isocyanate compound used to synthesize the compound represented by the general formula (1) is selected from aromatic diisocyanates and araliphatic diisocyanates. is preferred.
• the isocyanate compound used to synthesize the isocyanate polymer is an aliphatic diisocyanate
• the isocyanate compound used to synthesize the compound represented by the general formula (1) is an aromatic diisocyanate, an araliphatic diisocyanate, an aliphatic diisocyanate. preferably selected.
• the isocyanate compound used to synthesize the isocyanate polymer is an alicyclic diisocyanate
• the isocyanate compound used to synthesize the compound represented by the general formula (1) is an aromatic diisocyanate, an araliphatic diisocyanate, an aliphatic diisocyanate. , alicyclic diisocyanates.
• the isocyanate used for synthesizing the polyisocyanate having a nurate structure is preferably at least one selected from the group consisting of araliphatic diisocyanates, alicyclic diisocyanates and aliphatic diisocyanates, and from alicyclic diisocyanates and aliphatic diisocyanates It is more preferable to include at least one selected.
• Another effect of containing the compound represented by the general formula (1), which is a polyisocyanate having a uretdione structure or a urea structure, is pinhole resistance, heat seal strength, aluminum adhesion, zipper heat seal resistance, and boiling resistance. , heat resistance, etc., can be expected due to the cohesive force of the adhesive. That is, since the urethane prepolymer (A1-1) has polyol-derived chains between the isocyanate groups, the crosslink density of the adhesive cured film obtained does not increase so much.
• the polyisocyanate of general formula (1) having a uretdione structure or a urea structure it is expected that a complex cross-linking density structure will be formed in the cured coating film of the adhesive and the cohesion will be improved. Such an effect of improving the cohesive force can be expressed even in a very small amount of the polyisocyanate of the general formula (1) having a uretdione structure or a urea structure.
• the addition amount of the polyisocyanate of general formula (1) may be 0.001% by mass or more, more preferably 0.01% by mass or more, relative to the solid content of the isocyanate composition of the present invention.
• the isocyanate composition (i) used for synthesizing the urethane prepolymer (A1-1) is selected from aromatic diisocyanate, araliphatic diisocyanate, and alicyclic diisocyanate. It preferably contains at least one selected, preferably contains at least one selected from aromatic diisocyanates and araliphatic diisocyanates, and more preferably aromatic diisocyanates. More preferably, the aromatic diisocyanate is toluene diisocyanate.
• the isocyanate monomer (A2) used in the present invention can be used without any particular limitation as long as it has a number average molecular weight of 140-280.
• aromatic diisocyanates include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (also known as MDI), 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate (alias: PPDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (alias: TDI), tolidine diisocyanate (alias: TODI), naphthalene diisocyanate (alias: NDI), etc., but not limited to these.
• MDI 1,3-phenylene diisocyanate
• 4,4'-diphenyl diisocyanate 1,4-phenylene diisocyanate
• 1,4-phenylene diisocyanate alias: PPDI
• the 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 (also known as PDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Examples include butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate (also known as LDI), and the like, but are not limited to these.
• alicyclic diisocyanates include isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 4,4′-methylenebiscyclohexyl isocyanate (alias: hydrogenated MDI or HMDI), 1,4-bis(isocyanatomethyl)cyclohexane or 1,3-bis(isocyanatomethyl)cyclohexane (alias: hydrogenated XDI or HXDI), norbornane diisocyanate (also known as NBDI), etc., but not limited thereto.
• IPDI isophorone diisocyanate
• 1,3-cyclopentane diisocyanate 1,3-cyclohexane di
• the polyisocyanate composition (X) of the present invention contains the isocyanate compound (A1) and the isocyanate monomer (A2), and the amount of the isocyanate monomer (A2) is 0.001% by mass relative to the solid content. It is characterized by being more than 0.1% mass or less.
• the solid content represents the solid content of the polyisocyanate composition.
• the polyisocyanate composition comprises the isocyanate compound (A1) and the isocyanate monomer (A2)
• the solid content is the sum of the mass of the urethane prepolymer (A1-1) and the mass of the isocyanate monomer (A2).
• the lower limit of the blending amount of the isocyanate monomer (A2) is preferably 0.005% by mass or more, most preferably 0.01% by mass or more, based on the solid content. Within this range, a cured film with a well-balanced cross-linking point density can be obtained, maintaining adhesive functions comparable to those of the currently available urethane reaction type two-component curing adhesives, and for example plastics with flexible substrates. It is possible to obtain a two-liquid curable adhesive that can follow even paper and is excellent in strength.
• the blending amount of the isocyanate monomer (A2) can be measured by gas chromatography using an internal standard, for example, according to ASTM D3432. Alternatively, it can be measured by liquid chromatography under the following conditions.
• viscosity When the polyisocyanate composition (X) of the present invention is used as a solvent-free two-part curing adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for non-solvent lamination. As an example, the viscosity at 40° C. is adjusted to be in the range of 100-20000 mPas, more preferably 500-10000 mPas. The viscosity of the polyisocyanate composition (X) can be adjusted, for example, by adjusting the amount of the urethane prepolymer and the isocyanate monomer.
• the viscosity of the polyisocyanate composition (X) can be measured, for example, using a rotational viscometer at cone/plate: 1° ⁇ diameter 50 mm, shear rate: 100 sec ⁇ 1 , 40° C. ⁇ 1° C.
• the polyisocyanate composition (X) of the present invention can be obtained by mixing the isocyanate compound (A1) and the isocyanate monomer (A2). Further, when the isocyanate monomer (A2) is one of the raw materials of the isocyanate compound (A1), after synthesizing the isocyanate compound (A1), the remaining isocyanate monomer (A2) is added to the composition. It may be adjusted to be 0.001% by mass or more and 0.1% by mass or less with respect to the solid content of. Moreover, you may combine these methods.
• the isocyanate compound (A1) and the isocyanate monomer (A2) are mixed, they can be mixed using a known stirrer or the like to obtain the polyisocyanate composition (X) of the present invention.
• the solid content of the composition is adjusted to 0.001% by mass or more and 0.1% by mass or less.
• the solid content of the composition is 0.001% by mass or more and 0.1% by mass or less.
• the method of adjusting so as to be is simple and preferable.
• the polyisocyanate composition (X) of the present invention is used together with the composition (Y) containing a compound having a group capable of reacting with an isocyanate group, such as a polyol composition, as a urethane-reactive two-component curing adhesive.
• a compound having a group capable of reacting with an isocyanate group such as a polyol composition
• an isocyanate group such as a polyol composition
• the two-component curable adhesive of the present invention contains the polyisocyanate composition (X) and the composition (Y) containing a compound having a group reactive with an isocyanate group.
• composition (Y) containing a compound having a group capable of reacting with an isocyanate group the compound having a group capable of reacting with an isocyanate group specifically includes a polyol compound (B) having a hydroxyl group, and a polyol compound (B) having an amino group.
• An amine compound (C), a compound having a carboxyl group, an epoxy compound having an epoxy group, and the like can be mentioned.
• a composition containing a polyol compound (B) is preferable, and a polyol composition (Y) containing a polyol compound (B) having a plurality of hydroxyl groups is preferable from the viewpoint of obtaining an appropriate crosslink density.
• the polyol composition (Y) contains a polyol compound (B) having multiple hydroxyl groups.
• the polyol compound (B) is not particularly limited, and any polyol compound that is usually used for a urethane-reactive two-liquid curing adhesive can be used. Specifically, for example, polyether polyol, polyester polyol, polyester polyether polyol, polyurethane polyol, polyester polyurethane polyol, polyether polyurethane polyol, vegetable oil polyol, sugar alcohol, polycarbonate polyol, acrylic polyol, hydroxyl group-containing olefin resin, hydroxyl group-containing fluorine resins, (poly)alkanolamines, and the like.
• Polyether polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol and 1,6-hexanediol.
• neopentyl glycol methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1, 4-cyclohexanedimethanol, glycols such as triethylene glycol; glycerin, trimethylolpropane, pentaerythritol, in the presence of a polymerization initiator such as trifunctional or tetrafunctional aliphatic alcohols such as triols of polypropylene glycol, ethylene oxide , propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene. Preference is given to using polypropylene glycol.
• Polyester polyols are reaction products of polyhydric alcohols and polycarboxylic acids.
• the polyhydric alcohol used for synthesizing the polyester polyol may be a diol or a trifunctional or higher polyol.
• Polyester polyether polyols using the above polyether polyols as diols and polyester polyurethane polyols using polyurethane polyols described below may also be used.
• diols include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propane.
• 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
• a lactone-based polyester polyol obtained by a polycondensation reaction between an aliphatic diol and various lactones such as lactanoids and ⁇ -caprolactone;
• Bisphenols such as bisphenol A and bisphenol F;
• Examples include alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F.
• trifunctional or higher polyols are 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 ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether.
• Examples include lactone-based polyester polyols obtained by polycondensation reaction between aliphatic polyols and various lactones such as ⁇ -caprolactone.
• Polyvalent carboxylic acids used in the synthesis of polyester polyols include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4- aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid aromatic dicarboxylic acids such as 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids; p-hydroxybenzoic acid, p-(
• vegetable oil polyols examples include castor oil, dehydrated castor oil, hydrogenated castor oil, which is a hydrogenated product of castor oil, and adducts of 5 to 50 moles of alkylene oxide of castor oil.
• a polyurethane polyol is a reaction product of a low-molecular-weight or high-molecular-weight polyol and a polyisocyanate compound.
• the low-molecular-weight polyol the same polyhydric alcohol as exemplified as the raw material of the polyester polyol can be used.
• high-molecular-weight polyols include polyether polyols and polyester polyols.
• the polyisocyanate compound the same polyisocyanate as used in the urethane prepolymer (A1-1) can be used.
• Sugar alcohols include pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, and mannitol sugar.
• the viscosity of the polyol composition (Y) is adjusted within a range suitable for non-solvent lamination.
• 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 (Y) can be adjusted by the skeleton of the polyol compound (B), the plasticizer described below, and the like.
• the viscosity can be lowered by using, for example, polypropylene glycol or a polyester polyol obtained by reacting an aliphatic carboxylic acid and a polyol.
• the viscosity can be increased by using a polyester polyol obtained by reacting an aromatic carboxylic acid and a polyol.
• the two-component curing adhesive of the present invention may contain components other than the components described above. Other components may be contained in either or both of the polyisocyanate composition (X) and the polyol composition (Y), or may be prepared separately from these, and may be added to the polyisocyanate composition (X) immediately before coating the adhesive. It may be used by mixing with the isocyanate composition (X) and the polyol composition (Y). Each component will be described below.
• the polyol composition (Y) may contain an amine compound (C) having an amino group.
• an amino group means an NH2 group or an NHR group (R is an alkyl group or an aryl group which may have a functional group).
• amine compound (C) known compounds can be used without particular limitation, and methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxapyrodundecane, lysine, , 2,2,4-trimethylhexamethylenediamine, hydrazine, piperazine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxy propylethylenediamine, poly(propylene glycol) diamine, poly(propylene glycol) triamine, poly(propylene glycol) tetraamine, 1,2-diaminopropane, 1,3-diaminopropane,
• 1,4-diaminobutane 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, diethylenetriamine, Dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, tetra(aminomethyl)methane, tetrakis(2-aminoethylamino) methyl)methane, 1,3-bis(2′-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine
• primary or secondary alkanolamine such as monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, diisopropanolamine,
• C2 primary or secondary alkanolamine
• Primary or secondary amines such as ethylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, diethylamine, dibutylamine, distearylamine, and the like.
• the amount of the amine compound (C) is preferably blended so that the amine value of the polyol composition (Y) is 20-70 mgKOH/g, more preferably 25-50 mgKOH/g.
• the amine value in this specification means the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of the sample, and is not particularly limited, and can be calculated using a known method. can.
• the chemical structure of the amine compound (C) and, optionally, the average molecular weight, etc. are known, it can be calculated from (number of amino groups per molecule/average molecular weight) x 56.1 x 1000. can.
• the chemical structure, average molecular weight, etc. of the amine compound are unknown, it can be measured according to a known amine value measuring method such as JISK7237-1995.
• the polyol composition (Y) may contain a monool compound (D) having one alcoholic hydroxyl group.
• the main chain of the monool compound (D) is not particularly limited, and includes vinyl resins having one hydroxyl group, acrylic resins, polyesters, epoxy resins, urethane resins, and the like. Aliphatic alcohols, alkyl alkylene glycols, and the like can also be used.
• the main chain of the monool compound (D) 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.
• the monool compound (D) examples include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol, aliphatic monools such as 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.
• catalysts examples include metal-based catalysts, amine-based catalysts, aliphatic cyclic amide compounds, and quaternary ammonium salts.
• Metal-based catalysts 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)
• 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 quaternary ammonium salts include hydroxy salts such as alkyl ammonium and aromatic ammonium, alkyl acid salts, halide salts and the like.
• Examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium Examples include, but are not limited to, butylammonium iodide, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, and the like.
• the acid anhydrides include cycloaliphatic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, and the like, and may be used alone or in combination of two or more. More specifically, for example, 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
• 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. Furthermore, two or more of these glycols and/or copolymerized polyether glycols of polyether glycols can also be used.
• coupling agent examples include silane coupling agents, titanate-based coupling agents, and aluminum-based coupling agents.
• 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.
• Pigments are not particularly limited, and include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, pigments described in the 1970 edition of Handbook of Paint Raw Materials (edited by the Japan Paint Manufacturers Association). Examples include organic pigments such as metal powder pigments, luminescent pigments, and pearlescent pigments, inorganic pigments, and plastic pigments.
• 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 to be used may be appropriately selected according to the purpose.
• inorganic oxides such as titanium oxide and zinc oxide are preferably used as white pigments because they are excellent in durability, weather resistance, and design.
• Carbon black is preferably used as the pigment.
• the amount of the pigment compounded is, for example, 1 to 400 parts by mass with respect to 100 parts by mass of the total non-volatile content of the polyol composition (X) and the polyisocyanate composition (Y). 10 to 300 parts by mass is more preferable.
• plasticizers 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 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, isododecyl acid phosphate, butoxy Ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate and the like.
• the two-component curing adhesive of the present invention may be in the form of either a solvent type or a non-solvent type.
• solvent-based adhesive means that after the adhesive is applied to the base material, it is heated in an oven or the like to evaporate the organic solvent in the coating film, and then bonded to another base material. It refers to a form used in a method, a so-called dry lamination method.
• Either one or both of the polyisocyanate composition (X) and the polyol composition (Y) dissolve (dilute) the components of the polyisocyanate composition (X) and the polyol composition (Y) used in the present invention. Contains organic solvents that can
• organic solvents examples include esters such as ethyl acetate, butyl acetate and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; and aromatic hydrocarbons such as toluene and xylene. , methylene chloride, halogenated hydrocarbons such as ethylene chloride, dimethylsulfoxide, dimethylsulfamide and the like.
• the organic solvent used as the reaction medium during the production of the constituent components of the polyisocyanate composition (X) and the polyol composition (Y) may also be used as a diluent during coating.
• solvent-free adhesive means that the polyisocyanate composition (X) and the polyol composition (Y) are esters such as ethyl acetate, butyl acetate and cellosolve acetate, acetone, methyl ethyl ketone, isobutyl ketone, Highly soluble 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, dimethylsulfoxide and dimethylsulfamide.
• esters such as ethyl acetate, butyl acetate and cellosolve acetate, acetone, methyl ethyl ketone, isobutyl ketone, Highly soluble ketones such as cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic
• a method in which an adhesive that does not substantially contain an organic solvent, particularly ethyl acetate or methyl ethyl ketone, is applied to a substrate, and then bonded to another substrate without a step of heating in an oven or the like to volatilize the solvent It refers to the form of adhesive used in the so-called non-solvent lamination method.
• the constituent components of the polyisocyanate composition (X) or the polyol composition (Y) 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 (X) and the polyol composition ( If a small amount of organic solvent remains in Y), it is understood that the organic solvent is not substantially contained.
• the polyol composition (Y) contains a low-molecular-weight alcohol
• the low-molecular-weight alcohol reacts with the polyisocyanate composition (X) 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 two-component curable adhesive of the present invention is a ratio of the number of moles [NCO] of isocyanate groups contained in the polyisocyanate composition (X) to the number of moles [OH] of hydroxyl groups contained in the polyol composition (Y) [ It is preferable to mix and use so that NCO]/[OH] is 1.0 to 3.0. Thereby, appropriate curability can be obtained without depending on the environmental humidity at the time of coating.
• the polyisocyanate composition (X) and the polyol composition (Y) are mixed in advance, then applied to the first substrate, and then the second substrate is applied to the coated surface.
• the first substrate and the second substrate are laminated by contacting and crimping the respective coated surfaces, and obtained by a method having a two-liquid separate coating step obtained by curing the adhesive layer. be done.
• the film to be used is not particularly limited, and a suitable film can be selected according to the application.
• polyethylene terephthalate (PET) film polystyrene film, polyamide film, polyacrylonitrile film
• polyethylene film LLDPE: low density polyethylene film
• HDPE high density polyethylene film
• MDOPE uniaxially oriented polyethylene film
• OPE Biaxially stretched polyethylene film
• polypropylene film CPP: non-stretched polypropylene film
• OPP biaxially stretched polypropylene film
• ethylene vinyl alcohol copolymer polyvinyl alcohol
• polyvinyl alcohol or other gas-barrier resins with olefin on one or both sides
• Polyolefin films such as gas-barrier heat-sealable films provided with a heat-sealable resin layer, polyvinyl alcohol films, ethylene-vinyl alcohol copolymer films, and the like.
• Biomass films, biodegradable films, and recycled plastic films are sold by various companies. It is possible to use films certified in each country, such as films listed in the list of eco-mark certified products listed by the Environment Association and films with the symbol mark specified by the Japan Bioplastics Association.
• biomass film Specific well-known biomass films include those made from biomass-derived ethylene glycol as a raw material.
• Biomass-derived ethylene glycol is produced from biomass-derived ethanol (biomass ethanol).
• biomass-derived ethylene glycol can be obtained by a method in which biomass ethanol is converted into ethylene glycol via ethylene oxide by a conventionally known method.
• commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be preferably used.
• films containing biomass polyester, biomass polyethylene terephthalate, etc. having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. It has been known.
• the dicarboxylic acid unit of biomass polyester uses the dicarboxylic acid derived from a fossil fuel.
• dicarboxylic acids aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation.
• a difunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polycarboxylic acid and/or its anhydride in addition to the above diol component and dicarboxylic acid component, a difunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polycarboxylic acid and/or its anhydride.
• a copolymerization component such as at least one polyfunctional compound selected from the group consisting of polycarboxylic acids and tri- or more functional oxycarboxylic acids.
• biomass polyolefin films such as biomass polyethylene films containing polyethylene resins made from biomass-derived ethylene glycol, biomass polyethylene-polypropylene films, etc. Films are also known.
• the polyethylene-based resin is not particularly limited except that the biomass-derived ethylene glycol is used as a part of the raw material.
• the ⁇ -olefin constituting the copolymer of ethylene and ⁇ -olefin is not particularly limited, and may be 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, or the like having 4 to 10 carbon atoms. 8 ⁇ -olefins.
• Known polyethylene resins such as low density polyethylene resins, medium density polyethylene resins and linear low density polyethylene resins can be used.
• linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or ethylene and 1 - octene) are preferred, and linear low density polyethylene resins with densities between 0.910 and 0.925 g/cm 3 are more preferred.
• Radiocarbon 14C exists in the atmosphere at a rate of 1 in 1012, and this rate does not change even with carbon dioxide in the atmosphere. Therefore, the carbon of the plant-derived resin contains radioactive carbon 14C. In contrast, the carbon of the fossil fuel-derived resin contains almost no radioactive carbon 14C. Therefore, by measuring the concentration of radioactive carbon 14C in the resin with an accelerator mass spectrometer, the content ratio of the plant-derived resin in the resin, that is, the degree of biomass plasticity can be obtained.
• plant-derived low-density polyethylene which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866
• plant-derived low-density polyethylene which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866
• Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866 include, for example, Braskem's product names "SBC818" and "SPB608". "SBF0323HC”, “STN7006”, “SEB853", “SPB681” and the like can be mentioned, and films using these as raw materials can be preferably used.
• Films and sheets containing starch which is a biomass raw material, and polylactic acid are also known. These can be appropriately selected and used depending on the application.
• the biomass film may be a laminate obtained by laminating a plurality of biomass films, or may be a laminate of a conventional petroleum-based film and a biomass film. Moreover, these biomass films may be either unstretched films or stretched films, and the manufacturing method thereof is not limited.
• biodegradable film Specific well-known biodegradable films include those made from commonly available biodegradable resins. Examples thereof include polycaprolactone, polyvinyl alcohol, polyamide, cellulose ester, lactic acid polyester resin, aliphatic polyester resin, and aliphatic aromatic polyester resin. These biodegradable resins may be used singly or in combination of two or more. Among them, aliphatic polyester-based resins or aliphatic-aromatic polyester-based resins are preferably used. Aliphatic polyester resins include aliphatic polyesters obtained by a polycondensation reaction between an aliphatic diol and an aliphatic dicarboxylic acid.
• Aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, Methanol is mentioned. These may be used alone or as a mixture thereof. Among them, it is preferable to use 1,4-butanediol.
• aliphatic dicarboxylic acids examples include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, and dodecanedioic acid, and acid anhydrides, which are derivatives thereof, may be used.
• succinic acid, succinic anhydride, or a mixture of these and adipic acid is preferred.
• polybutylene succinate (PBS) obtained from 1,4-butanediol and succinic acid (for example, BioPBS manufactured by PPT MCC Biochem), polybutylene succinate adipate (PBSA) obtained by copolymerizing PBS with adipic acid, etc. is mentioned.
• Aliphatic-aromatic polyester-based resins include copolymers containing aliphatic dicarboxylic acid units, aromatic dicarboxylic acid units, and linear aliphatic and/or alicyclic diol units.
• the diol component that provides the diol unit usually has 2 to 10 carbon atoms, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like. .
• diols having 2 to 4 carbon atoms are preferable, ethylene glycol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable.
• the dicarboxylic acid component that provides the dicarboxylic acid unit usually has 2 to 10 carbon atoms, and examples thereof include succinic acid, adipic acid, suberic acid, sebacic acid and dodecanedioic acid. Among them, succinic acid or adipic acid is preferred.
• aromatic dicarboxylic acid components that give aromatic dicarboxylic acid units include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Among them, terephthalic acid and isophthalic acid are preferred, and terephthalic acid is more preferred. Specific examples include PBAT (eg, Ecoflex manufactured by BAS F Co., Ltd.), which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid.
• PBAT eg, Ecoflex manufactured by BAS F Co., Ltd.
• Others include, for example, poly(3-hydroxyalkanoates) of aliphatic polyester copolymers obtained from hydroxyalkanoic acid and polyvalent carboxylic acid (among them, poly(3-hydroxybutyrate-co-3-hydroxyhexa Noate) (PHBH) (eg, Kaneka Aonylex), polylactic acid (PLA) (eg, Kaisho Biomaterials REVODE, NatureWorks Ingeo).
• PHBH poly(3-hydroxybutyrate-co-3-hydroxyhexa Noate)
• PLA polylactic acid
• Kaisho Biomaterials REVODE NatureWorks Ingeo
• the biodegradable film may be a laminate obtained by laminating a plurality of biodegradable films, or may be a laminate of a conventional petroleum-based film and a biodegradable film. Moreover, these biodegradable films may be either unstretched films or stretched films, and the manufacturing method thereof is not limited.
• 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 transverse 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 such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used in combination. good too.
• 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, acidic/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.
• Base material 1/adhesive layer 1/sealant film (2) Base material 1/adhesive layer 1/metal vapor deposition unstretched film (3) Base material 1/adhesive layer 1/metal vapor deposition stretched film (4) Transparent vapor deposition stretching Film/adhesive layer 1/sealant film (5) Substrate 1/adhesive layer 1/substrate 2/adhesive layer 2/sealant film (6) Substrate 1/adhesive layer 1/stretched metal deposition film/adhesive layer 2/sealant Film (7) Substrate 1/adhesive layer 1/transparent evaporated stretched film/adhesive layer 2/sealant film (8) Substrate 1/adhesive layer 1/metal layer/adhesive layer 2/sealant film (9) Substrate 1/ Adhesive layer 1/subsive layer 1/subsive layer
• Examples of the base material 1 used in configuration (1) include MDOPE film, OPE film, OPP film, PET film, nylon film, paper, and the like. Further, as the base material 1, a material coated for the purpose of improving gas barrier properties and ink receptivity when providing a printing layer, which will be described later, may be used. Commercially available products of the coated base film 1 include K-OPP film and K-PET film.
• the adhesive layer 1 is a cured coating film of the adhesive of the present invention. Sealant films include CPP films, LLDPE films, gas barrier heat seal films, and the like.
• a printing layer may be provided on the surface of the substrate 1 on the side of the adhesive layer 1 (the surface of the coating layer on the side of the adhesive layer 1 when a coated substrate film 1 is used) or the surface opposite to the adhesive layer 1, A printing layer may be provided.
• the printing layer is formed by general printing methods conventionally used for printing on polymer films and paper using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink.
• the base material 1 used in configurations (2) and (3) examples include MDOPE film, OPE film, OPP film, PET film, paper, and the like.
• the adhesive layer 1 is a cured coating film of the adhesive of the present invention.
• unstretched metal-deposited films include CPP films, LLDPE films, and VM-CPP films and VM-LLDPE films obtained by subjecting a gas-barrier heat seal film to metal deposition such as aluminum.
• An OPE film, a VM-MDOPE film obtained by subjecting an OPP film to vapor deposition of metal such as aluminum, a VM-OPE film, and a VM-OPP film can be used.
• a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
• Examples of transparent vapor-deposited stretched films used in configuration (4) include films obtained by vapor-depositing silica or alumina on MDOPE films, OPE films, OPP films, PET films, nylon films, and the like.
• a film obtained by coating the deposition layer may be used.
• the adhesive layer 1 is a cured coating film of the adhesive of the present invention.
• Examples of the sealant film include those similar to those of the configuration (1).
• a printed layer may be provided on the adhesive layer 1 side of the transparent vapor deposited stretched film (when using a film having a coated inorganic vapor deposited layer, the surface of the coating layer on the adhesive layer 1 side). The method of forming the printed layer is the same as that of configuration (1).
• Examples of the base material 1 used in configuration (5) include PET film, paper, and the like.
• Examples of the base material 2 include a nylon film and the like.
• At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention.
• Examples of the sealant film include those similar to those of the configuration (1).
• a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
• the base material 1 of configuration (6) As the base material 1 of configuration (6), the same ones as those of configurations (2) and (3) can be mentioned.
• the metallized stretched film include MDOPE film, OPE film, OPP film, VM-MDOPE film obtained by vapor-depositing metal such as aluminum on PET film, VM-OPE film, VM-OPP film and VM-PET film.
• At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention.
• the sealant film include those similar to those of the configuration (1).
• a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
• Examples of the base material 1 of configuration (7) include PET film, paper, and the like. Examples of the transparent vapor-deposited stretched film include those similar to those of the configuration (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
• Examples of the base material 1 of configuration (8) include PET film, paper, and the like. Aluminum foil etc. are mentioned as a metal layer. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
• Examples of the base material 1 of configurations (9) and (10) include PET film, paper, and the like.
• Examples of the base material 2 include a nylon film and the like. Aluminum foil etc. are mentioned as a metal layer.
• At least one of the adhesive layers 1, 2 and 3 is a cured coating film of the adhesive of the present invention.
• Examples of the sealant film include those similar to those of the configuration (1).
• a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
• the laminate of the present invention includes at least one of a metal vapor deposition film, a transparent vapor deposition film, and a metal layer
• the metal vapor deposition layer, the transparent vapor deposition layer, and the adhesive layer in contact with the metal layer are cured coating films of the adhesive of the present invention. is preferably
• the adhesion aid of the present invention is applied to a film material that serves as a substrate using a roll such as a gravure roll, and the organic solvent is volatilized by heating in an oven or the like. After that, the laminate of the present invention is obtained by laminating the polymer material melted by an extruder.
• the laminate of the present invention may further contain other films and substrates in addition to the above-described structures (1) to (10).
• other substrates in addition to the stretched film, unstretched film, and transparent vapor-deposited film described above, porous substrates such as paper, wood, and leather, which will be described later, can also be used.
• the adhesive used when bonding other substrates may or may not be the adhesive of the present invention.
• “Other layers” may contain known additives and stabilizers, such as antistatic agents, easy-adhesion coating agents, plasticizers, lubricants, and antioxidants.
• the "other layers” are pre-treated with corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. in order to improve adhesion when laminated with other materials. may
• the laminate of the present invention can be used in various applications, such as packaging materials for foods, pharmaceuticals, and daily necessities, lids, paper straws, paper napkins, paper spoons, paper plates, paper tableware such as paper cups, barrier materials, and roofs. materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive components, signboards, outdoor industrial applications such as stickers, decorative sheets used for injection molding simultaneous decoration methods, etc. It can be suitably used as packaging materials for liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and the like.
• the laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, medicines, and the like.
• the layer structure may vary depending on the contents, usage environment, and usage pattern.
• the package of the present invention may be appropriately provided with an easy-opening treatment or a resealing means.
• the laminate of the present invention is folded or overlapped so that the inner layer surface (sealant film surface) faces each other, and the peripheral edge is sealed, for example, by a side seal type, a two-sided seal type, There are three-sided seal type, four-sided seal type, envelope pasted seal type, palm pasted seal type, pleated seal type, flat bottom seal type, square bottom seal type, gusset type, and other heat seal methods. be done.
• the packaging material of the present invention can take various forms depending on the contents, environment of use, and form of use. A self-supporting packaging material (standing pouch) or the like is also possible.
• a heat sealing method known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing can be used.
• the opening is heat-sealed to manufacture a product using the packaging material of the present invention.
• filling contents include foods such as rice confectionery, bean confectionery, nuts, biscuits and cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snacks, bread, snack noodles, and instant noodles.
• Non-food items include cigarettes, disposable body warmers, medicines such as infusion packs, liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, cosmetics such as lotions and milky lotions, and vacuum cleaners. It can also be used as various packaging materials such as heat insulators, batteries and the like.
• Polyisocyanate composition (X-1) 500.0 parts of tolylene diisocyanate (TDI) was charged into a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and heated to 60° C. while stirring under a nitrogen gas stream. After that, 657.6 parts of bifunctional polypropylene glycol (Exenol 420 manufactured by AGC) was added while taking care of heat generation, and then heated to 80° C. and reacted at 80° C. for 2 hours.
• TDI tolylene diisocyanate
• TDI in the urethane prepolymer which is a reaction product of TDI and polypropylene glycol, is 0.05% by mass in solid content.
• a polyisocyanate composition (X-1) was obtained by purifying until The NCO% of the polyisocyanate composition (X-1) was 8.9%.
• Polyisocyanate composition (X-2) 1000.0 parts of hexamethylene diisocyanate (HDI) was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a condenser, and the mixture was heated to 60°C while stirring. 0.5 part of a quaternary ammonium salt was added dropwise thereto, and when a predetermined refractive index was reached, a deactivator was added as appropriate to complete the reaction. Next, using a thin film distillation apparatus, purify at a pressure of about 0.02 Torr and a temperature of 160° C. until HDI in the nurate body, which is a reaction product of HDI, reaches 0.05% by mass in the solid content. Thus, a polyisocyanate composition (X-2) was obtained. The NCO% of the polyisocyanate composition (X-2) was 21.8%.
• Polyisocyanate composition (X-4) 1045.2 parts of tolylene diisocyanate (TDI) and 134.0 parts of trimethylolpropane (TMP) were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a condenser, and stirred under a nitrogen gas stream. The mixture was heated to 90° C. while stirring, and reacted at 90° C. for 2 hours. Next, using a thin film distillation apparatus, at a pressure of about 0.02 Torr and a temperature of 160° C., the TDI in the urethane prepolymer, which is the reaction product of TDI and TMP, is reduced to 0.05% by mass in the solid content. Refined until A polyisocyanate composition (X-4) was obtained by diluting this with ethyl acetate so that the NV% was 75%. The solid conversion NCO% of the polyisocyanate composition (X-4) was 17.0%.
• Polyisocyanate composition (X-1M) 500.0 parts of tolylene diisocyanate (TDI) was charged into a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and heated to 60° C. while stirring under a nitrogen gas stream. After that, 657.6 parts of bifunctional polypropylene glycol (Exenol 420 manufactured by AGC) was added while taking care of heat generation, and then heated to 80° C. and reacted at 80° C. for 2 hours.
• TDI tolylene diisocyanate
• TDI in the urethane prepolymer which is a reaction product of TDI and polypropylene glycol
• TDI a reaction product of TDI and polypropylene glycol
• X-1M a polyisocyanate composition
• the NCO% of the polyisocyanate composition (X-1M) was 8.9%.
• Polyisocyanate composition (X-2M) 1000.0 parts of hexamethylene diisocyanate (HDI) was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a condenser, and the mixture was heated to 60°C while stirring. 0.5 part of a quaternary ammonium salt was added dropwise thereto, and when a predetermined refractive index was reached, a deactivator was added as appropriate to complete the reaction. Next, using a thin-film distillation apparatus, purification was carried out at a pressure of about 0.02 Torr and a temperature of 160° C.
• HDI hexamethylene diisocyanate
• Polyisocyanate composition (X-4M) 1045.2 parts of tolylene diisocyanate (TDI) and 134.0 parts of trimethylolpropane (TMP) were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a condenser, and stirred under a nitrogen gas stream. The mixture was heated to 90° C. while stirring, and reacted at 90° C. for 2 hours. Next, using a thin film distillation apparatus, at a pressure of about 0.02 Torr and a temperature of 160° C., the TDI in the urethane prepolymer, which is the reaction product of TDI and TMP, was reduced to 0.03% by mass in the solid content.
• TDI tolylene diisocyanate
• TMP trimethylolpropane
• a polyisocyanate composition (X-4M) was obtained by diluting this with ethyl acetate so that the NV% was 75%.
• the polyisocyanate composition (X-4M) had an NCO% of 17.0% in terms of solids.
• a urea derivative (U-1) was obtained by purifying to The urea derivative (U-1) is a compound represented by the above general formula (1), wherein R 1 is a residue of tolylene diisocyanate.
• the NCO% of the urea derivative composition (U-1) was 22.9%.
• a polyisocyanate composition (X-1U) was obtained by adding 0.5 parts of the urea derivative (U-1) to 99.5 parts of the polyisocyanate composition (X-1).
• a urea derivative (U-2) was obtained by purifying to The urea derivative (U-2) is a compound represented by the above general formula (1), wherein R 1 is a residue of hexamethylene diisocyanate.
• the NCO% of the urea derivative (U-2) was 23.7%.
• a polyisocyanate composition (X-2U) was obtained by adding 0.05 parts of the urea derivative (U-2) to 99.95 parts of the polyisocyanate composition (X-2M).
• Polyisocyanate composition (X-3U) A polyisocyanate composition (X-3U) was obtained by adding 0.01 part of the urea derivative (U-2) to 99.99 parts of the polyisocyanate composition (X-3).
• Polyisocyanate composition (X-4U) A polyisocyanate composition (X-4U) was obtained by adding 5.0 parts of the urea derivative (U-1) to 95.0 parts of the polyisocyanate composition (X-4).
• Polyisocyanate composition (X-1X) 500.0 parts of tolylene diisocyanate (TDI) was charged into a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and heated to 60° C. while stirring under a nitrogen gas stream. After that, 657.6 parts of bifunctional polypropylene glycol (Exenol 420 manufactured by AGC) was added while taking care of heat generation, and then heated to 80° C. and reacted at 80° C. for 2 hours.
• TDI tolylene diisocyanate
• Polyisocyanate composition (X-2X) 1000.0 parts of hexamethylene diisocyanate (HDI) was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a condenser, and the mixture was heated to 60°C while stirring. 0.5 part of a quaternary ammonium salt was added dropwise thereto, and when a predetermined refractive index was reached, a deactivator was added as appropriate to complete the reaction.
• HDI hexamethylene diisocyanate
• Polyisocyanate composition (X-3X) 1000.0 parts of isophorone diisocyanate (IPDI) was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a condenser, and the mixture was heated to 60° C. while stirring. 0.5 part of a quaternary ammonium salt was added dropwise thereto, and when a predetermined refractive index was reached, a deactivator was added as appropriate to complete the reaction.
• IPDI isophorone diisocyanate
• Polyisocyanate composition (X-4X) 1045.2 parts of tolylene diisocyanate (TDI) and 134.0 parts of trimethylolpropane (TMP) were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a condenser, and stirred under a nitrogen gas stream. The mixture was heated to 90° C. while stirring, and reacted at 90° C. for 2 hours. Next, using a thin film distillation apparatus, at a pressure of about 0.007 Torr and a temperature of 160° C., until TDI in the urethane prepolymer, which is the reaction product of TDI and TMP, is no longer detected (0.001 mass %) purified.
• a polyisocyanate composition (X-4X) was obtained by diluting this with ethyl acetate so that the NV% was 75%.
• the polyisocyanate composition (X-4X) had an NCO% of 17.0% in terms of solids.
• Polyol composition (Y-1) A polyol composition (Y-1) was obtained by mixing 90 parts by mass of commercially available castor oil (manufactured by Ito Oil Co., Ltd.) and 10 parts by mass of trifunctional polypropylene glycol (EXENOL 430 manufactured by AGC). The hydroxyl value of the polyol composition (Y-1) was 184.0 mgKOH/g.
• Polyol composition (Y-2) 7.2 parts of ethylene glycol, 15.8 parts of diethylene glycol, and 22.5 parts of neopentyl glycol were introduced into a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, water separator, etc. under nitrogen gas introduction. 21.9 parts of adipic acid, 4.6 parts of sebacic acid and 28.0 parts of isophthalic acid were charged. The temperature was gradually raised to 250° C. while performing a dehydration reaction under a normal pressure nitrogen stream, and the reaction was carried out at 250° C. for 2 hours.
• reaction product (Y-2) had an acid value of 0.7 mgKOH/g and a hydroxyl value of 159.0 mgKOH/g.
• Polyol composition (Y-3) 7.2 parts of ethylene glycol, 3.6 parts of neopentyl glycol, and 26.6 parts of diethylene glycol were introduced into a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, water separator, etc. under the introduction of nitrogen gas. The mixture was heated and dissolved while stirring. Then, 20.0 parts of adipic acid, 29.8 parts of isophthalic acid and 12.3 parts of terephthalic acid were charged at 120-130°C. The temperature was gradually raised to 260° C. while dehydration reaction was carried out under normal pressure nitrogen stream.
• the temperature is lowered to 240°C
• the rectifying column is switched to the condenser, and the line is connected to the vacuum pump to reduce the pressure to 30 to 60 Torr.
• the reaction was continued until the predetermined acid number and viscosity were reached.
• the polyol composition (Y-3) was obtained by diluting with ethyl acetate so that the NV% became 70%.
• the polyol composition (Y-3) had an acid value of 1.0 mgKOH/g in terms of solids and a hydroxyl value of 15.0 mgKOH/g in terms of solids.
• Example 1 Separate coating method Polyisocyanate composition (X-1) on nylon film (ON, 15 ⁇ m, manufactured by Unitika Ltd.), polyol on polyethylene film (LLDPE, TUX-HC, 60 ⁇ m, manufactured by Mitsui Chemicals Tocello Co., Ltd.)
• the composition (Y-1) was applied, and the nylon and LLDPE were pressure-bonded with a nip roll (50° C.) to obtain a laminate 1 of nylon/adhesive layer/LLDPE.
• the coating amounts of the polyisocyanate composition (X-1) and the polyol composition (Y-1) were 1.5 g/m 2 and 0.5 g/m 2 , respectively.
• Example 2 Separate coating method A laminate 2 was obtained in the same manner as in Example 1, except that the polyisocyanate composition was changed to (X-1M).
• the coating amounts of the polyisocyanate composition (X-1M) and polyol composition (Y-1) were 1.5 g/m 2 and 0.5 g/m 2 , respectively.
• Example 3 Separate coating method A laminate 3 was obtained in the same manner as in Example 1, except that the polyisocyanate composition was changed to (X-2).
• the coating amounts of the polyisocyanate composition (X-2) and the polyol composition (Y-1) were 1.0 g/m 2 and 1.0 g/m 2 , respectively.
• Example 4 Separate coating method A laminate 4 was obtained in the same manner as in Example 1, except that the polyisocyanate composition was changed to (X-2M).
• the coating amounts of the polyisocyanate composition (X-2M) and polyol composition (Y-1) were 1.0 g/m 2 and 1.0 g/m 2 , respectively.
• Non-solvent lamination method (non-solvent lamination) After stirring and mixing the polyisocyanate composition (X-3) and the polyol composition (Y-2), a nylon film (manufactured by Unitika Ltd., ON, 15 ⁇ m) was coated so as to be 2.0 g/m 2 , and a polyethylene film was coated. (LLDPE, TUX-HC, 60 ⁇ m, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was press-bonded with a nip roll (50° C.) to obtain a laminate 5 of nylon/adhesive layer/LLDPE. The mixing ratio of the polyisocyanate composition (X-3) and the polyol composition (Y-2) was 1:1.
• Non-solvent lamination method (non-solvent lamination) A laminate 6 was obtained in the same manner as in Example 5 except that the polyisocyanate composition was changed to (X-3M). The mixing ratio of the polyisocyanate composition (X-3M) and the polyol composition (Y-2) was 1:1.
• Example 7 Dry lamination method (dry lamination) After mixing and stirring the polyisocyanate composition (X-4), the polyol composition (Y-3) and ethyl acetate so that the solid content becomes 30%, it is applied to a nylon film (manufactured by Unitika Ltd. ON, 15 ⁇ m), Ethyl acetate was dried. The coating amount after drying with ethyl acetate was 2.5 g/m 2 .
• nylon and a polyethylene film (LLDPE, TUX-HC, 60 ⁇ m, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) were press-bonded with a nip roll (50° C.) to obtain a laminate 7 of nylon/adhesive layer/LLDPE.
• the mixing ratio of the polyisocyanate composition (X-4) and the polyol composition (Y-3) was 6:1.
• Example 8 Dry lamination method (dry lamination) A laminate 8 was obtained in the same manner as in Example 7, except that the polyisocyanate composition was changed to (X-4M). The mixing ratio of the polyisocyanate composition (X-4M) and the polyol composition (Y-3) was 6:1.
• Example 9 Separate coating method A laminate 9 was obtained in the same manner as in Example 1, except that the polyisocyanate composition was changed to (X-1U).
• the coating amounts of the polyisocyanate composition (X-1U) and polyol composition (Y-1) were 1.5 g/m 2 and 0.5 g/m 2 , respectively.
• Example 10 Separate coating method A laminate 10 was obtained in the same manner as in Example 1, except that the polyisocyanate composition was changed to (X-2U).
• the coating amounts of the polyisocyanate composition (X-2U) and polyol composition (Y-1) were 1.5 g/m 2 and 0.5 g/m 2 , respectively.
• Non-solvent lamination method (non-solvent lamination) A laminate 11 was obtained in the same manner as in Example 5 except that the polyisocyanate composition was changed to (X-3U). The mixing ratio of the polyisocyanate composition (X-3U) and the polyol composition (Y-2) was 1:1.
• Example 12 Dry lamination method (dry lamination) A laminate 8 was obtained in the same manner as in Example 7, except that the polyisocyanate composition was changed to (X-4U). The mixing ratio of the polyisocyanate composition (X-4M) and the polyol composition (Y-3) was 6:1.
• Example 2 Separate coating method A laminate 14 was obtained in the same manner as in Example 1, except that the polyisocyanate composition was changed to (X-2X).
• the coating amounts of the polyisocyanate composition (X-2X) and polyol composition (Y-1) were 1.5 g/m 2 and 0.5 g/m 2 , respectively.
• Non-solvent lamination method (non-solvent lamination) A laminate 15 was obtained in the same manner as in Example 5 except that the polyisocyanate composition was changed to (X-3X). The mixing ratio of the polyisocyanate composition (X-3X) and the polyol composition (Y-2) was 1:1.
• Viscosity change rate is less than 5%
• Viscosity change rate is 5% or more and less than 10%
• Viscosity change rate is 10% or more and less than 15%
• Viscosity change rate is 15% or more and less than 20%

Landscapes

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

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=86730217

Family Applications (2)

Family Applications After (1)

Country Status (5)

Cited By (1)

Families Citing this family (3)

Citations (7)

Family Cites Families (10)

• 2022
  • 2022-12-01 EP EP22904122.3A patent/EP4446392A4/en active Pending
  • 2022-12-01 EP EP22904117.3A patent/EP4446356A4/en active Pending
  • 2022-12-01 WO PCT/JP2022/044320 patent/WO2023106186A1/ja not_active Ceased
  • 2022-12-01 CN CN202280075143.1A patent/CN118234771A/zh active Pending
  • 2022-12-01 JP JP2023566266A patent/JP7485239B2/ja active Active
  • 2022-12-01 WO PCT/JP2022/044344 patent/WO2023106191A1/ja not_active Ceased
  • 2022-12-01 US US18/712,081 patent/US20250019581A1/en active Pending
  • 2022-12-01 JP JP2023545823A patent/JP7396547B2/ja active Active
  • 2022-12-01 CN CN202280075151.6A patent/CN118234824A/zh active Pending

Patent Citations (7)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events