Stacked body and frame

Abstract

The present invention provides a laminate characterized by having a substrate, a primer layer formed from a resin composition containing a urethane resin (A) having a glass transition temperature of 0°C or lower and water, and an adhesive layer formed from a moisture-curing polyurethane hot melt resin composition. In addition, the present invention provides a frame characterized by having a decorative sheet on the adhesive layer in the laminate. The urethane resin (A) is preferably prepared using a polyester polyol as a raw material. The substrate is preferably polyvinyl chloride. The laminate of the present invention has excellent adhesive strength.

Description

Technical Field

[0001] This invention relates to laminates and frames (Japanese original: サッシ). Background Technology

[0002] As adhesives for building materials, the shift from solvent-based materials to moisture-curing polyurethane hot-melt adhesives is accelerating due to environmental concerns (see, for example, Patent Document 1). In the case of polyvinyl chloride (PVC) frames, during the grinding and processing of decorative panels, a process is employed where an existing solvent-based primer is applied to the PVC substrate, followed by bonding with a moisture-curing polyurethane hot-melt adhesive. However, there is a strong demand for a transition from solvent-based to water-based primers. Nevertheless, in reality, a system with high bonding strength has not yet been discovered.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2005-232437 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] The problem to be solved by the present invention is to provide a laminate with excellent adhesive strength.

[0008] Methods for solving problems

[0009] The present invention provides a laminate comprising a substrate, a primer layer and an adhesive layer, wherein the primer layer is formed of a resin composition comprising a urethane resin (A) having a glass transition temperature of 0°C or less and water, and the adhesive layer is formed of a moisture-curing polyurethane hot melt resin composition.

[0010] In addition, the present invention provides a framework characterized in that a decorative sheet is provided on the adhesive layer in the above-described laminate.

[0011] Invention Effects

[0012] The laminate of the present invention exhibits excellent adhesive strength. In particular, the above-described laminate maintains excellent adhesive strength even when using polyvinyl chloride (PVC) as the substrate, and can be used particularly effectively as a PVC-based frame. Detailed Implementation

[0013] The laminate of the present invention has a substrate, a specific primer layer and a specific adhesive layer.

[0014] Examples of suitable substrates include: fiber substrates; glass substrates; wood-based substrates such as plywood, MDF (medium-density fiberboard), and particleboard; metal substrates; and resin-based substrates such as polyester, nylon, polystyrene, polycarbonate, polyvinyl chloride, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyethylene, and polypropylene. It should be noted that, even when polyvinyl chloride is used as the substrate in this invention, excellent adhesive strength is maintained.

[0015] The aforementioned primer layer is formed from a resin composition containing a urethane resin (A) with a glass transition temperature below 0°C and water. By using a urethane resin (A) with a glass transition temperature below 0°C, the primer layer exhibits improved mobility when bonded to a molten hot-melt adhesive, allowing for integration of the substrate and adhesive layer, thus demonstrating excellent adhesive strength. Furthermore, by using a water-containing resin composition, the primer layer becomes an environmentally friendly material.

[0016] From the perspective of obtaining even better adhesive strength, the glass transition temperature of the above-mentioned urethane resin (A) is preferably -50°C to 0°C, and more preferably -30°C to 0°C. It should be noted that, regarding the method for determining the glass transition temperature of the above-mentioned urethane resin (A), the value measured by DSC according to JIS K 7121-1987 is shown. Specifically, the glass transition temperature (Tmg) at the midpoint of the differential scanning calorimeter curve is shown, obtained by placing a resin composition (excluding the crosslinking agent) containing the above-mentioned urethane resin (A) into a differential scanning calorimeter apparatus, heating it to (Tmg+50°C) at a heating rate of 10°C / min, holding it for 3 minutes, then rapidly cooling it.

[0017] The aforementioned urethane resin (A) can be dispersed in water, and is, for example, a urethane resin having hydrophilic groups such as anionic groups, cationic groups, and nonionic groups. These urethane resins (A) can be used alone or in combination of two or more. Among these, from the perspective of manufacturing stability and water dispersion stability, urethane resins having anionic groups and / or nonionic groups are more preferred.

[0018] As a method for obtaining the above-mentioned urethane resin having anionic groups, for example, one method is to use one or more compounds selected from diol compounds having carboxyl groups and compounds having sulfonyl groups as raw materials.

[0019] Examples of the carboxyl-containing diol compounds mentioned above include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvalerate. These compounds can be used alone or in combination of two or more.

[0020] As the aforementioned compounds having a sulfonyl group, examples include: 3,4-diaminobutyric acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N-(2-aminoethyl)-2-aminosulfonic acid, N-(2-aminoethyl)-2-aminoethylsulfonic acid, N-2-aminoethane-2-aminosulfonic acid, N-(2-aminoethyl)-β-alanine; and salts of these. These compounds can be used alone or in combination of two or more.

[0021] As a method for obtaining the above-mentioned urethane resin having nonionic groups, for example, a method using a compound having an oxyethylene structure as a raw material can be cited.

[0022] As compounds with the aforementioned oxyethylene structure, examples include polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene tetramethylene glycol, and polyethylene glycol dimethyl ether, which are polyether polyols with an oxyethylene structure. These compounds can be used alone or in combination of two or more. Among these, polyethylene glycol and / or polyethylene glycol dimethyl ether are preferred for easier control of hydrophilicity.

[0023] The number-average molecular weight of the raw materials used to obtain the above-mentioned urethane resin having nonionic groups is preferably in the range of 200 to 10,000, more preferably in the range of 300 to 3,000, and even more preferably in the range of 300 to 2,000, from the viewpoint of obtaining further superior emulsifying properties and water dispersion stability. It should be noted that the number-average molecular weight of the raw materials used to obtain the above-mentioned urethane resin having nonionic groups is a value determined by gel permeation chromatography (GPC).

[0024] As a method for obtaining the above-mentioned urethane resin having cationic groups, for example, a method using one or more compounds having amino groups as raw materials can be cited.

[0025] As the aforementioned compounds containing amino groups, examples include: triethylenetetramine, diethylenetriamine, and other compounds containing primary and secondary amino groups; N-alkyldialkylolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-alkyldiaminoalkylamines such as N-methyldiaminoethylamine and N-ethyldiaminoethylamine, and other compounds containing tertiary amino groups. These compounds can be used alone or in combination of two or more.

[0026] Specifically, the above-mentioned urethane resin (A) can be, for example, a polyol (a1), a polyisocyanate (a2), and a compound (a3) ​​having a hydrophilic group as needed (a raw material for obtaining the above-mentioned urethane resin having anionic groups, urethane resin having cationic groups, and urethane resin having nonionic groups).

[0027] As the aforementioned polyol (a1), for example, polyether polyols, polyester polyols, polyacrylic acid polyols, polycarbonate polyols, polybutadiene polyols, etc., can be used. These polyols can be used alone or in combination of two or more. It should be noted that when using the aforementioned urethane resin with nonionic groups as the aforementioned urethane resin (A), the aforementioned polyol (a1) is a substance other than the raw material used to obtain the aforementioned urethane resin with nonionic groups. It should be noted that, from the viewpoint of obtaining even more superior adhesive strength, polyester polyols are preferred as the aforementioned polyol (a1).

[0028] The number-average molecular weight of the polyol (a1) is preferably in the range of 500 to 100,000, more preferably in the range of 800 to 10,000, from the perspective of the mechanical strength and adhesive strength of the resulting film. It should be noted that the number-average molecular weight of the polyol (a1) mentioned above is a value obtained by gel permeation chromatography (GPC).

[0029] From the perspective of obtaining even better mechanical strength and adhesive strength, the usage ratio of the polyol (a1) is more preferably 40 to 90% by mass of the total mass of the raw materials constituting the urethane resin (A), and particularly preferably 50 to 80% by mass.

[0030] Regarding the aforementioned polyol (a1), a chain extender (a1-1) may also be used in conjunction as needed. As the aforementioned chain extender (a1-1), substances with a molecular weight less than 500 (preferably in the range of 50 to 450) can be used. Specifically, the following can be used: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerol, sorbitol, bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, etc. Chain extenders containing hydroxyl groups, such as hydroxyl diphenyl ether and trimethylolpropane; and chain extenders containing amino groups, such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophorone diamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, and hydrazine, etc. These chain extenders can be used alone or in combination of two or more. It should be noted that the molecular weights of the above chain extenders (a1-1) represent values ​​calculated from the chemical formula.

[0031] As for the proportion of the chain extender (a1-1) used, from the viewpoint of obtaining even better mechanical strength and adhesive strength, it is more preferably 0.1 to 30% by mass of the total mass of the raw materials constituting the urethane resin (A), and particularly preferably 0.5 to 10% by mass.

[0032] As the aforementioned polyisocyanate (a2), for example, aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimide diphenylmethane polyisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, phenylene diisocyanate, tetramethylphenylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate can be used. These polyisocyanates can be used alone or in combination of two or more.

[0033] From the perspective of obtaining even better mechanical strength and adhesive strength, the usage ratio of the polyisocyanate (a2) is more preferably 5 to 40% by mass of the total mass of the raw materials constituting the urethane resin (A), and particularly preferably 10 to 35% by mass.

[0034] As for the proportion of the compound (a3) ​​having the hydrophilic group mentioned above, from the viewpoint of obtaining further superior emulsifying properties, water dispersion stability and film-forming properties, it is more preferably 0.25 to 2% by mass, and particularly preferably 0.5 to 1.8% by mass, in the total mass of the raw materials constituting the urethane resin (A).

[0035] The average particle size of the aforementioned urethane resin (A) is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.05 to 0.9 μm, from the perspective of obtaining even better film-forming properties. It should be noted that the method for determining the average particle size of the aforementioned urethane resin (A) shows the value obtained by measuring the average particle size of a resin composition containing urethane resin (A) using a laser diffraction / scattering particle size distribution measuring device (Horiba Manufacturing Co., Ltd. "LA-910") with water as the dispersion, when the relative refractive index is 1.10 and the particle size is based on area.

[0036] The content of the above-mentioned urethane resin (A) in the resin composition for forming the primer layer of the present invention is preferably 10 to 90% by mass, more preferably 20 to 70% by mass.

[0037] The water contained in the above-mentioned resin composition can be ion-exchanged water, distilled water, etc. These waters can be used alone or in combination of two or more.

[0038] Next, a method for manufacturing the resin composition comprising the above-described urethane resin (A) used in this invention will be described.

[0039] The method for manufacturing the resin composition used in this invention includes the following steps: reacting the polyol (a1), the polyisocyanate (a2), and the compound having a hydrophilic group (a3) ​​in a solvent-free environment to obtain a urethane prepolymer (i) having an isocyanate group (hereinafter referred to as the "prepolymer step"); then dispersing the urethane prepolymer (i) in the water (hereinafter referred to as the "emulsification step"); and then reacting the chain extender (a1-1) to obtain a urethane resin (X) (hereinafter referred to as the "chain extension step").

[0040] Regarding the aforementioned prepolymer process, the following methods can be cited: methods carried out in organic solvents such as methyl ethyl ketone (MEK) and acetone; methods carried out using solvent-free equipment such as reaction vessels with stirring blades, kneaders, continuous kneaders, conical rollers, single-spindle extruders, twin-spindle extruders, triaxial extruders, universal mixers, plastic mills, vortex mixers, TK homogenizers, rotary dispersion mixers such as Filmix, Ebara Milder, Claire mix, ULTRA-TURRAX, Cavitron, and bio-mixers, ultrasonic dispersion devices, and online mixers, etc., which have no moving parts and can mix through the flow of the fluid itself.

[0041] Regarding the molar ratio of the total number of hydroxyl groups in the polyol (a1) and the hydroxyl and amino groups in the compound (a3) ​​having hydrophilic groups to the isocyanate groups in the polyisocyanate (a2) [isocyanate groups / (hydroxyl and amino groups)] in the prepolymer process, from the viewpoint of obtaining even better adhesive strength and mechanical strength, it is preferably 1.1 to 3, more preferably 1.2 to 2.

[0042] The reaction in the above-mentioned prepolymer process can be, for example, carried out at 50 to 120°C for 1 to 10 hours.

[0043] The above chain extension process is a process of increasing the molecular weight of the urethane prepolymer (i) by reacting the isocyanate groups of the urethane prepolymer (i) with the chain extender (a1-1) to obtain urethane resin (A).

[0044] Regarding the molar ratio of the isocyanate groups in the urethane prepolymer (i) to the hydroxyl and amino groups in the chain extender (a1-1) in the chain extension process [(hydroxyl and amino) / isocyanate groups], from the viewpoint of obtaining even better adhesive strength and mechanical strength, it is preferably 0.8 to 1.1, more preferably 0.9 to 1.

[0045] The chain extension process described above can be performed using the same equipment as the prepolymer process described above.

[0046] The above-mentioned resin composition contains the above-mentioned urethane resin (A) and water as essential components, but may also contain other additives as needed.

[0047] Other additives mentioned above may include surfactants, crosslinking agents, emulsifiers, neutralizers, thickeners, carbamate catalysts, fillers, pigments, dyes, flame retardants, leveling agents, and antiblocking agents. These additives may be used alone or in combination of two or more.

[0048] From the perspective of being solvent-free, environmentally friendly, and providing excellent adhesive strength, the adhesive layer is formed from a moisture-curing polyurethane hot melt resin composition.

[0049] As an example of the above-mentioned moisture-curing polyurethane hot melt resin composition, a composition containing a urethane prepolymer having an isocyanate group can be cited. The urethane prepolymer having an isocyanate group is a reaction product of a polyol (X) and a polyisocyanate (Y).

[0050] As the aforementioned polyol (X), for example, polyester polyol, polycarbonate polyol, polyether polyol, etc., can be used. These polyols can be used alone or in combination of two or more. Among these, polyester polyol is preferred, especially from the perspective of further superior adhesion strength to polyvinyl chloride materials. The content of the aforementioned polyester polyol in the aforementioned polyol (X) is preferably 50% by mass or more, more preferably 70% by mass or more.

[0051] For example, the following polyester polyols can be used: long-chain crystalline polyester polyol (x1), aliphatic polyester polyol (x2) other than the long-chain crystalline polyester polyol (x1) which is made from a diol having a 2,2-dimethyl-1,3-propylene group, aromatic polyester polyol (x3), and amorphous polyester polyols other than these. These polyester polyols can be used alone or in combination of two or more. Among these, from the viewpoint of further improving the adhesion strength with polyvinyl chloride materials, it is preferable to select one or more polyester polyols selected from the long-chain crystalline polyester polyol (x1), aliphatic polyester polyol (x2), and aromatic polyester polyol (x3), and more preferably, all three components can be used in combination.

[0052] As the aforementioned long-chain crystalline polyester polyol (x1), for example, the reaction product of a compound having hydroxyl groups and a polybasic acid can be used. It should be noted that in this invention, "crystalline" means that the peaks of heat of crystallization or heat of fusion can be confirmed in DSC (differential scanning calorimetry) measurements according to JIS K7121:2012, and "amorphous" means that the aforementioned peaks cannot be confirmed.

[0053] Examples of compounds containing hydroxyl groups include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptahydrate, octanediol, nonanediol, decanediol, trimethylolpropane, trimethylolethane, and glycerol. These compounds can be used alone or in combination of two or more. Among these, from the perspective of improving crystallinity and obtaining even better adhesive strength, one or more compounds selected from butanediol, hexanediol, octanediol, and decanediol are preferred.

[0054] Examples of the aforementioned polyacids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and dodecanoic acid. These compounds can be used alone or in combination of two or more. Among these, one or more of adipic acid, sebacic acid, and dodecanoic acid are preferred from the perspective of obtaining even better adhesive strength.

[0055] The number-average molecular weight of the aforementioned long-chain crystalline polyester polyol (x1) is preferably 500 to 10,000, more preferably 1,000 to 7,000, from the viewpoint of obtaining even better adhesive strength. It should be noted that the number-average molecular weight of the aforementioned crystalline polyester polyol (x1) represents a value obtained by gel permeation chromatography (GPC).

[0056] As for the amount of the long-chain crystalline polyester polyol (x1) used, from the viewpoint of obtaining even better adhesive strength, it is preferably 32 to 40% by mass relative to the total amount of the polyol (x) and the polyisocyanate (y), more preferably 33 to 37% by mass.

[0057] The aforementioned aliphatic polyester polyol (x2) is a substance other than the aforementioned long-chain crystalline polyester polyol (x1), and is a substance made from a diol having a 2,2-dimethyl-1,3-propylene group.

[0058] Furthermore, in terms of achieving excellent adhesive strength, the aforementioned aliphatic polyester polyol (a2) is further preferably composed of an aliphatic polyester polyol (x2-1) with a number average molecular weight of 1,000 to 3,000 and an aliphatic polyester polyol (x2-2) with a number average molecular weight of 5,000 to 9,000, with a preferred mass ratio [(x2-1) / (x2-2)] of 1 to 3. With this configuration, since the glass transition temperature and viscosity of the aliphatic polyester polyol as a whole are increased, excellent adhesive strength, particularly for polyvinyl chloride, can be obtained.

[0059] Both the aforementioned aliphatic polyester polyols (x2-1) and (x2-2) can be the reaction products of compounds with hydroxyl groups containing a diol having a 2,2-dimethyl-1,3-propylene group as an essential component and polybasic acids.

[0060] Examples of diols containing 2,2-dimethyl-1,3-propylene groups include neopentyl glycol, its dimers, and trimers. These compounds can be used alone or in combination of two or more. Among these, neopentyl glycol is preferred from the viewpoint of obtaining even better adhesive strength.

[0061] As for the amount of the diol having 2,2-dimethyl-1,3-propylidene used, it is preferably 10% by mass or more, and more preferably 10 to 20% by mass, in the total amount of the compounds having hydroxyl groups.

[0062] Other compounds containing hydroxyl groups that can be used besides the diols containing 2,2-dimethyl-1,3-propylene groups include, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanediol, bisphenol A, bisphenol F, their epoxide adducts, triethylene glycol, trimethylolpropane, trimethylolethane, glycerol, etc.

[0063] Examples of the aforementioned polyacids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and dodecanoic acid. These compounds can be used alone or in combination of two or more.

[0064] The number-average molecular weight of the aliphatic polyester polyol (x2-1) is preferably 1,500 to 2,500, from the viewpoint of obtaining even better adhesive strength, and the number-average molecular weight of the aliphatic polyester polyol (x2-2) is preferably 6,000 to 8,000. It should be noted that the number-average molecular weights of the aliphatic polyester polyols (x2-1) and (x2-2) are values ​​obtained by gel permeation chromatography (GPC).

[0065] Furthermore, from the viewpoint of obtaining even better adhesive strength, the mass ratio of the above-mentioned aliphatic polyester polyol (x2-1) to the above-mentioned aliphatic polyester polyol (x2-2) [(x2-1) / (x2-2)] is more preferably 1 to 2.5.

[0066] As for the total amount of the aliphatic polyester polyol (x2) used, from the viewpoint of obtaining even better adhesive strength, it is preferably 15 to 38% by mass, more preferably 20 to 37% by mass, relative to the total amount of the polyol (X) and the polyisocyanate (Y).

[0067] As the above-mentioned aromatic polyester polyol (x3), for example, the reaction product of a compound having hydroxyl groups and a polyacid containing an aromatic polyacid can be used; the reaction product of an aromatic compound having two or more hydroxyl groups and a polyacid; the reaction product of an aromatic compound having two or more hydroxyl groups and a polyacid containing an aromatic polyacid, etc.

[0068] As the aforementioned compounds containing hydroxyl groups, for example, the following can be used: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, etc. Alcohols, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,4-diethyl-1,5-pentanediol, trimethylolethane, trimethylolpropane, pentaerythritol, and other aliphatic compounds; cyclopentanediol, cyclohexanediol, cyclohexanediol, hydrogenated bisphenol A, and their epoxide alkane adducts, and other alicyclic compounds, etc. These compounds can be used alone or in combination of two or more.

[0069] As aromatic compounds having two or more hydroxyl groups, bisphenol A, bisphenol F, and their alkylene oxide (ethylene oxide, propylene oxide, butane oxide, etc.) adducts can be used, for example. These compounds can be used alone or in combination of two or more.

[0070] Examples of aromatic polybasic acids include phthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride. Other polybasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and 1,12-dodecanedicarboxylic acid. These polybasic acids can be used alone or in combination of two or more.

[0071] Other polyacids that can be used include succinic acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, decanoic acid, dodecanoic acid, eicosanoic acid, citacic acid, itaconic acid, citacic anhydride, itaconic anhydride, etc.

[0072] From the perspective of obtaining even better adhesive strength, the aromatic polyester polyol (x3) mentioned above is preferably a substance made from one or more phthalic acid compounds selected from phthalic acid, isophthalic acid, terephthalic acid and phthalic anhydride.

[0073] The number-average molecular weight of the aromatic polyester polyol (x3) is preferably 500 to 10,000, more preferably 1,000 to 5,000, from the perspective of obtaining even better adhesion. It should be noted that the number-average molecular weight of the aromatic polyester polyol (x3) is a value obtained by gel permeation chromatography (GPC).

[0074] From the perspective of obtaining even better adhesive strength, the amount of the aromatic polyester polyol (x3) used is preferably 15 to 35% by mass relative to the total amount of the polyol (x) and the polyisocyanate (y), more preferably 18 to 32% by mass.

[0075] As the aforementioned polyisocyanate (Y), for example, aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, phenyl diisocyanate, toluene diisocyanate, and naphthalene diisocyanate can be used; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylphenylmethylene diisocyanate can also be used. These polyisocyanates can be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferred from the viewpoint of obtaining even better adhesive strength, and diphenylmethane diisocyanate is more preferred.

[0076] The above-mentioned urethane prepolymer is a substance obtained by reacting the above-mentioned polyol (X) with the above-mentioned polyisocyanate (Y), and has isocyanate groups that can react with moisture present in the air or in a substrate coated with a moisture-curing polyurethane hot melt resin composition to form a cross-linked structure.

[0077] As a method for manufacturing the above-mentioned urethane prepolymer, it can be manufactured, for example, by placing the above-mentioned polyisocyanate (Y) into a reaction vessel containing the above-mentioned polyol (X), and reacting it under the condition that the isocyanate groups of the above-mentioned polyisocyanate (Y) are in excess relative to the hydroxyl groups of the above-mentioned polyol (X).

[0078] The equivalent ratio [NCO / OH] of the isocyanate group in the polyisocyanate (Y) and the hydroxyl group in the polyol (X) during the manufacture of the above-mentioned urethane prepolymer is preferably 1.5 to 4, more preferably 1.8 to 3.0, from the viewpoint of obtaining even better adhesive strength.

[0079] The isocyanate group content (hereinafter referred to as "NCO%)" of the urethane prepolymer obtained by the above method is preferably 1 to 6% by mass, more preferably 2 to 4% by mass, from the viewpoint of obtaining even better adhesive strength. It should be noted that the NCO% of the above-mentioned hot melt urethane prepolymer represents the value obtained by potentiometric titration according to JIS K1603-1:2007.

[0080] The moisture-curing polyurethane hot melt resin composition used in this invention preferably contains the above-mentioned urethane prepolymer, and other additives may be used further as needed.

[0081] Other additives mentioned above may include, for example, light stabilizers, curing catalysts, plasticizers, stabilizers, fillers, dyes, pigments, carbon black, color carriers, fluorescent whitening agents, silane coupling agents, waxes, and thermoplastic resins. These additives may be used alone or in combination of two or more.

[0082] As described above, the laminate of the present invention exhibits excellent adhesive strength. In particular, the laminate maintains excellent adhesive strength even when using polyvinyl chloride (PVC) as the substrate, and can be used particularly effectively as a PVC-based frame.

[0083] Examples of PVC-based frames include those comprising polyvinyl chloride as the substrate, a primer layer, an adhesive layer, and decorative sheets such as wood grain decorative paper on the adhesive layer.

[0084] As a method for manufacturing the PVC frame, for example, the following method can be used: coating a resin composition that forms the primer layer onto a PVC substrate, drying it, and then coating the moisture-curing polyurethane hot melt resin composition onto a decorative sheet, so that the two are bonded together and cured.

[0085] As a method for coating the above-mentioned resin composition and the above-mentioned moisture-curing polyurethane hot melt resin composition, a roller coater, a spray coater, a T-die coater, a doctor blade coater, a comma coater, etc. can be used.

[0086] Examples of the thickness of the primer layer are 0.5 to 20 μm, and examples of the thickness of the adhesive layer are 20 to 150 μm.

[0087] The curing conditions after bonding can be appropriately determined, for example, between a temperature of 20–50°C, a relative humidity of 40%–90%RH, and 0.5–5 days.

[0088] [Example]

[0089] The present invention will be described in more detail below using examples.

[0090] [Synthetic Example 1] Method for manufacturing resin composition <P1> for primer layer formation

[0091] In a nitrogen-purged container equipped with a thermometer, nitrogen inlet tube, and stirrer, 155 parts by weight of 1,6-hexanediol (hereinafter referred to as "HG"), 137 parts by weight of neopentyl glycol, and 424 parts by weight of adipic acid were added and melted at 120°C. Next, while stirring, the mixture was heated to 220°C over 3–4 hours and held for 5 hours, then cooled to 150°C. Then, 88 parts by weight of 2,2-dimethylolpropionic acid (hereinafter referred to as "DMPA") were added, and the mixture was held at 150°C while stirring for 5–10 hours. Finally, 300 parts by weight of methyl ethyl ketone (MEK) were added, thereby preparing a MEK solution (P1-A) of a carboxyl-containing polyester polyol with 70% by weight of non-volatile components.

[0092] In a nitrogen-purged container equipped with a thermometer, a nitrogen inlet tube, and a stirrer, 198 parts by mass of a methyl ethyl ketone solution of the aforementioned carboxyl-containing polyester polyol (P1-A), 160 parts by mass of the polyester polyol ("Crisvon CMA-654", manufactured by DIC Corporation, number average molecular weight: 1,500), 19 parts by mass of HG, 75 parts by mass of toluene diisocyanate, and 152 parts by mass of methyl ethyl ketone were reacted at 70°C until the time point at which the prescribed NCO% of the reaction product was reached, thereby obtaining a methyl ethyl ketone solution of a urethane prepolymer with isocyanate groups at the ends.

[0093] Next, 17.2 parts by mass of triethylamine as a neutralizing agent were added to the organic solvent solution of the urethane prepolymer and stirred. Then, 653 parts by mass of water and 7.7 parts by mass of piperazine were added and mixed to carry out a chain extension reaction, thereby obtaining an aqueous dispersion of the urethane resin. Next, the aqueous dispersion was desolventized to obtain a primer layer forming resin composition (P1) with a non-volatile component content of 40% by mass. The glass transition temperature of the obtained urethane resin was -30°C.

[0094] [Synthetic Example 2] Method for manufacturing resin composition <P2> for primer layer formation

[0095] Add 2 parts by mass of silane coupling agent ("KBM-403" manufactured by Shin-Etsu Silicones Co., Ltd.) and 5 parts by mass of water to 100 parts by mass of the above-mentioned primer layer forming resin composition (P1) to obtain 40% by mass of primer layer forming resin composition (P2).

[0096] [Comparative Synthesis Example 1] Method for manufacturing resin composition <RP1> for primer layer formation

[0097] In a reaction vessel equipped with a thermometer, a nitrogen inlet pipe, and a stirrer, nitrogen gas was introduced while 33.3 parts by mass of isophthalic acid, 16.7 parts by mass of sebacic acid, 7.3 parts by mass of adipic acid, 6 parts by mass of ethylene glycol, 11.0 parts by mass of 1,6-hexanediol, and 22.5 parts by mass of neopentyl glycol were added. The reaction was carried out at 230°C for 24 hours until the acid value reached below 1. The mixture was then cooled to below 90°C, and 20.4 parts by mass of methyl ethyl ketone were added and mixed to obtain an aromatic polyester polyol (RP1-A).

[0098] In a reaction vessel, 207 parts by weight of aromatic polyester polyol (RP1-A), 7.4 parts by weight of 1,4-butanediol, and 17.0 parts by weight of methyl ethyl ketone were added, stirred, and mixed evenly. Next, 14.7 parts by weight of DMPA were added, followed by 46.8 parts by weight of toluene diisocyanate. The reaction was carried out at 70°C for 12 hours to perform the urethane esterification process. Once the isocyanate value was confirmed to be below 0.1%, 97 parts by weight of methyl ethyl ketone and 0.7 parts by weight of 1,3-butanediol were added to obtain an organic solvent solution of the urethane prepolymer. Next, 11.6 parts by weight of triethylamine as a neutralizing agent were added to the organic solvent solution of the urethane prepolymer and stirred. Then, 1000 parts by weight of water were added and mixed to obtain an aqueous dispersion of the urethane resin. Next, the aqueous dispersion was desolventized to obtain a primer layer forming resin composition (RP1) with a non-volatile component of 23% by weight. The glass transition temperature of the obtained urethane resin was 5°C.

[0099] [Comparative Synthesis Example 2] Method for manufacturing resin composition <RP2> for primer layer formation

[0100] In a reaction vessel equipped with a thermometer, a nitrogen inlet pipe, and a stirrer, nitrogen gas was introduced while 29.3 parts by mass of isophthalic acid, 29.3 parts by mass of terephthalic acid, 13 parts by mass of ethylene glycol, and 22.3 parts by mass of diethylene glycol were added. The reaction was carried out at 230°C for 24 hours until the acid value reached below 1. The mixture was then cooled to below 90°C, and 26.3 parts by mass of methyl ethyl ketone were added and mixed to obtain aromatic polyester polyol (RP2-A).

[0101] 226 parts by weight of aromatic polyester polyol (RP2-A) and 40.0 parts by weight of methyl ethyl ketone were added to a reaction vessel, and the mixture was stirred and homogenized. Next, 13 parts by weight of 2,2-dimethylolpropionic acid were added, followed by 44.3 parts by weight of isophorone diisocyanate and 0.2 parts by weight of stannous octoate. The reaction was carried out at 70°C for 12 hours to perform the urethane esterification process. Once the isocyanate content was confirmed to be below 0.1%, 25 parts by weight of methyl ethyl ketone and 0.4 parts by weight of methanol were added to obtain an organic solvent solution of the urethane prepolymer.

[0102] Next, 7.1 parts by mass of an aqueous ammonia solution as a neutralizing agent were added to the organic solvent solution of the urethane prepolymer and stirred. Then, 877 parts by mass of water were added and mixed to obtain an aqueous dispersion of the urethane resin. Next, the aqueous dispersion was desolventized to obtain a primer layer forming resin composition (RP-2) with a non-volatile component content of 22% by mass. The glass transition temperature of the obtained urethane resin was 50°C.

[0103] [Synthesis Example 3] Moisture-curing polyurethane hot melt resin composition for adhesive layer formation <PUR1>

[0104] In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 34 parts by mass of long-chain crystalline polyester polyol (the reaction product of 1,6-hexanediol and dodecanoic acid, number average molecular weight: 3,500, hereinafter referred to as "crystalline PEs (1)") and 10 parts by mass of aliphatic polyester polyol (the reaction product of diethylene glycol, neopentyl glycol, 1,6-hexanediol and adipic acid, number average molecular weight: 2,000, the amount of neopentyl glycol used in the total amount of all diols: 14% by mass, hereinafter referred to as "aliphatic PEs (1)") were added. 10 parts by mass of aliphatic polyester polyol (the reaction product of diethylene glycol, neopentyl glycol, 1,6-hexanediol and adipic acid, number average molecular weight: 7,000, the amount of neopentyl glycol used in the total amount of all diols: 14% by mass, hereinafter referred to as "aliphatic PEs (2)") and 30 parts by mass of aromatic polyester polyol (the reaction product of neopentyl glycol and phthalic acid, number average molecular weight: 2,000, hereinafter referred to as "aromatic PEs (1)") were heated under reduced pressure at 100°C and dehydrated until the water content in the flask was 0.05% by mass. After cooling the flask to 90°C, 16 parts by mass of 4,4'-diphenylmethane diisocyanate (hereinafter referred to as "MDI") which had been melted at 70°C were added, and the mixture was reacted at 110°C for about 2 hours under a nitrogen atmosphere until NCO% became constant, thereby obtaining a moisture-curing polyurethane hot melt resin composition <PUR1> for forming an adhesive layer containing urethane prepolymer.

[0105] [Synthesis Example 4] Moisture-curing polyurethane hot melt resin composition for adhesive layer formation <PUR2>

[0106] In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 34 parts by weight of crystalline PEs (1), 20 parts by weight of aliphatic PEs (1), 10 parts by weight of aliphatic PEs (2), and 20 parts by weight of aromatic PEs (1) were added. The mixture was heated under reduced pressure at 100°C and dehydrated until the water content in the flask was 0.05% by weight. After cooling the flask to 90°C, 16 parts by weight of MDI that had been melted at 70°C were added. The mixture was reacted at 110°C for about 2 hours under a nitrogen atmosphere until the NCO% became constant, thereby obtaining a moisture-curing polyurethane hot melt resin composition <PUR2> for adhesive layer formation containing urethane prepolymer (i-2).

[0107] [Example 1]

[0108] On a polyvinyl chloride (PVC) material, the primer layer forming resin composition <P1> obtained in Synthesis Example 1 was applied using a roller to a dried thickness of 3 μm, and dried at 60°C for 10 minutes in a dryer. Next, the adhesive layer forming moisture-curing polyurethane hot melt resin composition <PUR1> obtained in Synthesis Example 3, which had been melted at 120°C for 1 hour, was applied to the decorative sheet to a thickness of 50 μm and bonded to the primer layer. The laminate was cured at 23°C and 50% humidity for 48 hours to obtain a PVC-based laminate.

[0109] [Examples 2-3, Comparative Examples 1-3]

[0110] The type of resin composition used to form the primer layer was changed as shown in Tables 1-2. Otherwise, the same procedure as in Example 1 was followed to obtain the PVC laminate.

[0111] [Methods for determining number-average molecular weight and weight-average molecular weight]

[0112] The number-average molecular weights of the polyols used in the synthetic examples and comparative synthetic examples are expressed as values ​​obtained by gel permeation chromatography (GPC) under the conditions described below.

[0113] Measurement apparatus: High-speed GPC device (Tosoh Corporation "HLC-8220GPC") Column: The following columns manufactured by Tosoh Corporation are connected in series for use.

[0114] "TSKgel G5000" (7.8mm I.D. × 30cm) × 1 stick

[0115] "TSKgel G4000" (7.8mm I.D. × 30cm) × 1 stick

[0116] "TSKgel G3000" (7.8mm I.D. × 30cm) × 1 stick

[0117] "TSKgel G2000" (7.8mm I.D. × 30cm) × 1 stick

[0118] Detector: RI (Differential Refractometer)

[0119] Column temperature: 40℃

[0120] Eluent: Tetrahydrofuran (THF)

[0121] Flow rate: 1.0 mL / min

[0122] Injection volume: 100 μL (a tetrahydrofuran solution with a sample concentration of 0.4% by mass)

[0123] Standard samples: The standard curve was prepared using the following standard polystyrene.

[0124] (Standard polystyrene)

[0125] TSKgel Standard Polystyrene A-500 manufactured by Tosoh Corporation

[0126] TSKgel Standard Polystyrene A-1000 manufactured by Tosoh Corporation

[0127] TSKgel Standard Polystyrene A-2500 manufactured by Tosoh Corporation

[0128] TSKgel Standard Polystyrene A-5000 manufactured by Tosoh Corporation

[0129] TSKgel Standard Polystyrene F-1 manufactured by Tosoh Corporation

[0130] TSKgel Standard Polystyrene F-2 manufactured by Tosoh Corporation

[0131] TSKgel Standard Polystyrene F-4 manufactured by Tosoh Corporation

[0132] TSKgel Standard Polystyrene F-10 manufactured by Tosoh Corporation

[0133] TSKgel Standard Polystyrene F-20 manufactured by Tosoh Corporation

[0134] TSKgel Standard Polystyrene F-40 manufactured by Tosoh Corporation

[0135] TSKgel Standard Polystyrene F-80 manufactured by Tosoh Corporation

[0136] TSKgel Standard Polystyrene F-128 manufactured by Tosoh Corporation

[0137] TSKgel Standard Polystyrene F-288 manufactured by Tosoh Corporation

[0138] TSKgel Standard Polystyrene F-550 manufactured by Tosoh Corporation

[0139] [Methods for evaluating bond strength]

[0140] (1) 180-degree peel test

[0141] The PVC laminates obtained in the examples and comparative examples were cut into 1-inch wide pieces and used as test pieces. They were peeled along the 180-degree direction and their strength was measured by Autograph (Shimadzu Corporation "AG-1"), and evaluated as follows.

[0142] “○”: Above 40 N / inch

[0143] “×”: Other than those mentioned above

[0144] (2) Heat creep test

[0145] The PVC laminates obtained in the examples and comparative examples were cut into 1-inch wide pieces and used as test pieces. A load of 500 g / inch was applied to them in a 60°C dryer, and the distance they moved after 24 hours or the time it took for them to fall after moving 40 mm was measured.

[0146] “○”: Less than 5mm

[0147] “×”: Other than those mentioned above

[0148] [Table 1]

[0149]

[0150] [Table 2]

[0151]

[0152] It can be seen that the bonding strength of Examples 1 to 3, which are the laminates of the present invention, is excellent.

[0153] On the other hand, Comparative Examples 1 and 2 show poor adhesive strength because the glass transition temperature of the urethane resin used in the primer layer exceeds the range specified in this invention.

[0154] Comparative Example 3, which lacks a primer layer, exhibits poor adhesive strength.

Claims

1. A laminated body, characterized in that, It has a substrate, a primer layer and an adhesive layer, The primer layer is formed from a resin composition containing urethane resin (A) with a glass transition temperature below 0°C and water. The urethane resin (A) is made from at least a polyol (a1) containing a polyester polyol and a polyisocyanate (a2). The adhesive layer is formed from a moisture-curing polyurethane hot melt resin composition. The moisture-curing polyurethane hot melt resin composition is a reaction product of a polyol (X) containing a polyester polyol and a polyisocyanate (Y). The polyester polyol contained in the polyol (X) includes a long-chain crystalline polyester polyol (x1), an aliphatic polyester polyol (x2) other than the long-chain crystalline polyester polyol (x1) which is made from a diol having a 2,2-dimethyl-1,3-propylene group, and an aromatic polyester polyol (x3).

2. The laminated body according to claim 1, wherein, The substrate is polyvinyl chloride.

3. A framework, characterized in that, The adhesive layer in the laminate of claim 2 has decorative pieces.

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