CN116333662A - Moisture-curable polyurethane hot-melt resin composition, adhesive, and synthetic leather - Google Patents

Moisture-curable polyurethane hot-melt resin composition, adhesive, and synthetic leather Download PDF

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CN116333662A
CN116333662A CN202210924932.XA CN202210924932A CN116333662A CN 116333662 A CN116333662 A CN 116333662A CN 202210924932 A CN202210924932 A CN 202210924932A CN 116333662 A CN116333662 A CN 116333662A
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mass
hot
parts
melt
moisture
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千千和宏之
小松崎邦彦
藤原丰邦
南田至彦
金川善典
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DIC Corp
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DIC Corp
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    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

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  • 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)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The present invention aims to provide a moisture-curable polyurethane hot-melt resin composition which has excellent adhesion to a thermoplastic resin layer and excellent low-temperature flexibility. The present invention provides a moisture-curable polyurethane hot-melt resin composition comprising a hot-melt urethane prepolymer (A) having isocyanate groups and a phosphate ester (B), wherein the hot-melt urethane prepolymer (A) is prepared from a polyol (a) containing 50 mass% or more of a polyether polyol (a 1), and the content of the phosphate ester (B) exceeds 0.2 mass parts per 100 mass parts of the hot-melt urethane prepolymer (A).

Description

Moisture-curable polyurethane hot-melt resin composition, adhesive, and synthetic leather
Technical Field
The present invention relates to a moisture-curable polyurethane hot-melt resin composition, an adhesive and a synthetic leather.
Background
As the skin material, polyurethane (PU), polyvinyl chloride (PVC), olefin thermoplastic elastomer (TPO), and the like are used, and a material obtained by bonding these skin materials to a base fabric such as a cloth or a nonwoven fabric with an adhesive is generally used (for example, refer to patent document 1). Among them, the solvent-based adhesives have been widely used and generally used so far, but as an environmental measure, the reduction of VOC is required in regions, countries and enterprises, and the replacement of the solvent-based adhesives with aqueous and solvent-free adhesives is required.
As solvent-free adhesives, polyurethane-based moisture-curable hot melt adhesives (RHM) have been studied extensively. Conventional solvent systems and water systems are used to obtain a firm film by applying a low-viscosity compounding liquid to a skin layer, drying the skin layer to remove the solvent, and curing the skin layer if necessary. It is characterized in that the adhesive properties are easily obtained because the adhesive properties are low, and the wettability to the skin material is also good.
On the other hand, RHM uses a substance that dissolves by heat, but its viscosity is higher than that of a solvent system or water system, and it is difficult to obtain wettability of the skin layer. Among them, an adherend such as PVC skin material generally has low wettability with RHM, and even if conventional RHM is used, it is difficult to exhibit sufficient performance in terms of adhesion.
Prior art literature
Patent literature
Patent document 1: japanese patent publication No. 2008-514403, 2021-73135
Disclosure of Invention
Problems to be solved by the invention
The present invention aims to provide a moisture-curable polyurethane hot-melt resin composition which has excellent adhesion to a thermoplastic resin layer and excellent low-temperature flexibility.
Means for solving the problems
The present invention provides a moisture-curable polyurethane hot-melt resin composition comprising a hot-melt urethane prepolymer (a) having isocyanate groups and a phosphoric acid ester (B), wherein the hot-melt urethane prepolymer (a) is prepared from a polyol (a) containing 50 mass% or more of a polyether polyol (a 1), and the phosphoric acid ester (B) is contained in an amount exceeding 0.2 mass part per 100 mass parts of the hot-melt urethane prepolymer (a).
The present invention also provides an adhesive comprising the moisture-curable polyurethane hot-melt resin composition. The present invention also provides a synthetic leather comprising at least a thermoplastic resin layer and an adhesive layer.
Effects of the invention
The moisture-curable polyurethane hot-melt resin composition of the present invention is excellent in adhesion to a thermoplastic resin layer and low-temperature bendability. Therefore, the moisture-curable polyurethane hot-melt resin composition of the present invention can be particularly suitably used for the production of synthetic leather using a thermoplastic resin as a skin material.
Detailed Description
The moisture-curable polyurethane hot-melt resin composition of the present invention comprises a hot-melt urethane prepolymer (A) having isocyanate groups, which is produced from a specific polyol (a), and a specific amount of a phosphoric acid ester (B).
In order to obtain excellent low-temperature flexibility, the hot-melt urethane prepolymer (a) having isocyanate groups must be prepared from a polyol (a) containing 50 mass% or more of the polyether polyol (a 1). By such a design, the glass transition temperature of the adhesive can be reduced, and thus excellent low-temperature bendability can be obtained. The amount of the polyether polyol (a 1) used is preferably 50 to 90% by mass, more preferably 55 to 70% by mass, in the polyol (a) from the viewpoint of obtaining more excellent low-temperature bendability.
Examples of the polyether polyol (a 1) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, and the like. These polyols may be used alone or in combination of 2 or more. Among them, polypropylene glycol and/or polytetramethylene glycol are preferable from the viewpoint of obtaining more excellent low-temperature bendability, and polytetramethylene glycol is more preferable from the viewpoint of obtaining further more excellent wet heat resistance.
As the polyol (a), other polyols may be used in combination in addition to the polyether polyol (a). Examples of the other polyols include commercially available polyols such as polyester polyol, polycarbonate polyol, polybutadiene polyol, silicon diol and acrylic diol. These polyols may be used alone or in combination of 2 or more.
The number average molecular weight of the polyol (a) is preferably 500 to 10000, more preferably 1000 to 5000, from the viewpoint of obtaining more excellent adhesion, low-temperature bendability and mechanical strength. The number average molecular weight of the polyol (a) represents a value measured by a Gel Permeation Chromatography (GPC) method.
The hot-melt urethane prepolymer (a) having an isocyanate group may be, for example, a reaction product with the polyol (a) and the polyisocyanate (b).
Examples of the polyisocyanate (b) include aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like. Among them, aromatic polyisocyanates are preferable, and diphenylmethane diisocyanate is more preferable, from the viewpoint of obtaining more excellent reactivity and adhesion.
The hot-melt urethane prepolymer (A) has isocyanate groups at the polymer terminals and in the molecule, which can react with moisture present in the air, the substrate to which the urethane prepolymer is applied, and the adherend to form a crosslinked structure.
The method for producing the hot-melt urethane prepolymer (a) may be, for example, a method in which the polyol (a) is added dropwise to a reaction vessel containing the polyisocyanate (b) and then heated, and the isocyanate groups of the polyisocyanate (b) are reacted with each other under the condition that the isocyanate groups of the polyol (a) are excessive.
In order to obtain more excellent hot-melt property, adhesion property and low-temperature bendability, the molar ratio [ NCO/OH ] of the hydroxyl groups of the polyol (a) to the isocyanate groups of the polyisocyanate (b) is preferably 1.3 to 2.5, more preferably 1.5 to 2.0, when the polyol (a) and the polyisocyanate (b) are reacted.
The isocyanate group content (hereinafter abbreviated as "NCO%") of the hot-melt urethane prepolymer (a) is preferably 2.0 to 5.0 mass%, more preferably 2.5 to 3.5 mass% in terms of obtaining more excellent hot-melt property, adhesion property and low-temperature bendability. The NCO% of the hot-melt urethane prepolymer (A) represents a prepolymer obtained in accordance with JISK 1603-1: 2007. a value measured by a potentiometric titration method.
The phosphate (B) is an essential component in order to obtain excellent adhesion to the thermoplastic resin layer. By adding the phosphate (B), the compatibility of the interface between the thermoplastic resin and the RHM is improved, and excellent adhesion can be obtained.
As the phosphate (B), for example, a compound represented by the following formula (1) may be used, and 1 or 2 or more kinds may be used in combination.
[ chemical formula 1]
(HO) n P(O)(OR) 3-n (1)
(in the formula (1), n represents 1 or 2, and R represents an alkyl group.)
Among the compounds represented by the formula (1), the compound having 1 to 10 carbon atoms is preferable, and the compound having 1 to 8 carbon atoms is more preferable, in view of obtaining more excellent adhesion to the thermoplastic resin layer.
In addition, from the viewpoint of obtaining the effect, the content of the phosphoric acid ester (B) must exceed 0.2 parts by mass with respect to 100 parts by mass of the hot-melt urethane prepolymer (a). The content of the phosphoric acid ester (B) is preferably 0.2 to 1.0 parts by mass, more preferably 0.25 to 0.60 parts by mass, per 100 parts by mass of the hot-melt urethane prepolymer (a) in view of obtaining more excellent adhesion to the thermoplastic resin layer.
The moisture-curable polyurethane hot-melt resin composition of the present invention contains the hot-melt urethane prepolymer (a) and the phosphate ester (B) as essential components, but may contain other additives as required.
Examples of the other additives include urethane catalysts, neutralizing agents, crosslinking agents, silane coupling agents, thickeners, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light stabilizers, fluorescent brighteners, foaming agents, pigments, dyes, conductivity-imparting agents, antistatic agents, moisture permeability improvers, water repellents, oleophobic agents, hollow foam bodies, flame retardants, water absorbents, moisture absorbents, deodorants, foam stabilizers, antiblocking agents, and water resolvers. These additives may be used alone or in combination of 2 or more. The moisture-curable polyurethane hot-melt resin composition of the present invention has excellent adhesion and low-temperature flexibility even when a foam is produced by adding a foaming agent.
As described above, the moisture-curable polyurethane hot-melt resin composition of the present invention is excellent in adhesion to a thermoplastic resin layer and low-temperature flexibility. Therefore, the moisture-curable polyurethane hot-melt resin composition of the present invention can be particularly suitably used for the production of synthetic leather using a thermoplastic resin as a skin material.
Next, the synthetic leather of the present invention will be described.
The synthetic leather includes at least a thermoplastic resin layer and an adhesive layer containing the moisture-curable polyurethane hot-melt resin composition, and examples thereof include a synthetic leather in which a base material, the adhesive layer, and a thermoplastic resin layer are laminated in this order.
Examples of the base material include nonwoven fabrics, woven fabrics, and knitted fabrics based on polyester fibers, polyethylene fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, hemp, silk, wool, glass fibers, carbon fibers, and blend fibers thereof.
As the thermoplastic resin layer, for example, a resin layer formed of known polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene, TPO (Thermoplastic Olefinic Elastomer: thermoplastic polyolefin elastomer), thermoplastic ester-based elastomer, thermoplastic polyurethane, or the like can be used. In the present invention, even when polyvinyl chloride, TPO, thermoplastic ester-based elastomer, thermoplastic polyurethane are used as the thermoplastic resin, the thermoplastic resin has excellent adhesion and low-temperature bendability, and particularly, even when polyvinyl chloride which is difficult to adhere is foamed or unfoamed, the thermoplastic resin has excellent adhesion and low-temperature bendability.
The adhesive layer is formed of the moisture-curable polyurethane hot-melt resin composition of the present invention, and examples of the method for forming the adhesive layer include a method of melting the moisture-curable polyurethane hot-melt resin composition at 100 to 140 ℃ and then applying the composition by a roll coater, a spray coater, a T-die coater, a knife coater, a comma coater, or the like; precise modes such as a dispenser, ink-jet printing, screen printing, offset printing and the like; a method of applying the thermoplastic resin layer or the base material by using a nozzle coating or the like, and then bonding the thermoplastic resin layer or the base material.
After the 2 layers are bonded with the adhesive, the adhesive may be dried and cured by a known method as needed.
As the synthetic leather, a surface treatment layer may be further provided on the thermoplastic resin layer. As the surface treatment layer, for example, a surface treatment layer formed of a known solvent-based urethane resin, aqueous urethane resin, solvent-based acrylic resin, aqueous acrylic resin, or the like can be used.
[ example ]
Hereinafter, the present invention will be described in more detail using examples.
Example 1
50 parts by mass of polytetramethylene glycol (number average molecular weight: 2000, hereinafter abbreviated as "PEt-1") and 30 parts by mass of an aromatic polyester polyol (obtained by reacting 1, 6-hexanediol with phthalic acid, number average molecular weight: 2000, hereinafter abbreviated as "PEs-1"), and 20 parts by mass of an aliphatic polyester polyol (obtained by reacting 1, 6-hexanediol with sebacic acid, number average molecular weight: 3500, hereinafter abbreviated as "PEs-2") were added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and the mixture was heated under reduced pressure at 100℃to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ℃, 23 parts by mass of 4,4' -diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") melted at 70 ℃ was added, and the reaction was carried out at 110 ℃ under a nitrogen atmosphere for about 3 hours until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. A moisture-curable polyurethane hot-melt resin composition (1) was obtained by blending 0.37 parts by mass of a phosphoric acid ester (a mixture of monobutyl phosphate and dibutyl phosphate, average molecular weight: 182, hereinafter abbreviated as "phosphoric acid ester (1)") with 100 parts by mass of the hot-melt urethane prepolymer.
Example 2
55 parts by mass of PEt-1, 30 parts by mass of PEs-1, and 15 parts by mass of an aliphatic polyester polyol (obtained by reacting ethylene glycol, 1, 6-hexanediol, neopentyl glycol, and adipic acid), which were each obtained by mixing them, a number average molecular weight of 5500, hereinafter abbreviated as "PEs-3"), were put into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and the mixture was heated under reduced pressure at 100℃to dehydrate the mixture until the water content in the flask became 0.05% by mass or less. Next, the flask was cooled to 90℃and 20 parts by mass of MDI melted at 70℃was added thereto, and the reaction was carried out at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. The moisture-curable polyurethane hot-melt resin composition (2) was obtained by blending 0.48 part by mass of the phosphate (1) with 100 parts by mass of the hot-melt urethane prepolymer.
Example 3
55 parts by mass of polypropylene glycol (number average molecular weight: 2000, hereinafter abbreviated as "PEt-2") was added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, followed by mixing with 20 parts by mass of PEs-1 and 25 parts by mass of PEs-2, and heating under reduced pressure at 100℃to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90℃and 21 parts by mass of MDI melted at 70℃was added thereto, and the reaction was carried out at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. The moisture-curable polyurethane hot-melt resin composition (3) was obtained by blending 0.30 part by mass of the phosphate (1) with 100 parts by mass of the hot-melt urethane prepolymer.
Example 4
60 parts by mass of PEt-1, 25 parts by mass of PEs-1 and 15 parts by mass of PEs-2 were added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, and the mixture was mixed, and heated under reduced pressure at 100℃to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90℃and 22 parts by mass of MDI melted at 70℃was added thereto, and the reaction was carried out at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. The moisture-curable polyurethane hot-melt resin composition (4) was obtained by blending 0.37 part by mass of the phosphate (1) with 100 parts by mass of the hot-melt urethane prepolymer.
Example 5
65 parts by mass of PEt-2, 25 parts by mass of PEs-1 and 15 parts by mass of PEs-2 were added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, and mixed, and heated under reduced pressure at 100℃to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ℃, 24 parts by mass of MDI melted at 70 ℃ was added, and the reaction was carried out at 110 ℃ under a nitrogen atmosphere for about 3 hours until the isocyanate group content reached a constant, to obtain a hot-melt urethane prepolymer. The moisture-curable polyurethane hot-melt resin composition (5) was obtained by blending 0.52 part by mass of the phosphate (1) with 100 parts by mass of the hot-melt urethane prepolymer.
Example 6
65 parts by mass of PEt-1, 15 parts by mass of PEs-1 and 20 parts by mass of PEs-3 were added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, and the mixture was mixed, and heated under reduced pressure at 100℃to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90℃and 21 parts by mass of MDI melted at 70℃was added thereto, and the reaction was carried out at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. The moisture-curable polyurethane hot-melt resin composition (6) was obtained by blending 0.30 part by mass of the phosphate (1) with 100 parts by mass of the hot-melt urethane prepolymer.
Example 7
To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 30 parts by mass of PEt-1, 30 parts by mass of PEt-2, 20 parts by mass of PEs-1, and 20 parts by mass of PEs-2 were added and mixed, and the mixture was heated under reduced pressure at 100℃to dehydrate the mixture to 0.05 mass% or less of water in the flask. Next, the flask was cooled to 90℃and 22 parts by mass of MDI melted at 70℃was added thereto, and the reaction was carried out at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. The moisture-curable polyurethane hot-melt resin composition (7) was obtained by blending 0.36 part by mass of the phosphate (1) with 100 parts by mass of the hot-melt urethane prepolymer.
Comparative example 1
55 parts by mass of PEt-1, 20 parts by mass of PEs-1 and 15 parts by mass of PEs-2 were added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, and mixed, and heated under reduced pressure at 100℃to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90℃and 20 parts by mass of MDI melted at 70℃was added thereto, and the reaction was carried out at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. The moisture-curable polyurethane hot-melt resin composition (R1) was obtained by blending 0.11 part by mass of the phosphate (1) with 100 parts by mass of the hot-melt urethane prepolymer.
Comparative example 2
60 parts by mass of PEt-1, 25 parts by mass of PEs-1 and 15 parts by mass of PEs-2 were added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, and the mixture was mixed, and heated under reduced pressure at 100℃to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90℃and 22 parts by mass of MDI melted at 70℃was added thereto, and the reaction was carried out at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. The moisture-curable polyurethane hot-melt resin composition (R2) was obtained by blending 0.06 parts by mass of the phosphate (1) with 100 parts by mass of the hot-melt urethane prepolymer.
Comparative example 3
35 parts by mass of PEt-1, 35 parts by mass of PEs-1 and 30 parts by mass of PEs-3 were added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, and the mixture was mixed and heated under reduced pressure at 100℃to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ℃, 19 parts by mass of MDI melted at 70 ℃ was added, and the reaction was carried out at 110 ℃ for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer, to obtain a moisture-curable polyurethane hot-melt resin composition (R3).
Comparative example 4
30 parts by mass of PEt-1, 45 parts by mass of PEs-1 and 25 parts by mass of PEs-3 were added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, and the mixture was mixed, and heated under reduced pressure at 100℃to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90℃and 20 parts by mass of MDI melted at 70℃was added thereto, and the reaction was carried out at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. The moisture-curable polyurethane hot-melt resin composition (R4) was obtained by blending 0.36 parts by mass of the phosphate (1) with 100 parts by mass of the hot-melt urethane prepolymer.
[ method for measuring number average molecular weight and weight average molecular weight ]
The number average molecular weight of the polyol used in examples and comparative examples represents values measured by gel permeation column chromatography (GPC) under the following conditions.
Measurement device: high-speed GPC apparatus (HLC-8220 GPC, manufactured by Tosoh Co., ltd.)
Column: the following columns manufactured by Tosoh corporation were connected in series and used.
"TSKgel G5000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G4000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G3000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G2000" (7.8 mmI.D..times.30 cm). Times.1 root
A detector: RI (differential refractometer)
Column temperature: 40 DEG C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100. Mu.L (tetrahydrofuran solution with sample concentration of 0.4% by mass)
Standard sample: standard curves were made using standard polystyrene as described below.
(Standard polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-5000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-1 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-2 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-4 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-10 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-20 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-40 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-80 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-128 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-288 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-550 manufactured by Tosoh Co., ltd "
[ method for producing synthetic leather ]
In a constant temperature and humidity chamber adjusted to a temperature of 23 ℃ and a humidity of 50+ -5%, a polyvinyl chloride sheet was coated with a gravure coater to a temperature of 40+ -5 g/m 2 The wet curable polyurethane hot melt resin compositions obtained in examples and comparative examples were intermittently applied, the resultant was bonded to a polyester-based preform, and the resultant was cured at a temperature of 23℃and a humidity of 50.+ -. 5% for 24 hours, whereby a synthetic leather was obtained.
[ method of evaluating adhesion ]
For each of the obtained synthetic leathers, tensilon (Tensilon Universal tester "RTC-1210A" from Orientec Co., ltd.) was used at the crosshead: peel strength was measured under 200 mm/min, adhesive strength was measured, and it was evaluated as "O" for 6N/cm or more and "X" for less than 6N/cm.
[ method of evaluating Low-temperature bendability ]
The obtained synthetic leathers were subjected to a bending test (-10 ℃ C., 100 times/min) using a bending meter, and the number of times until cracks were generated on the surface of the synthetic leathers was measured, and the synthetic leathers were evaluated as "O" for 20000 times or more and as "X" for less than 20000 times.
[ Table 1]
Figure BDA0003778059080000121
[ Table 2]
Figure BDA0003778059080000131
[ Table 3]
Figure BDA0003778059080000141
The numerals in tables 1 to 3 represent parts by mass. The amount of the phosphoric acid ester (B) to be blended is 100 parts by mass based on 100 parts by mass of the hot-melt urethane prepolymer (a).
Examples 1 to 7, which are moisture-curable polyurethane hot-melt resin compositions of the present invention, are excellent in adhesion to polyvinyl chloride and low-temperature flexibility.
On the other hand, comparative examples 1 and 2 were poor in adhesion in such a manner that the content of the phosphate (B) was lower than the range defined in the present invention.
Comparative example 3 shows that the polyether polyol (a 1) was used in an amount lower than the range defined in the present invention and that the phosphate (B) was not used, and that the adhesiveness and the low-temperature bendability were poor.
Comparative example 4 shows that the amount of polyether polyol (a 1) used was less than the range defined in the present invention, and the low-temperature bendability was poor.

Claims (3)

1. A moisture-curable polyurethane hot-melt resin composition comprising a hot-melt urethane prepolymer (A) having isocyanate groups and a phosphoric acid ester (B),
the hot-melt urethane prepolymer (A) is produced from a polyol (a) containing 50 mass% or more of a polyether polyol (a 1),
the content of the phosphoric acid ester (B) exceeds 0.2 parts by mass with respect to 100 parts by mass of the hot-melt urethane prepolymer (a).
2. An adhesive comprising the moisture-curable polyurethane hot-melt resin composition according to claim 1.
3. A synthetic leather comprising at least a thermoplastic resin layer and an adhesive layer containing the moisture-curable polyurethane hot-melt resin composition according to claim 1.
CN202210924932.XA 2021-12-23 2022-08-02 Moisture-curable polyurethane hot-melt resin composition, adhesive, and synthetic leather Pending CN116333662A (en)

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