CN119677791A - 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 PDFInfo
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- CN119677791A CN119677791A CN202380061768.7A CN202380061768A CN119677791A CN 119677791 A CN119677791 A CN 119677791A CN 202380061768 A CN202380061768 A CN 202380061768A CN 119677791 A CN119677791 A CN 119677791A
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- 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
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- 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
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- 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
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- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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Abstract
本发明提供以下的湿固化型聚氨酯热熔树脂组合物，其特征在于，含有具有异氰酸酯基的热熔氨基甲酸酯预聚物（A）和阻燃剂（B），上述热熔预聚物（A）以包含50质量%以上的聚醚多元醇（a1）的多元醇（a）为原料，相对于上述热熔氨基甲酸酯预聚物（A）100质量份，上述阻燃剂（B）的含量超过15质量份。本发明还提供以下的粘接剂，其特征在于，含有上述湿固化型聚氨酯热熔树脂组合物。上述阻燃剂（B）优选为具有3个以上芳香环的磷酸酯。The present invention provides the following moisture-curable polyurethane hot-melt resin composition, characterized in that it contains a hot-melt urethane prepolymer (A) having an isocyanate group and a flame retardant (B), wherein the hot-melt prepolymer (A) is made of a polyol (a) containing 50% by mass or more of a polyether polyol (a1), and the content of the flame retardant (B) exceeds 15 parts by mass relative to 100 parts by mass of the hot-melt urethane prepolymer (A). The present invention also provides the following adhesive, characterized in that it contains the moisture-curable polyurethane hot-melt resin composition. The flame retardant (B) is preferably a phosphate having three or more aromatic rings.
Description
Technical Field
The present invention relates to a moisture-curable polyurethane hot-melt resin composition, an adhesive and a synthetic leather.
Background
In synthetic leather, polyurethane (PU), polyvinyl chloride (PVC), olefin thermoplastic elastomer (TPO), and the like are used as skin materials, and materials obtained by bonding these skin materials to a base fabric such as a cloth or a nonwoven fabric with an adhesive are 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 demanded in regions, countries and enterprises, and the replacement of the solvent-based adhesives with aqueous and solvent-free adhesives is required.
On the other hand, synthetic leather used for interior materials for vehicles and indoor furniture is required to have flame retardancy from the viewpoint of fire resistance, but it is assumed that the level of flexibility at low temperatures used in cold regions is also increasing. However, no material having all of these characteristics has been found.
Prior art literature
Patent literature
Patent document 1 Japanese patent laid-open No. 2008-514403
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 is excellent in adhesion, low-temperature flexibility and flame retardance.
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 flame retardant (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 flame retardant (B) exceeds 15 parts by mass per 100 parts by mass of the hot-melt urethane prepolymer (a).
The present invention also provides the following adhesive, which is characterized by 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 the adhesive layer.
Effects of the invention
The moisture-curable polyurethane hot-melt resin composition of the present invention is excellent in adhesion, low-temperature flexibility and flame retardance. Therefore, the moisture-curable polyurethane hot-melt resin composition of the present invention can be particularly suitably used for producing 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 flame retardant (B).
In order to obtain excellent low-temperature flexibility, the hot-melt urethane prepolymer (a) having an isocyanate group 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 terms 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 these, 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 more excellent heat resistance and moist heat. As the polyether polyol, a plant-derived polyether polyol may be used. The plant-derived polyether polyol may be obtained as a commercially available product such as "Bio PTG" manufactured by Mitsubishi Chemical, "Bio PTG" manufactured by Baotu chemical Co., ltd., or "biomass polypropylene glycol manufactured by Vithal Castor Polyols.
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, and may be derived from petroleum or from plants. Among the other polyols, polyester polyols are preferred in view of obtaining more excellent adhesion.
The number average molecular weight of the polyol (a) is preferably 500 to 10,000, more preferably 1,000 to 6,000, from the viewpoint of obtaining more excellent adhesion, low-temperature bendability and mechanical strength. The number average molecular weight of the polyol (a) is a value measured by Gel Permeation Chromatography (GPC).
The isocyanate group-containing hot-melt urethane prepolymer (a) may be, for example, a reaction product of 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, xylylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate, aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. These polyisocyanates may be used alone or in combination of 2 or more, and may be derived from petroleum or plant. Among these, 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 an isocyanate group in a molecule at a polymer end, and the isocyanate group can react with moisture existing in air, a substrate coated with the urethane prepolymer, and an adherend to form a crosslinked structure.
The method for producing the hot-melt urethane prepolymer (A) can be produced, for example, by dropping the polyol (a) into a reaction vessel containing the polyisocyanate (b) and heating the reaction vessel, and reacting the reaction vessel under such conditions that the isocyanate groups of the polyisocyanate (b) are excessive relative to the hydroxyl groups of the polyol (a).
The molar ratio [ NCO/OH ] of the hydroxyl groups of the polyol (a) to the isocyanate groups of the polyisocyanate (b) in the reaction of the polyol (a) with the polyisocyanate (b) is preferably 1.3 to 2.5, more preferably 1.5 to 2.0, from the viewpoint of obtaining more excellent hot-melt property, adhesion property and low-temperature bendability.
The isocyanate group content (hereinafter abbreviated as "NCO%") of the hot-melt urethane prepolymer (a) is preferably 1.2 to 5.0 mass%, more preferably 1.7 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) was measured according to the potential difference titration method in accordance with JISK 1603-1:2007.
The flame retardant (B) is an essential component in order to obtain excellent flame retardancy, and the content thereof must exceed 15 parts by mass with respect to 100 parts by mass of the hot-melt urethane prepolymer (a). The content of the flame retardant (B) is preferably 17.5 to 55 parts by mass relative to 100 parts by mass of the hot-melt urethane prepolymer (a) in order to maintain the low-temperature flexibility and the adhesiveness at a high level and to obtain more excellent flame retardancy.
As the flame retardant (B), for example, a phosphate ester, a phosphate-containing flame retardant, red phosphorus, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide, graphite, a phosphorus-boron compound, a vinyl polymer, or the like can be used. These flame retardants may be used alone or in combination of 2 or more. Among these, from the viewpoint of maintaining the low-temperature flexibility and the adhesiveness at a high level and obtaining more excellent flame retardancy, a phosphate having 3 or more aromatic rings is preferable, and a phosphate having 4 or more aromatic rings is more preferable.
The moisture-curable polyurethane hot-melt resin composition of the present invention contains the hot-melt urethane prepolymer (a) and the flame retardant (B) as essential components, but may contain other additives as required.
Examples of the other additives include urethane catalyst, neutralizing agent, crosslinking agent, silane coupling agent, thickener, filler, thixotropic agent, thickener, wax, heat stabilizer, light stabilizer, fluorescent whitening agent, foaming agent, pigment, dye, conductivity-imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam, water absorbent, moisture absorbent, deodorant, foam stabilizer, plasticizer, antiblocking agent, and water repellent. These additives may be used alone or in combination of 2 or more.
As described above, the moisture-curable polyurethane hot-melt resin composition of the present invention is excellent in adhesion, low-temperature flexibility and flame retardancy. Therefore, the moisture-curable polyurethane hot-melt resin composition of the present invention can be particularly suitably used for producing 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 the thermoplastic resin layer are laminated in this order.
Examples of the base material include nonwoven fabrics, woven fabrics, and knit fabrics formed of 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, TPO, thermoplastic ester-based elastomer, thermoplastic polyurethane is hardly adhered, the thermoplastic resin has excellent adhesion and low-temperature bendability, regardless of whether it is a foamed or unfoamed product.
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 in which the moisture-curable polyurethane hot-melt resin composition is melted at 100 to 140 ℃ and then applied to the thermoplastic resin layer or the base material by using a coater system such as a roll coater, a spray coater, a T-die coater, a doctor blade coater, or a comma coater, a precision system such as a dispenser, ink jet printing, screen printing, or offset printing, or a nozzle coating, and then bonded.
After the 2 layers are bonded with the adhesive, the adhesive may be dried and cured by a known method as needed.
In 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, water-based urethane resin, solvent-based acrylic resin, water-based acrylic resin, or the like can be used.
Examples
Hereinafter, the present invention will be described in more detail using examples.
Example 1
To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 171 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000, hereinafter abbreviated as "PEt-1"), 78 parts by mass of polyester polyol (a substance obtained by reacting 1, 6-hexanediol with phthalic acid, number average molecular weight: 2,000, hereinafter abbreviated as "PEs-1"), 62 parts by mass of polyester polyol (a substance obtained by reacting 1, 6-hexanediol with sebacic acid, number average molecular weight: 3,500, hereinafter abbreviated as "PEs-2"), were added, and the mixture was mixed, and heated under reduced pressure at 100 ℃. Next, the flask was cooled to 90 ℃, 71 parts by mass of 4,4' -diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") which had been 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. 35 parts by mass of a phosphoric acid ester (1, 3-phenylenebis (2, 6-dimethylphenyl=phosphoric acid ester), hereinafter abbreviated as "flame retardant (B1)") was blended with 100 parts by mass of the hot-melt urethane prepolymer, to obtain a moisture-curable polyurethane hot-melt resin composition (1).
Example 2
Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 74 parts by mass of PEt-1, 31 parts by mass of PEs-1, and 18 parts by mass of PEs-2 were added and mixed, and the mixture was heated under reduced pressure at 100 ℃. Next, the flask was cooled to 90 ℃, 27 parts by mass of MDI which had been 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. 25 parts by mass of a flame retardant (B1) was blended with 100 parts by mass of the hot-melt urethane prepolymer to obtain a moisture-curable polyurethane hot-melt resin composition (2).
Example 3
48 Parts by mass of polypropylene glycol (number average molecular weight: 2,000, hereinafter abbreviated as "PEt-2") and 17 parts by mass of PEs-1, and 22 parts by mass of polyester polyol (obtained by reacting ethylene glycol, neopentyl glycol, 1, 6-hexanediol and adipic acid) 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 flask until the water content in the flask became 0.05% by mass or less. Next, the flask was cooled to 90℃and 18 parts by mass of MDI, which had been melted at 70℃was added thereto, and reacted at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. 35 parts by mass of a flame retardant (B1) was blended with 100 parts by mass of the hot-melt urethane prepolymer to obtain a moisture-curable polyurethane hot-melt resin composition (3).
Example 4
133 Parts by mass of PEt-1, 56 parts by mass of PEs-1 and 33 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 49 parts by mass of MDI, which had been melted at 70℃was added thereto, and reacted at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. 30 parts by mass of a flame retardant (B1) was blended with 100 parts by mass of the hot-melt urethane prepolymer to obtain a moisture-curable polyurethane hot-melt resin composition (4).
Example 5
139 Parts by mass of PEt-2, 32 parts by mass of PEs-1 and 43 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 47 parts by mass of MDI, which had been melted at 70℃was added thereto, and reacted at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. 35 parts by mass of a flame retardant (B1) was blended with 100 parts by mass of the hot-melt urethane prepolymer to obtain a moisture-curable polyurethane hot-melt resin composition (5).
Example 6
83 Parts by mass of PEt-1, 19 parts by mass of PEs-1 and 26 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 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 26 parts by mass of MDI melted at 70℃was added thereto, and reacted 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 40 parts by mass of the flame retardant (B1) with 100 parts by mass of the hot-melt urethane prepolymer.
Example 7
121 Parts by mass of PEt-1, 121 parts by mass of PEt-2, 81 parts by mass of PEs-1 and 81 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 87 parts by mass of MDI which had been melted at 70℃was added thereto, and reacted at 110℃for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot-melt urethane prepolymer. 30 parts by mass of a flame retardant (B1) was blended with 100 parts by mass of the hot-melt urethane prepolymer to obtain a moisture-curable polyurethane hot-melt resin composition (7).
Example 8
A moisture-curable polyurethane hot-melt resin composition (8) was obtained in the same manner as in example 1 except that the type of PEt-1 was changed to biomass polytetramethylene glycol (Mitsubishi Chemical, co., ltd. "Bio PTMG", number average molecular weight: 2,000).
Comparative example 1
92 Parts by mass of PEt-1, 33 parts by mass of PEs-1 and 25 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 ℃, 33 parts by mass of MDI which had been 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. 10 parts by mass of a flame retardant (B1) was blended with 100 parts by mass of the hot-melt urethane prepolymer to obtain a moisture-curable polyurethane hot-melt resin composition (R1).
Comparative example 2
109 Parts by mass of PEt-2, 45 parts by mass of PEs-1 and 27 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 ℃, 40 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 (R2).
Comparative example 3
111 Parts by mass of PEt-1, 77 parts by mass of PEs-1 and 66 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 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 50 parts by mass of MDI, which had been melted at 70℃was added thereto, and reacted 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 (R3) was obtained by blending 65 parts by mass of the flame retardant (B1) with 100 parts by mass of the hot-melt urethane prepolymer.
Comparative example 4
27 Parts by mass of PEt-1, 41 parts by mass of PEs-1 and 23 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 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 18 parts by mass of MDI, which had been melted at 70℃was added thereto, and reacted 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 40 parts by mass of the flame retardant (B1) 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 a value obtained by measurement by gel permeation column chromatography (GPC) under the following conditions.
Measurement device high-speed GPC apparatus (HLC-8220 GPC, manufactured by Tosoh Co., ltd.)
The column was used by connecting the following columns in series.
"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
Detector RI (differential refractometer)
Column temperature of 40 DEG C
Tetrahydrofuran (THF)
Flow Rate 1.0 mL/min
Injection amount 100. Mu.L (tetrahydrofuran solution with sample concentration of 0.4% by mass)
Standard samples a calibration curve was prepared using the following standard polystyrene.
(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 ]
The moisture-curable polyurethane hot melt resin compositions obtained in examples and comparative examples were intermittently applied to a polyvinyl chloride sheet using a gravure coater in a constant temperature and humidity chamber adjusted to a temperature of 23 ℃ and a humidity of 50±5% so as to be 40±5g/m 2, and bonded to a polyester-based cloth, and the resultant was cured at a temperature of 23 ℃ and a humidity of 50±5% for 24 hours, thereby obtaining synthetic leather.
[ Method of evaluating adhesion ]
For each of the obtained synthetic leathers, peel strength was measured using Tensilon (Tensilon Universal tester "RTC-1210A" manufactured by ORIENTEC Co., ltd.) under the condition of a crosshead measurement speed of 200 mm/min, and a value of 6N/cm or more was evaluated as "O", and a value of less than 6N/cm was evaluated as "X".
[ Method of evaluating Low-temperature bendability ]
The obtained synthetic leathers were subjected to a bending test (-10 ℃ C., 100 times/min) using a deflectometer, and the number of times until cracks were generated on the surface of the synthetic leathers was measured, and 20,000 or more times were evaluated as "O", and less than 20,000 times were evaluated as "X".
[ Method of evaluating flame retardancy ]
The moisture-curable polyurethane hot-melt resin compositions obtained in examples and comparative examples were applied by a roll coater so that the thickness became 300 μm, and then cured at a temperature of 23 ℃ and a humidity of 50±5% for 72 hours or more, to prepare a film. Next, the obtained film was cut into a rectangular shape having a width of 102mm and a length of 356mm, and a flammability test (FMVSS 302) was performed. Test pieces that did not catch fire or self-extinguished before reaching the A mark, test pieces that self-extinguished within a burning distance of 51mm (and within 60 seconds), test pieces with a burning rate of 102 mm/min or less were evaluated as "O", and other test pieces were evaluated as "X".
TABLE 1
TABLE 2
TABLE 3
Examples 1 to 8, which are moisture-curable polyurethane hot-melt resin compositions of the present invention, are excellent in adhesion, low-temperature flexibility and flame retardancy.
On the other hand, comparative example 1 was a case where the content of the flame retardant (B) was lower than the range defined in the present invention, and the flame retardancy was poor.
Comparative example 2 was a case where the flame retardant (B) was not used, and the flame retardancy was poor.
Comparative examples 3 and 4 are defects such as low-temperature bendability in such a manner that the amount of the polyether polyol (a 1) used is less than the range defined in the present invention.
Claims (4)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2022-166839 | 2022-10-18 | ||
| JP2022166839 | 2022-10-18 | ||
| PCT/JP2023/019460 WO2024084729A1 (en) | 2022-10-18 | 2023-05-25 | Moisture-curable polyurethane hot melt resin composition, adhesive, and synthetic leather |
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| JP (1) | JPWO2024084729A1 (en) |
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| JP2003049147A (en) * | 2001-08-08 | 2003-02-21 | Dainippon Ink & Chem Inc | Solvent-free moisture-curable hot melt urethane resin adhesive for synthetic leather and synthetic leather component using the same |
| JP5142309B2 (en) * | 2003-12-25 | 2013-02-13 | Ｄｉｃ株式会社 | Moisture curable polyurethane hot melt resin composition |
| CN104099055B (en) * | 2013-04-07 | 2016-02-17 | 广东国望精细化学品有限公司 | A kind of halogen-free anti-inflaming polyurethane seal gum and preparation method |
| JP7196435B2 (en) * | 2018-06-28 | 2022-12-27 | Dic株式会社 | Moisture-curable polyurethane hot-melt resin composition |
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