CN119998350A - Moisture curing polyurethane hot melt resin composition, cured product, laminate and skin material - Google Patents
Moisture curing polyurethane hot melt resin composition, cured product, laminate and skin material Download PDFInfo
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- CN119998350A CN119998350A CN202380070821.XA CN202380070821A CN119998350A CN 119998350 A CN119998350 A CN 119998350A CN 202380070821 A CN202380070821 A CN 202380070821A CN 119998350 A CN119998350 A CN 119998350A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
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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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Laminated Bodies (AREA)
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，含有作为多元醇（A）与多异氰酸酯（B）的反应产物的具有异氰酸酯基的氨基甲酸酯预聚物（i），上述多元醇（A）含有：以分子量小于500、具有支链结构、并且在1分子中具有2～4个羟基的化合物（x）作为原料的芳香族聚酯多元醇（a1）；除了上述（a1）以外的芳香族聚酯多元醇（a2）；脂肪族聚酯多元醇（a3）；除了上述（a3）以外的结晶性聚酯多元醇（a4）；以及聚醚多元醇（a5）。另外，本发明提供以下的固化物，其特征在于，其是由上述湿固化型聚氨酯热熔树脂组合物形成的。The present invention provides the following moisture-curable polyurethane hot-melt resin composition, characterized in that it contains a urethane prepolymer (i) having an isocyanate group as a reaction product of a polyol (A) and a polyisocyanate (B), wherein the polyol (A) contains: an aromatic polyester polyol (a1) made of a compound (x) having a molecular weight of less than 500, a branched structure, and 2 to 4 hydroxyl groups in one molecule; an aromatic polyester polyol (a2) other than the above (a1); an aliphatic polyester polyol (a3); a crystalline polyester polyol (a4) other than the above (a3); and a polyether polyol (a5). In addition, the present invention provides the following cured product, characterized in that it is formed from the above moisture-curable polyurethane hot-melt resin composition.
Description
Technical Field
The present invention relates to a moisture-curable polyurethane hot-melt resin composition, a cured product, a laminate, and a skin material.
Background
Laminates such as synthetic leather and artificial leather are used for the surface of furniture and vehicle sheets, and a buffer layer such as urethane foam (PUF) is generally provided for the purpose of exhibiting vibration damping properties (for example, see patent literature 1). Conventionally, in bonding a synthetic leather to a PUF/PUF and a mesh cloth for imparting slip at the time of sewing, the PUF is flame-melted by flame fusion (flame fusion) to bond the PUF to a surface/back substrate of the synthetic leather or the like.
However, in the bonding by the flame fusion lamination method, since flame is used, hydrogen Cyanide (HCN) is generated at the time of production, and deterioration of the working environment becomes a problem. Instead, an aqueous adhesive or a solvent adhesive is used, but since a drying step is required, there is a concern that the productivity is lowered, and it is considered that the adhesive oozes out to the back surface of the base fabric (penetration of the adhesive) when the drying is insufficient, and blocking occurs at the time of winding.
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2017-136735
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 initial strength, mechanical strength and adhesiveness and can inhibit penetration.
Means for solving the problems
The present invention provides a moisture-curable polyurethane hot-melt resin composition comprising an isocyanate group-containing urethane prepolymer (i) which is a reaction product of a polyol (A) and a polyisocyanate (B), wherein the polyol (A) comprises an aromatic polyester polyol (a 1) which is a compound (x) having a branched structure and having 2 to 4 hydroxyl groups in1 molecule and having a molecular weight of less than 500, an aromatic polyester polyol (a 2) other than the above (a 1), an aliphatic polyester polyol (a 3), a crystalline polyester polyol (a 4) other than the above (a 3), and a polyether polyol (a 5).
The present invention also provides a cured product comprising the moisture-curable polyurethane hot-melt resin composition. The present invention also provides a laminate and a skin material characterized by comprising a polyurethane foam, a layer formed from the cured product, and a base fabric.
Effects of the invention
The moisture-curable polyurethane hot-melt resin composition of the present invention is excellent in initial strength, mechanical strength and adhesion, and can suppress penetration. Further, by using the moisture-curable polyurethane hot-melt resin composition, flame lamination which has been conventionally performed is not required, and thus improvement of the working environment can be facilitated.
Detailed Description
The moisture-curable polyurethane hot-melt resin composition of the present invention comprises a urethane prepolymer (i) having isocyanate groups, which is a reaction product of a polyol (A) and a polyisocyanate (B), wherein the polyol (A) comprises an aromatic polyester polyol (a 1) starting from a compound (x) having a branched structure and having 2 to 4 hydroxyl groups in 1 molecule and having a molecular weight of less than 500, an aromatic polyester polyol (a 2) other than the above (a 1), an aliphatic polyester polyol (a 3), a crystalline polyester polyol (a 4) other than the above (a 3), and a polyether polyol (a 5).
The urethane prepolymer (i) is a reaction product of a specific polyol (a) and a polyisocyanate (B).
The polyol (A) contains the components (a 1) to (a 5) as essential components.
In order to exhibit excellent initial strength and suppress penetration, the aromatic polyester polyol (a 1) must be prepared from a compound (x) having a molecular weight of less than 500, a branched structure, and 2 to 4 hydroxyl groups in 1 molecule. The molecular weight of the compound (x) represents a value calculated from the chemical formula.
Examples of the compound (x) include 2-methyl-1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 2-butanediol, 1, 3-butanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 2-propanediol, 2-methyl-1, 3-propanediol, 2-ethyl-1, 3-hexanediol, neopentyl glycol, 2-isopropyl-1, 4-butanediol, 2, 4-dimethyl-1, 5-pentanediol, 2-ethyl-1, 6-hexanediol, 3, 5-heptanediol, 2-methyl-1, 8-octanediol, and trimethylolpropane. These compounds may be used alone or in combination of 2 or more. Among these, neopentyl glycol is preferable in terms of obtaining a more excellent penetration-inhibiting effect.
The amount of the compound (x) used is preferably in the range of 0.1 to 30 mass%, more preferably in the range of 0.2 to 20 mass%, and even more preferably in the range of 0.3 to 15 mass% based on the total mass of the polyol (a) and the polyisocyanate (B), from the viewpoint of maintaining an excellent penetration-inhibiting effect, having a moderate viscosity, and obtaining a good cured film.
The aromatic polyester polyol (a 1) is specifically a reaction product of a compound having 2 or more hydroxyl groups containing the compound (x) and a polybasic acid.
Examples of the compounds having at least 2 hydroxyl groups other than the above-mentioned compound (x) include aliphatic compounds such as ethylene glycol, 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 and tetraethylene glycol, alicyclic compounds such as cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A and alkylene oxide adducts thereof, and aromatic compounds such as bisphenol A, bisphenol F and alkylene oxide (ethylene oxide, propylene oxide, butylene oxide and the like) adducts thereof. These compounds may be used alone or in combination of 2 or more. Among these, aliphatic compounds are preferable, and diethylene glycol is more preferable, from the viewpoint of obtaining more excellent penetration-inhibiting effect and flexibility.
Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride. Examples of the other polybasic acids include aromatic polybasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, 1, 12-dodecanedicarboxylic acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, citraconic acid, itaconic acid, citraconic anhydride, and itaconic anhydride. These polybasic acids may be used alone or in combination of 2 or more. Among these, aromatic polybasic acids are preferable, and phthalic acid (1 or more compounds selected from phthalic acid, isophthalic acid, terephthalic acid and phthalic anhydride) is more preferable from the viewpoint of obtaining more excellent penetration-inhibiting effect, adhesion, reactivity and flexibility.
The number average molecular weight of the aromatic polyester polyol (a 1) is preferably 700 to 10,000, more preferably 800 to 5,000, from the viewpoint of obtaining more excellent penetration-inhibiting effect and flexibility. The number average molecular weight of the aromatic polyester polyol (a 1) is a value measured by a Gel Permeation Chromatography (GPC) method.
The content of the aromatic polyester polyol (a 1) is preferably 10 to 40% by mass, more preferably 15 to 30% by mass, in the polyol (a) in view of obtaining more excellent penetration-inhibiting effect and flexibility.
The aromatic polyester polyol (a 2) is a material other than the aromatic polyester polyol (a 1) (not based on the compound (x)) and is used for prolonging the bonding time and obtaining excellent handleability.
As the raw material of the aromatic polyester polyol (a 2), the compound having 2 or more hydroxyl groups and the polybasic acid which can be used as the raw material of the aromatic polyester polyol (a 1) are used, and the aliphatic compound is preferable in the case of the compound having 2 or more hydroxyl groups, and the phthalic acid is preferable in the case of the polybasic acid.
The number average molecular weight of the aromatic polyester polyol (a 2) is more preferably 700 to 10,000, and still more preferably 800 to 5,000. The number average molecular weight of the aromatic polyester polyol (a 1) is a value measured by a Gel Permeation Chromatography (GPC) method.
The content of the aromatic polyester polyol (a 2) is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, based on the polyol (a).
The aliphatic polyester polyol (a 3) is used for adjusting the curing time, and may be a reaction product of an aliphatic compound having at least 2 hydroxyl groups and an aliphatic polybasic acid.
Examples of the aliphatic compound having at least 2 hydroxyl groups include the above-mentioned compound (x), and aliphatic compounds such as ethylene glycol, 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, and tetraethylene glycol. These compounds may be used alone or in combination of 2 or more. Among these, the above-mentioned compound (x) is preferably used in combination with the above-mentioned aliphatic compound.
Examples of the aliphatic polybasic acid include succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, citraconic acid, itaconic acid, citraconic anhydride, and itaconic anhydride. These polybasic acids may be used alone or in combination of 2 or more.
The number average molecular weight of the aliphatic polyester polyol (a 3) is more preferably 700 to 50,000, and still more preferably 800 to 7,000. The number average molecular weight of the aromatic polyester polyol (a 1) is a value measured by a Gel Permeation Chromatography (GPC) method.
The content of the aliphatic polyester polyol (a 3) is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, based on the polyol (a).
The crystalline polyester polyol (a 4) is used to obtain excellent adhesiveness, and is other than the aliphatic polyester polyol (a 3), and for example, a reaction product of a compound having a hydroxyl group and a polybasic acid can be used. In the present invention, "crystallinity" means that a peak of crystallization heat or melting heat can be confirmed in a DSC (differential scanning calorimeter) measurement according to JISK 7121:2012.
Examples of the compound having a hydroxyl group include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, trimethylol propane, trimethylol ethane, and glycerin. These compounds may be used alone or in combination of 2 or more. Among these, 1 or more selected from butanediol, hexanediol, octanediol and decanediol is preferably used in order to improve crystallinity and obtain more excellent adhesion.
Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, and the like. These compounds may be used alone or in combination of 2 or more.
The number average molecular weight of the crystalline polyester polyol (a 4) is preferably 600 to 50,000, more preferably 1,000 to 10,000, from the viewpoint of obtaining more excellent adhesion. The number average molecular weight of the crystalline polyester polyol (a 4) is a value measured by Gel Permeation Chromatography (GPC).
The content of the crystalline polyester polyol (a 4) is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, based on the polyol (a).
The polyether polyol (a 5) is used for adjustment of low viscosity and bonding time, and for example, polyalkylene glycol such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, derivatives of the polyalkylene glycol (for example, derivatives of alkyl-substituted tetrahydrofuran and derivatives of neopentyl glycol) and the like can be used. These polyether polyols may be used alone or in combination of 2 or more. Among these, polypropylene glycol and/or polytetramethylene glycol are preferable.
The number average molecular weight of the polyether polyol (a 5) is preferably 300 to 10,000, more preferably 350 to 4,000. The number average molecular weight of the polyether polyol (a 5) is a value measured by Gel Permeation Chromatography (GPC).
The content of the polyether polyol (a 5) is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, based on the polyol (a).
The polyol (A) contains the components (a 1) to (a 5) as essential components, but other polyols may be used in combination as required.
Examples of the other polyols include polyester polyols, acrylic polyols, polycarbonate polyols, polybutadiene polyols, and the like other than the above (a 1) to (a 4). These polyols may be used alone or in combination of 2 or more.
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, and aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate. These polyisocyanates may be used alone or in combination of 2 or more. Among these, aromatic polyisocyanates are preferable, and diphenylmethane diisocyanate is more preferable, from the viewpoint of mechanical strength.
The method for producing the urethane prepolymer (i) can be carried out, for example, by dropping a mixture of the polyol (A) into a reaction vessel in which the polyisocyanate (B) is placed, heating the mixture, and reacting the mixture under a condition that the isocyanate groups of the polyisocyanate (B) are excessive relative to the hydroxyl groups of the polyol (A).
In the production of the urethane prepolymer (i), the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group of the polyisocyanate (B) to the hydroxyl group of the polyol (a) is preferably 1.5 to 5, more preferably 1.6 to 2.5.
The isocyanate group content (hereinafter abbreviated as "NCO%") of the urethane prepolymer (i) is preferably 1.0 to 5.0 mass%, more preferably 2.3 to 4.8 mass%. The NCO% of the urethane prepolymer (i) was a value obtained by a potentiometric titration method in accordance with JISK 1603-1:2007.
The moisture-curable polyurethane hot-melt resin composition of the present invention contains the urethane prepolymer (i) as an essential component, but may contain other additives as required.
As the other additives, for example, curing catalysts, antioxidants, tackifiers, plasticizers, stabilizers, flame retardants, fillers, dyes, pigments, optical brighteners, silane coupling agents, waxes, thermoplastic resins, and the like can be used. These additives may be used alone or in combination of 2 or more.
The laminate of the present invention comprises a polyurethane foam, a cured layer of the moisture-curable polyurethane hot-melt resin composition, and a base fabric.
The polyurethane foam imparts cushioning properties, vibration damping properties, air permeability, and the like, and a known polyurethane foam can be used. The thickness of the polyurethane foam may be, for example, 1.5 to 20 mm.
The base fabric is one which is bonded to the polyurethane foam and has improved workability by imparting slidability when it is provided in a molded article such as an automobile seat, and examples thereof 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. In the present invention, the use of the moisture-curable polyurethane hot-melt resin composition can provide an excellent penetration-inhibiting effect even when a base fabric of a mesh fabric is used.
Examples of the method for producing the laminate include a method of coating the moisture-curable polyurethane hot-melt resin composition on the polyurethane foam. Examples of the method for coating the moisture-curable polyurethane hot-melt resin composition include a method using a coater such as a gravure coater, a roll coater, a spray coater, a T-die coater, a doctor blade coater, or a comma coater, a precision method such as a dispenser, ink jet printing, screen printing, or offset printing, a nozzle coating method, a spray coating method, or a film lamination method. Among these, intermittent coating is preferable in view of obtaining more excellent mechanical strength, adhesive strength and penetration-inhibiting effect. The moisture-curable polyurethane hot-melt resin composition may be melted at 70 to 120 ℃ before the coating.
The coating amount of the moisture-curable polyurethane hot-melt resin composition is, for example, 5 to 35g/m 2.
After the moisture-curable polyurethane hot-melt resin composition is applied, cooling may be performed in order to accelerate the curing speed of the moisture-curable polyurethane hot-melt resin composition.
After the moisture-curable polyurethane hot-melt resin composition is cured, a release paper or a carrier sheet may be placed on the cured product. When used as a skin material, it is preferably peeled off.
The thickness of the cured product of the moisture-curable polyurethane hot-melt resin composition may be, for example, in the range of 5 to 200. Mu.m.
The laminate of the present invention is particularly suitable for use as a skin material because of the above-described effects. Examples of the structure of the skin material include a structure in which the base fabric, the cured product layer of the moisture-curable polyurethane hot-melt resin composition, the polyurethane foam, and the skin layer are laminated.
A base fabric may be further provided between the polyurethane foam and the skin layer as needed, and these may be bonded using a known adhesive. As the above known adhesive, for example, an acrylic adhesive, a urethane adhesive, a moisture-curable polyurethane hot-melt adhesive, or the like can be used.
The skin layer may be formed of a known material, and for example, solvent-based polyurethane, aqueous polyurethane, polyvinyl chloride, thermoplastic urethane (TPU), thermoplastic Polyolefin (TPO), thermoplastic Polyester (TPE), or the like may be used.
The skin material may cover, for example, a seat of a vehicle.
Examples
Hereinafter, the present invention will be described in more detail using examples.
EXAMPLE 1 preparation of moisture-curable polyurethane Hot melt resin composition (1)
Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, a reaction product of an aromatic polyester polyol (neopentyl glycol, diethylene glycol, and phthalic anhydride, the number average molecular weight: 1,000, hereinafter abbreviated as "aromatic PEs (a 1-1)") was charged with 35 parts by mass, a reaction product of an aromatic polyester polyol (hexanediol and phthalic anhydride, the number average molecular weight: 2,000, hereinafter abbreviated as "aromatic PEs (a 2-1)") 15 parts by mass, a reaction product of an aliphatic polyester polyol (ethylene glycol, neopentyl glycol, hexanediol, and adipic acid, the number average molecular weight: 5,500, hereinafter abbreviated as "aliphatic PEs (a 3-1)") 10 parts by mass, a reaction product of a crystalline polyester polyol (1, 6-hexanediol, and adipic acid, the number average molecular weight: 8,000, hereinafter abbreviated as "crystalline PEs (a 4-1)") 15 parts by mass, and a polyether polyol (polypropylene glycol, hereinafter abbreviated as "aromatic PEs (a 2-1)") were charged with water, and the mixture was heated until the mixture was dehydrated at a temperature of 0% by mass and a temperature of 0% to 0% or lower than the flask. Next, the flask was cooled to 90 ℃, 22 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 ℃ for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, thereby obtaining a hot-melt urethane prepolymer (i-1) having an NCO% of 2.5% by mass, and a moisture-curable polyurethane hot-melt resin composition (1) was produced.
EXAMPLE 2 preparation of moisture-curable polyurethane Hot melt resin composition (2)
Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 25 parts by mass of aromatic PEs (a 1-1), 10 parts by mass of aromatic PEs (a 2-1), 10 parts by mass of aliphatic PEs (a 3-1), 10 parts by mass of crystalline PEs (a 4-1), 10 parts by mass of PEt (a 5-1), and 15 parts by mass of polyether polyol (polypropylene glycol, number average molecular weight: 400, hereinafter abbreviated as "PEt (a 5-2)") were added, and the mixture was mixed and heated under reduced pressure at 70 ℃. 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 ℃ for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, thereby obtaining a hot-melt urethane prepolymer (i-2) having an NCO% of 4.0 mass%, and a moisture-curable polyurethane hot-melt resin composition (2) was produced.
EXAMPLE 3 preparation of moisture-curable polyurethane Hot melt resin composition (3)
Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 35 parts by mass of aromatic PEs (a 1-1), 15 parts by mass of aromatic PEs (a 2-1), 10 parts by mass of aliphatic PEs (a 3-1), 15 parts by mass of crystalline PEs (a 4-1), and 15 parts by mass of polyether polyol (polytetramethylene glycol, number average molecular weight: 2,000, hereinafter abbreviated as "PEt (a 5-3)") were added, followed by mixing and heating under reduced pressure at 70 ℃. Next, the flask was cooled to 90 ℃, 22 parts by mass of MDI which had been 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, thereby obtaining a hot-melt urethane prepolymer (i-3) having an NCO% of 2.5 mass%, and a moisture-curable polyurethane hot-melt resin composition (3) was produced.
EXAMPLE 4 preparation of moisture-curable polyurethane Hot melt resin composition (4)
15 Parts by mass of aromatic PEs (a 1-1), 35 parts by mass of aromatic PEs (a 2-1), 10 parts by mass of aliphatic PEs (a 3-1), 15 parts by mass of crystalline PEs (a 4-1) and 15 parts by mass of PEt (a 5-1) are put into 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 70 ℃ to dehydrate until the water content in the flask becomes 0.05 mass% or less. Next, the flask was cooled to 90℃and 25 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, thereby obtaining a hot-melt urethane prepolymer (i-4) having an NCO% of 4.0% by mass, and a moisture-curable polyurethane hot-melt resin composition (4) was produced.
EXAMPLE 5 preparation of moisture-curable polyurethane Hot melt resin composition (5)
35 Parts by mass of aromatic PEs (a 1-1), 15 parts by mass of aromatic PEs (a 2-1), 10 parts by mass of aliphatic polyester polyol (a reaction product of neopentyl glycol, diethylene glycol, hexanediol and adipic acid, number average molecular weight: 2,000, hereinafter abbreviated as "aliphatic PEs (a 3-2)"), 15 parts by mass of crystalline PEs (a 4-1) and 15 parts by mass of PEt (a 5-1) 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 70℃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 22 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, thereby obtaining a hot-melt urethane prepolymer (i-5) having an NCO% of 2.3% by mass, and a moisture-curable polyurethane hot-melt resin composition (5) was produced.
EXAMPLE 6 preparation of moisture-curable polyurethane Hot melt resin composition (6)
To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 20 parts by mass of aromatic PEs (a 1-1), 10 parts by mass of aromatic PEs (a 2-1), 10 parts by mass of aliphatic PEs (a 3-1), 10 parts by mass of crystalline PEs (a 4-1), and 40 parts by mass of PEt (a 5-1) were added, followed by mixing and heating under reduced pressure at 70 ℃. Next, the flask was cooled to 90℃and 26 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, thereby obtaining a hot-melt urethane prepolymer (i-6) having an NCO% of 4.0% by mass, and a moisture-curable polyurethane hot-melt resin composition (6) was produced.
EXAMPLE 7 preparation of moisture-curable polyurethane Hot melt resin composition (7)
35 Parts by mass of aromatic PEs (a 1-1), a reaction product of aromatic polyester polyol (ethylene glycol, adipic acid, phthalic anhydride and terephthalic acid, and a number average molecular weight: 2,000, hereinafter abbreviated as "aromatic PEs (a 2-2)") 15 parts by mass, 10 parts by mass of aliphatic PEs (a 3-1), 10 parts by mass of crystalline PEs (a 4-1) and 15 parts by mass of PEt (a 5-1) were charged into 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 70℃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 27 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, thereby obtaining a hot-melt urethane prepolymer (i-7) having an NCO% of 4.0% by mass, and a moisture-curable polyurethane hot-melt resin composition (7) was produced.
Comparative example 1 preparation of moisture-curable polyurethane Hot melt resin composition (R1)
Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 15 parts by mass of an aromatic polyester polyol (a reaction product of neopentyl glycol and phthalic anhydride, having a number average molecular weight of 1,000, hereinafter abbreviated as "aromatic PEs (a 1-2)"), 35 parts by mass of a crystalline polyester polyol (a reaction product of hexanediol and sebacic acid, having a number average molecular weight of 4,000, hereinafter abbreviated as "crystalline PEs (a 4-2)") and 50 parts by mass of PEt (a 5-1) were charged, and the mixture was mixed and heated under reduced pressure at 70 ℃. Next, the flask was cooled to 90 ℃, 24 parts by mass of MDI which had been melted at 70 ℃ was added, and reacted at 110 ℃ for about 3 hours under a nitrogen atmosphere until the isocyanate group content reached a constant, thereby obtaining a hot-melt urethane prepolymer (iR-1) having an nco% of 3.2 mass%, and a moisture-curable polyurethane hot-melt resin composition (R1) was produced.
Comparative example 2 preparation of moisture-curable polyurethane Hot melt resin composition (R2)
A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 20 parts by mass of crystalline PEs (a 4-2) and 80 parts by mass of PEt (a 5-1), and the mixture was mixed and heated under reduced pressure at 70 ℃. Next, the flask was cooled to 90 ℃, 18 parts by mass of MDI which had been 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, thereby obtaining a hot-melt urethane prepolymer (iR-2) having an nco% of 1.9 mass%, and a moisture-curable polyurethane hot-melt resin composition (R2) was produced.
[ Method for measuring number average molecular weight ]
The number average molecular weight of the polyol used in the synthesis examples and comparative synthesis examples represents values 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 of evaluating mechanical Strength ]
The moisture-curable polyurethane hot-melt resin compositions obtained in examples and comparative examples, which had been melted at 110℃for 1 hour, were applied to a 100 μm-thick release PET using a 50 μm applicator on a hot plate set at 110℃and left at an ambient temperature of 23℃and an ambient humidity of 50% for 3 days, to obtain films. The obtained film was cut into a long strip having a width of 5mm and a length of 50mm, and the film was stretched at a temperature of 23℃under an atmosphere of a crosshead speed of 300 mm/sec using a tensile tester "Autograph AG-I" (manufactured by Shimadzu corporation), whereby 100% modulus (MPa) of the test piece was measured. The distance between chucks at this time was set to 40mm.
[ Evaluation method of initial Strength ]
The moisture curable polyurethane hot melt resin compositions obtained in examples and comparative examples were applied to a corona-treated PET having a thickness of 100 μm using a 100 μm applicator on a hot plate having a temperature of 110 ℃ in a constant temperature and humidity chamber having a temperature of 23 ℃ and a humidity of 50±5%, and after being bonded to the corona-treated PET by a rubber roll, the PET was cut at a predetermined time and a width of 1 inch, and the tensile strength was measured by a tensile tester "Autograph AG-I" (manufactured by shimadzu corporation, h·s=200 mm/min).
[ Evaluation method of adhesion and penetration inhibition ]
The moisture curable polyurethane hot melt resin compositions obtained in examples and comparative examples were intermittently applied to polyurethane foam using a gravure coater so as to be 20.+ -.5 g/m 2, and then bonded to a back side base fabric nylon net, and cured at an ambient temperature of 23 ℃ and an ambient humidity of 50% for 24 hours under a load of 2kg/A4 size, and then the adhesiveness was measured by a tensile tester "Autograph AG-I" (manufactured by Shimadzu corporation, H.S=200 mm/min). The penetration of the laminate into the back base web was visually confirmed. The moisture-curable polyurethane hot-melt resin composition was evaluated as "good" when no penetration was observed, and "x" when no penetration was observed. Incidentally, "PUF" in the table means polyurethane foam.
The moisture-curable polyurethane hot-melt resin composition of the present invention is excellent in mechanical strength, initial strength and adhesion, and can suppress penetration.
On the other hand, comparative example 1 was a system in which the aromatic polyester polyol (a 2) and the aliphatic polyester polyol (a 3) were not used, and the initial strength was low and penetration was found.
On the other hand, in comparative example 2, the initial strength was lower than that of comparative example 1, and penetration was found in a case where the aromatic polyester polyols (a 1), (a 2) and the aliphatic polyester polyol (a 3) were not used.
Claims (9)
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| JP2022-166840 | 2022-10-18 | ||
| JP2022166840 | 2022-10-18 | ||
| PCT/JP2023/019461 WO2024084730A1 (en) | 2022-10-18 | 2023-05-25 | Moisture-curable polyurethane hot-melt resin composition, cured product, laminate, and skin material |
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| CN119998350A true CN119998350A (en) | 2025-05-13 |
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| FR2772778B1 (en) * | 1997-12-19 | 2002-03-29 | Ato Findley Sa | MOISTURE CROSS-LINKABLE POLYURETHANE ADHESIVE, PROCESS FOR ADHESIVING A TEXTILE AND A CELLULAR MATERIAL USING SAID ADHESIVE AND ADHESIVE ASSEMBLY THUS OBTAINED |
| DE102004028488A1 (en) * | 2004-02-20 | 2005-09-08 | Degussa Ag | Moisture-cured hot melt adhesive for immediate processing of bonded substrates, contains reaction product of polyisocyanate with hydroxy-polyester based on linear aliphatic dicarboxylic acid with 13-22 methylene groups |
| DE102007033651A1 (en) * | 2007-07-17 | 2009-01-22 | Evonik Degussa Gmbh | Moisture-curing hotmelt adhesive with good adhesion |
| JP5770551B2 (en) * | 2011-07-22 | 2015-08-26 | 矢崎総業株式会社 | Service plug mounting structure |
| JP5360516B1 (en) * | 2012-04-12 | 2013-12-04 | Ｄｉｃ株式会社 | Moisture curable polyurethane hot melt resin composition, adhesive and article |
| JP6344877B1 (en) * | 2017-10-26 | 2018-06-20 | 太陽精機株式会社 | Moisture curable polyurethane hot melt adhesive and method for producing the same |
| TWI894158B (en) * | 2019-08-08 | 2025-08-21 | 日商Ｄｉｃ股份有限公司 | Moisture-curing polyurethane hot-melt resin composition |
| CA3165506A1 (en) * | 2020-02-28 | 2021-09-02 | Marietta B. Helmeke | Heat resistant hot melt moisture cure adhesive composition and articles including the same |
| JP7516816B2 (en) * | 2020-03-31 | 2024-07-17 | 株式会社レゾナック | Reactive hot melt adhesive, adhesive body and manufacturing method thereof, and clothing |
| CN116635501A (en) * | 2020-12-21 | 2023-08-22 | 汉高股份有限及两合公司 | Oil resistant adhesive composition |
| CN112552859B (en) * | 2020-12-29 | 2022-07-15 | 烟台信友新材料有限公司 | A kind of high initial viscosity low shrinkage high strength polyurethane hot melt adhesive and preparation method thereof |
| CN113046014A (en) * | 2021-03-22 | 2021-06-29 | 杭州之江新材料有限公司 | Low-viscosity high-initial-viscosity polyurethane hot melt adhesive and preparation method thereof |
| CN114015402A (en) * | 2021-11-25 | 2022-02-08 | 万华生态科技有限公司 | High-temperature reaction type hot melt adhesive composition for PVC edge sealing and preparation method thereof |
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