CN111741992B - Moisture-curable polyurethane hot-melt resin composition - Google Patents
Moisture-curable polyurethane hot-melt resin composition Download PDFInfo
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- CN111741992B CN111741992B CN201980014195.6A CN201980014195A CN111741992B CN 111741992 B CN111741992 B CN 111741992B CN 201980014195 A CN201980014195 A CN 201980014195A CN 111741992 B CN111741992 B CN 111741992B
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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
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Abstract
The present invention addresses the problem of providing a moisture-curable polyurethane hot-melt resin composition that has excellent initial adhesion strength and can form a cured coating film having excellent flexibility. The present invention provides a moisture-curable polyurethane hot-melt resin composition, characterized in that the storage elastic modulus (G ') of the melt viscoelasticity at 20 ℃ before curing is 0.1MPa or more, and the Young's modulus of the cured coating film is 20MPa or less. The moisture-curable polyurethane hot-melt resin composition preferably contains an isocyanate group-containing urethane prepolymer (i) prepared from a polyol (a) and a polyisocyanate (B), and the amount of the crystalline polyester polyol is less than 10% by mass of the total mass of the polyol (a) and the polyisocyanate (B).
Description
Technical Field
The present invention relates to a moisture-curable polyurethane hot-melt resin composition.
Background
Since moisture-curable polyurethane hot-melt adhesives are solvent-free, various studies have been made up to now as environmentally compatible adhesives, mainly for fiber bonding and building material lamination, and they are also widely used in the industrial field.
The moisture-curable polyurethane adhesive exhibits final adhesive strength by moisture curing of an isocyanate group of a urethane prepolymer as a main component thereof, but in bonding to various substrates, high initial adhesive strength is also required immediately after application of the adhesive.
In order to obtain high initial adhesion strength, it is common to use a large amount of crystalline polyesterpolyol (for example, see patent document 1). However, since the cured coating film is hardened by such a method, it is not used in the field where flexibility is required, for example, in fiber applications, because of deterioration of the hand feeling.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-190309
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a moisture-curable polyurethane hot-melt resin composition that has excellent initial adhesion strength and is capable of forming a cured coating film having excellent flexibility.
Means for solving the problems
The present invention provides a moisture-curable polyurethane hot-melt resin composition, characterized in that the storage elastic modulus (G ') of the melt viscoelasticity at 20 ℃ before curing is 0.1MPa or more, and the Young's modulus of the cured coating film is 20MPa or less.
Effects of the invention
The moisture-curable polyurethane hot-melt resin composition of the present invention is excellent in initial adhesion strength and final adhesion strength, and can give a cured coating film excellent in flexibility. Therefore, the moisture-curable polyurethane hot-melt resin composition of the present invention can be particularly suitably used for fiber applications.
Detailed Description
The moisture-curable polyurethane hot-melt resin composition of the present invention has a storage elastic modulus (G ') of melt viscoelasticity at 20 ℃ before curing of 0.1MPa or more and a Young's modulus of a cured coating of 20MPa or less.
In order to obtain excellent initial adhesion strength, the moisture-curable polyurethane hot-melt resin composition of the present invention must have a storage elastic modulus (G') of melt viscoelasticity at 20 ℃ before curing of 0.1MPa or more, and it is presumed that in this range, the moisture-curable urethane resin composition before curing has a hard structure, and thus excellent initial adhesion strength can be obtained. The storage elastic modulus (G') is preferably in the range of 0.2 to 1,000mpa, and more preferably in the range of 0.3 to 500MPa, from the viewpoint of obtaining a further excellent initial adhesion strength. The method for measuring the storage elastic modulus (G') of the melt viscoelasticity at 20 ℃ before curing of the moisture-curable polyurethane hot-melt resin composition is described in examples.
In order to obtain excellent flexibility, the young's modulus of the cured coating film of the moisture-curable polyurethane hot-melt resin composition of the present invention must be 20MPa or less, preferably 0.5 to 15MPa, and more preferably 1 to 10 MPa. The method for measuring the young's modulus of the cured film of the moisture-curable polyurethane hot-melt resin composition is described in examples.
As the moisture-curable polyurethane hot-melt resin composition, specifically, for example, a moisture-curable polyurethane hot-melt resin composition containing a urethane prepolymer having an isocyanate group obtained by reacting a polyol (a) and a polyisocyanate (B) can be used.
The technical idea of setting the storage elastic modulus and the young's modulus of the moisture-curable polyurethane hot-melt resin composition in the above ranges includes, for example: the dosage of the crystalline polyester polyol is reduced; using a liquid polyol in combination with a polyol other than the liquid polyol; a polyol having a small number average molecular weight is used; the reaction ratio of the polyol to the polyisocyanate is adjusted, and the urethane bond amount is increased; the isocyanate group at the molecular end or the like is reduced, and the urea concentration by moisture curing is reduced.
Examples of the polyol (A) include crystalline polyester polyols, amorphous polyester polyols, polyether polyols, polycarbonate polyols, polyacrylic polyols, dimer alcohols (Japanese: 1248012452125400\125724012540), polybutadiene polyols, and the like. These polyols may be used alone, or 2 or more kinds may be used in combination. As the polyol (a), a crystalline polyester polyol is used in a proportion of preferably less than 10% by mass, more preferably less than 5% by mass of the total mass of the polyol (a) and the polyisocyanate (B), from the viewpoint of easily setting the young's modulus of the cured film within the range specified in the present invention and obtaining further excellent flexibility.
Further, the polyol (a) preferably contains a liquid polyol (a 1) and other polyols (a 2) in view of easy setting of the storage elastic modulus and young's modulus in the above ranges and obtaining more excellent initial adhesive strength and flexibility. In the present invention, the liquid polyol (a 1) is a polyol having a viscosity of 100,000mpa · s or less at 25 ℃.
As the liquid polyol (a 1), a polyether polyol is preferably used. As the polyether polyol, for example, a polymer of a polyol and an alkylene oxide can be used.
As the above polyol, for example, there can be used: diols such as ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 1, 8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1, 4-diol, and cyclohexane-1, 4-dimethanol; polyester polyols, and the like. These compounds can be used alone, also can be used in combination of 2 or more.
As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and the like can be used. These compounds can be used alone, also can be used in combination of 2 or more.
As the polyether polyol, polypropylene glycol is preferably used because the storage elastic modulus and young's modulus can be easily set in the above ranges, and further excellent initial adhesion strength and flexibility can be obtained.
As the polyol (a 2) other than the above, an aromatic polyester polyol is preferably used. As the aromatic polyester polyol, for example, there can be used: a reaction product of a compound having a hydroxyl group and a polybasic acid comprising an aromatic polybasic acid; a reaction product of an aromatic compound having 2 or more hydroxyl groups and a polybasic acid, and the like.
Examples of the compound having a hydroxyl group include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonanediol, decanediol, trimethylolpropane, trimethylolethane, glycerol, and neopentyl glycol. These compounds may be used alone, or 2 or more of them may be used in combination.
Examples of the aromatic compound having 2 or more hydroxyl groups include 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 2 or more of them may be used in combination. Among them, an alkylene oxide adduct of bisphenol a is preferably used from the viewpoint of obtaining still more excellent initial adhesive strength and flexibility, and the number of moles of alkylene oxide added is preferably in the range of 1 to 10 moles.
Examples of the aromatic polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride. Examples of the other polybasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and 1, 12-dodecanedicarboxylic acid. These polybasic acids may be used alone, or 2 or more kinds may be used in combination. The aromatic polybasic acid is preferably 1 or more compounds selected from phthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride, from the viewpoint of obtaining still more excellent initial adhesive strength and flexibility.
The number average molecular weights of the polyol (a 1) and the polyol (a 2) are preferably less than 2,800, more preferably in the range of 300 to 2,500, and still more preferably in the range of 600 to 2,200, from the viewpoint of easily setting the storage elastic modulus and the young's modulus in the above ranges and obtaining further excellent initial adhesive strength and flexibility. The number average molecular weights of the polyol (a 1) and the polyol (a 2) are values measured by a Gel Permeation Chromatography (GPC) method.
The mass ratio [ (a 1)/(a 2) ] between the polyol (a 1) and the polyol (a 2) is preferably in the range of 20/80 to 90/10, more preferably in the range of 30/70 to 85/15, and even more preferably in the range of 40/60 to 80/20, from the viewpoint of easily setting the storage elastic modulus and the young's modulus in the above ranges and obtaining further excellent low viscosity, initial adhesive strength, and flexibility.
As the polyisocyanate (B), for example, there can be used: aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, phenylene diisocyanate, tolylene 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. Among them, aromatic polyisocyanates are preferably used, and diphenylmethane diisocyanate is more preferably used, from the viewpoint of obtaining further excellent reactivity and final adhesive strength.
The amount of the polyisocyanate (B) used is preferably in the range of 5 to 60% by mass, more preferably in the range of 15 to 50% by mass, in the raw material of the urethane prepolymer (i), from the viewpoint of obtaining a further excellent adhesive strength.
The urethane prepolymer (i) is obtained by reacting the polyol (a) with the polyisocyanate (B), and has an isocyanate group at a polymer end and in a molecule, which is capable of reacting with moisture present in air, a frame to which the urethane prepolymer is applied, and an adherend to form a crosslinked structure.
The urethane prepolymer (i) can be produced, for example, by the following method: the polyol (a) is dropped into a reaction vessel containing the polyisocyanate (B), and then heated to react under a condition that the isocyanate group of the polyisocyanate (B) is excessive with respect to the hydroxyl group of the polyol (a).
The urethane bond amount of the urethane prepolymer (i) is preferably in the range of 0.5 to 3mol/kg, more preferably in the range of 0.9 to 2.7mol/kg, and still more preferably in the range of 1.1 to 2.4mol/kg, from the viewpoint that the storage elastic modulus and young's modulus are easily set in the above ranges and further excellent low viscosity, initial adhesive strength, and flexibility can be obtained.
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 in the range of 1.1 to 1.5, more preferably in the range of 1.15 to 1.45, from the viewpoints that the storage elastic modulus and young's modulus can be easily set in the above ranges and further excellent low viscosity, initial adhesive strength and flexibility can be obtained.
The content of the isocyanate group (hereinafter abbreviated as "NCO%") in the urethane prepolymer (i) is preferably in the range of 1 to 4% by mass, more preferably in the range of 1.2 to 3.5% by mass, from the viewpoint of easily setting the storage elastic modulus and young's modulus in the above ranges and obtaining further excellent low viscosity, initial adhesive strength and flexibility. The NCO% of the urethane prepolymer (i) is expressed in terms of JIS K1603-1: 2007. values determined by potentiometric titration.
The moisture-curable polyurethane hot-melt resin composition of the present invention may contain other additives as needed in addition to the urethane prepolymer (i).
Examples of a method for obtaining a cured coating film of the moisture-curable polyurethane hot-melt resin composition include a method in which the moisture-curable polyurethane hot-melt resin composition is melted at 50 to 130 ℃, applied to a substrate, and moisture-cured.
As the substrate, for example, there can be used: resin films such AS acrylic resins, urethane resins, silicon resins, epoxy resins, fluorine resins, polystyrene resins, polyester resins, polysulfone resins, polyarylate resins, polyvinyl chloride resins, polyvinylidene chloride resins, cycloolefin resins, polyolefin resins, polyimide resins, alicyclic polyimide resins, cellulose resins, PC (polycarbonate), PBT (polybutylene terephthalate), modified PPE (polyphenylene ether), PEN (polyethylene naphthalate), PET (polyethylene terephthalate), lactic acid polymers, ABS resins, and AS resins; wood substrates such as MDF, plywood, particle board, etc.; fibrous base materials such as nonwoven fabrics, woven fabrics, and knitted fabrics. The base material may be subjected to corona treatment, plasma treatment, primer treatment, or the like as required.
Examples of a method for applying the moisture-curable polyurethane hot-melt resin composition include a method using a roll coater, a spray coater, a T-die coater, a knife coater, a comma coater, and the like.
After the above coating, the final adhesive strength can be obtained by aging the coating at 20 to 80 ℃ and 50 to 90% relative humidity RH for 0.5 to 3 days.
As described above, the moisture-curable polyurethane hot-melt resin composition of the present invention is excellent in initial adhesion strength and final adhesion strength, and can provide a cured coating film excellent in flexibility. Therefore, the moisture-curable polyurethane hot-melt resin composition of the present invention can be particularly suitably used for fiber applications.
Examples
The present invention will be described in more detail below with reference to examples.
[ example 1]
Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 51 parts by mass of polypropylene glycol (number average molecular weight: 1000, hereinafter abbreviated as "PPG 1000") and 24 parts by mass of aromatic polyester polyol (obtained by reacting neopentyl glycol with phthalic anhydride, number average molecular weight: 1,000, hereinafter abbreviated as "NPG/oPA 1000") were charged, and the mixture was heated under reduced pressure at 90 ℃.
Subsequently, after the temperature in the vessel was cooled to 60 ℃, 25 parts by mass of 4,4' -diphenylmethane diisocyanate (hereinafter abbreviated as "MDI-1") was added, the temperature was raised to 110 ℃, and the reaction was carried out for about 3 hours until the isocyanate group content became constant, to obtain a urethane prepolymer (i-1) having an isocyanate group, thereby obtaining a moisture-curable polyurethane hot-melt resin composition. The urethane prepolymer (i-1) had an NCO% of 1.8 mass%, an urethane bond amount of 1.50mol/kg and an [ NCO/OH ] at the time of synthesis of 1.33.
[ method for measuring number average molecular weight ]
In the above examples, the number average molecular weight of the polyol means a value measured by a Gel Permeation Chromatography (GPC) method under the following conditions.
Measurement device: high efficiency GPC apparatus (HLC-8220 GPC, manufactured by Tosoh corporation)
Column: the following columns, manufactured by Tosoh corporation, were connected in series for use.
"TSKgel G5000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSKgel G4000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSKgel G3000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSKgel G2000" (7.8mmI.D.. Times.30 cm). Times.1 roots
A detector: RI (differential refractometer)
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100 μ l (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: the calibration curve was prepared using the following standard polystyrene.
(Standard polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-5000 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-1 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-2 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-4 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-10 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-20 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-40, manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-80, manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-128 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-288 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-550 manufactured by Tosoh corporation "
[ example 2]
1000 parts by mass of PPG and 1000 parts by mass of NPG/oPA were put into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and heated at 90 ℃ under reduced pressure to dehydrate the mixture to a moisture content of 0.05 mass% or less.
Subsequently, the temperature in the vessel was cooled to 60 ℃, and then 1 part by mass of MDI-1 was added thereto, the temperature was raised to 110 ℃ and the reaction was carried out for about 3 hours until the isocyanate group content became constant to obtain an isocyanate group-containing urethane prepolymer (i-2), thereby obtaining a moisture-curable polyurethane hot-melt resin composition. The urethane prepolymer (i-2) had an NCO% of 1.8 mass%, an urethane bond amount of 1.50mol/kg and an [ NCO/OH ] at the time of synthesis of 1.33.
[ example 3]
Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 50 parts by mass of polypropylene glycol (number average molecular weight: 700, hereinafter abbreviated as "PPG 700") and 1000 parts by mass of NPG/oPA were charged and heated at 90 ℃ under reduced pressure, thereby dehydrating the mixture until the water content becomes 0.05% by mass or less.
Subsequently, the temperature in the vessel was cooled to 60 ℃, and then 29 parts by mass of MDI-was added thereto, the temperature was raised to 110 ℃ and the reaction was carried out for about 3 hours until the isocyanate group content became constant to obtain an isocyanate group-containing urethane prepolymer (i-3), thereby obtaining a moisture-curable polyurethane hot-melt resin composition. The urethane prepolymer (i-3) had an NCO% of 1.7% by mass, an urethane bond content of 1.85mol/kg and an [ NCO/OH ] value of 1.26 at the time of synthesis.
[ example 4]
1000 parts by mass of PPG, 22 parts by mass of polypropylene glycol (number average molecular weight: 2,000, hereinafter abbreviated as "PPG 2000"), and 33 parts by mass of NPG/oPA1000 were put into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and heated at 90 ℃ under reduced pressure to dehydrate the flask until the water content becomes 0.05% by mass or less.
Subsequently, the temperature in the vessel was cooled to 60 ℃, and then 1 part by mass of MDI-was added thereto, the temperature was raised to 110 ℃ and the reaction was carried out for about 3 hours until the isocyanate group content became constant to obtain an isocyanate group-containing urethane prepolymer (i-4) and thereby obtain a moisture-curable polyurethane hot-melt resin composition. The urethane prepolymer (i-4) had an NCO% of 1.9% by mass, an urethane bond content of 1.32mol/kg and an [ NCO/OH ] value of 1.39 at the time of synthesis.
[ example 5]
Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 1000 parts by mass of PPG and 35 parts by mass of aromatic polyester polyol (a reaction product of a 6-mole adduct of bisphenol A propylene oxide and sebacic acid, number average molecular weight: 1,000, hereinafter abbreviated as "SEBA/BisA6 PO") were charged, and the mixture was heated under reduced pressure at 90 ℃ to dehydrate the mixture until the water content became 0.05% by mass or less.
Subsequently, after the temperature in the vessel was cooled to 60 ℃, 25 parts by mass of an equal amount of a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate (hereinafter abbreviated as "MDI-2") was added, the temperature was raised to 110 ℃ and the reaction was carried out for about 3 hours until the isocyanate group content became constant to obtain a urethane prepolymer (i-5) having an isocyanate group, thereby obtaining a moisture-curable polyurethane hot-melt resin composition. The NCO% of the urethane prepolymer (i-5) was 1.8% by mass, the urethane bond content was 1.50mol/kg, and the [ NCO/OH ] at the time of synthesis was 1.33.
Comparative example 1
1000 parts by mass of PPG, 1000 parts by mass of NPG/oPA, and 18 parts by mass of a crystalline polyester polyol (obtained by reacting 1, 6-hexanediol with adipic acid, and having a number average molecular weight of 2,000, hereinafter abbreviated to "crystalline PEs") were placed in a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and the mixture was heated at 90 ℃ under reduced pressure to dehydrate the mixture until the water content became 0.05% by mass or less.
Subsequently, the temperature in the vessel was cooled to 60 ℃, and then 25 parts by mass of MDI-was added thereto, the temperature was raised to 110 ℃ and the reaction was carried out for about 3 hours until the isocyanate group content became constant to obtain an isocyanate group-containing urethane prepolymer (i' -1), thereby obtaining a moisture-curable polyurethane hot-melt resin composition. The urethane prepolymer (i' -1) had an NCO% of 1.7% by mass, an urethane bond content of 1.37mol/kg and an [ NCO/OH ] value of 1.34 in the synthesis.
Comparative example 2
Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 1000 parts by mass of NPG/oPA and 56 parts by mass of an amorphous polyester polyol (obtained by reacting ethylene glycol, 1, 6-hexanediol, neopentyl glycol and adipic acid at a molar ratio of 25/18/8/49, and having a number average molecular weight of 5,500, hereinafter abbreviated as "amorphous PEs") were charged, and the mixture was heated under reduced pressure at 90 ℃ to dehydrate the mixture until the moisture content became 0.05% by mass or less.
Subsequently, the temperature in the vessel was cooled to 60 ℃, and then 1 part by mass of MDI-1 was added thereto, and the temperature was raised to 110 ℃ to react for about 3 hours until the isocyanate group content became constant, thereby obtaining a urethane prepolymer (i' -2) having an isocyanate group, and a moisture-curable polyurethane hot-melt resin composition was obtained. The urethane prepolymer (i' -2) was obtained to obtain a moisture-curable polyurethane hot-melt resin composition. The urethane prepolymer (i' -2) had an NCO% of 1.9% by mass, an urethane bond content of 0.76mol/kg and an [ NCO/OH ] value of 1.68 at the time of synthesis.
[ method for measuring storage elastic modulus ]
The moisture-curable polyurethane hot-melt resin compositions obtained in examples and comparative examples were melted at 110 ℃ for 1 hour, 10ml of the composition was sampled and placed on a parallel plate of a melt viscoelasticity measuring apparatus ("MCR-302" manufactured by Anton Paar Co., ltd.), melt viscoelasticity was measured at a cooling rate of 1 ℃/min and a frequency of 1Hz from 110 ℃ to 10 ℃, and the storage elastic modulus (G') at 20 ℃ was measured.
[ method of measuring Young's modulus ]
The moisture-curable polyurethane hot-melt resin compositions obtained in examples and comparative examples were melted at 110 ℃ for 1 hour, then applied to a polyethylene terephthalate substrate subjected to mold release treatment using a blade coater so that the cured film thickness became 100 μm, and left to stand for 3 days, thereby obtaining a cured coating film. The cured film was peeled from the release PET, and a sheet obtained by punching with a No. 2 dumbbell was used as a test piece. The test piece was subjected to a tensile test using a TENSILON tensile tester ("RTM-100" manufactured by Orientec corporation) at a cross-head speed in an atmosphere of 25 ℃: a tensile test was conducted at 200 mm/min, and the Young's modulus was measured from the origin of the graph at the time of the tensile test and the stress at the time of elongation of 2.5%.
[ method for measuring initial adhesion Strength ]
The moisture-curable polyurethane hot melt compositions obtained in examples and comparative examples were respectively melted at a temperature of 120 ℃ for 1 hour. The adhesive was applied to a polyethylene terephthalate sheet with a thickness of 100 μm using an applicator. A polyethylene terephthalate sheet was bonded to the coating layer, and pressure-bonded by a pressure-bonding roller. After 5 minutes from the pressure bonding, the adhesive strength (N/25 mm) was measured using a precision universal tester "AG-10NX" manufactured by Shimadzu corporation, and the initial strength was evaluated as follows.
"T": the adhesive strength is 15 (N/25 mm) or more.
"F": the bonding strength is less than 15 (N/25 mm).
[ method of evaluating flexibility ]
The moisture-curable polyurethane hot-melt resin compositions obtained in examples and comparative examples were melted at 110 ℃ for 1 hour, then applied to a polyester nonwoven fabric using a blade coater so that the cured film thickness became 100 μm, and left to stand for 3 days, thereby obtaining a cured film. From the feel, flexibility was evaluated as follows.
"T": has high flexibility.
"F": a hard impression is obtained.
[ evaluation of Low viscosity ]
The moisture-curable polyurethane hot-melt resin compositions obtained in examples and comparative examples were melted at 120 ℃ for 1 hour, sampled at 1ml, and melt viscosity was measured with a cone-and-plate viscometer (40P cone, rotor speed: 50 rpm) to evaluate low-viscosity properties as follows.
"T": less than 30,000mPa s
"F":30,000mPa s or more
[ Table 1]
Examples 1 to 5, which are the moisture-curable polyurethane hot-melt resin compositions of the present invention, are excellent in initial adhesive strength and flexibility.
On the other hand, in comparative example 1, the cured coating film had a young's modulus exceeding the range defined in the present invention, and the flexibility was poor.
In comparative example 2, the initial adhesive strength was poor in such a manner that the storage elastic modulus before curing was lower than the range specified in the present invention.
Claims (6)
1. A moisture-curable polyurethane hot-melt resin composition characterized in that the storage elastic modulus G 'of the melt viscoelasticity at 20 ℃ before curing is 0.1MPa or more, the Young's modulus of the cured coating film is 0.5MPa or more and 20MPa or less,
the moisture-curable polyurethane hot-melt resin composition contains a urethane prepolymer i having an isocyanate group, which is prepared from a polyol A and a polyisocyanate B,
the urethane prepolymer i has a urethane bond amount in the range of 1.1 to 2.4mol/kg,
a crystalline polyester polyol is used in a proportion of less than 10% by mass of the total mass of the polyol A and the polyisocyanate B,
the polyol A contains only a liquid polyol a1 and the other polyols a2,
the polyol a1 is polyether polyol which is polypropylene glycol,
the polyol a2 is an aromatic polyester polyol which is at least one selected from the group consisting of a reaction product of a compound having a hydroxyl group and a polybasic acid comprising an aromatic polybasic acid, and a reaction product of an aromatic compound having 2 or more hydroxyl groups and a polybasic acid,
the compound having a hydroxyl group is at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, trimethylolpropane, trimethylolethane, and glycerin.
2. The moisture-curable polyurethane hot melt resin composition according to claim 1, wherein the pentanediol is neopentyl glycol.
3. The moisture-curable polyurethane hot-melt resin composition according to claim 1, wherein the number average molecular weight of the polyol a1 and the polyol a2 is less than 2,800.
4. The moisture-curable polyurethane hot-melt resin composition according to claim 1 or 3, wherein the molar ratio of the polyol A to the polyisocyanate B, i.e., NCO/OH, is in the range of 1.1 to 1.5.
5. The moisture-curable polyurethane hot-melt resin composition according to claim 1 or 3, wherein the urethane prepolymer i has an isocyanate group content in the range of 1% to 4%.
6. The moisture-curable polyurethane hot-melt resin composition according to claim 4, wherein the urethane prepolymer i has an isocyanate group content in the range of 1 to 4%.
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| JP2018-028794 | 2018-02-21 | ||
| JP2018028794 | 2018-02-21 | ||
| PCT/JP2019/005250 WO2019163622A1 (en) | 2018-02-21 | 2019-02-14 | Moisture-curable polyurethane hot melt resin composition |
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| JP6981578B2 (en) * | 2019-09-20 | 2021-12-15 | Dic株式会社 | Moisture-curable polyurethane resin composition, adhesive, and laminate |
| JP2022011881A (en) * | 2020-06-30 | 2022-01-17 | 東洋インキＳｃホールディングス株式会社 | Method for Producing Polyisocyanate Composition |
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| CN113308084B (en) * | 2021-06-25 | 2022-12-02 | 重庆沃特智成新材料科技有限公司 | Polyether ketone composite material and preparation method thereof |
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| JPWO2019163622A1 (en) | 2020-05-28 |
| JP6753550B2 (en) | 2020-09-09 |
| WO2019163622A1 (en) | 2019-08-29 |
| CN111741992A (en) | 2020-10-02 |
| TW201936686A (en) | 2019-09-16 |
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