CN118302468A - Moisture-curable polyurethane hot-melt resin composition, adhesive, and laminate - Google Patents

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

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Publication number
CN118302468A
CN118302468A CN202280078327.3A CN202280078327A CN118302468A CN 118302468 A CN118302468 A CN 118302468A CN 202280078327 A CN202280078327 A CN 202280078327A CN 118302468 A CN118302468 A CN 118302468A
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Prior art keywords
polyester polyol
mass
moisture
resin composition
aliphatic polyester
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Chinese (zh)
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长尾匡宪
南田至彦
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DIC Corp
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DIC Corp
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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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention provides a moisture-curable polyurethane hot-melt resin composition containing a urethane prepolymer (i), wherein the polyol (A) contains a long-chain crystalline polyester polyol (a 1), an aliphatic polyester polyol (a 2) starting from a diol having 2, 2-dimethyl-1, 3-propylene, and an aromatic polyester polyol (a 3), and the aliphatic polyester polyol (a 2) is used in combination with an aliphatic polyester polyol having a number average molecular weight of 1000 to 3000 and an aliphatic polyester polyol having a number average molecular weight of 5000 to 9000, and the mass ratio [ (a 2-1)/(a 2-2) ] is 1 to 3. The present invention also provides an adhesive comprising the moisture-curable polyurethane hot-melt resin composition.

Description

Moisture-curable polyurethane hot-melt resin composition, adhesive, and laminate
Technical Field
The present invention relates to a moisture-curable polyurethane hot-melt resin composition, an adhesive, and a laminate.
Background
The moisture-curable polyurethane hot-melt resin composition is used as an adhesive for various building material applications. In order to exhibit the desired adhesive property, the moisture-curable polyurethane hot-melt resin composition described above often contains polyester as its constitution. Among them, the inclusion of an amorphous linear aliphatic polyester polyol having a relatively low glass transition temperature is useful for exhibiting adhesion to a relatively smooth aluminum-based substrate or a polyvinyl chloride substrate (for example, refer to patent document 1). However, when the ratio of the polyol to be used is large as described above, there is a problem that the cohesive force at the initial stage of adhesion cannot be developed.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2018-16703
Disclosure of Invention
Problems to be solved by the invention
The invention aims to solve the problems that: provided is a moisture-curable polyurethane resin composition which has excellent initial adhesion to a substrate (particularly an aluminum substrate and/or a polyvinyl chloride substrate) and adhesion.
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) as a reaction product of a polyol (a) and a polyisocyanate (B), wherein the polyol (a) comprises: a long-chain crystalline polyester polyol (a 1); aliphatic polyester polyol (a 2) other than the long-chain crystalline polyester polyol (a 1) and starting from a diol having 2, 2-dimethyl-1, 3-propylene group; and an aromatic polyester polyol (a 3), wherein the aliphatic polyester polyol (a 2) is used in combination with the aliphatic polyester polyol (a 2-1) having a number average molecular weight of 1000 to 3000 and the aliphatic polyester polyol (a 2-2) having a number average molecular weight of 5000 to 9000, and the mass ratio [ (a 2-1)/(a 2-2) ] is 1 to 3.
The present invention also provides an adhesive comprising the moisture-curable polyurethane hot-melt resin composition. The present invention also provides a laminate characterized by comprising a substrate and a coating of the adhesive.
Effects of the invention
The moisture-curable polyurethane hot-melt resin composition of the present invention is excellent in initial adhesion to a substrate (particularly an aluminum-based substrate and/or a polyvinyl chloride substrate (hereinafter abbreviated as "PVC substrate")).
Detailed Description
The moisture-curable polyurethane hot-melt resin composition used in the present invention contains a urethane prepolymer (i) having isocyanate groups as a reaction product of a specific polyol (a) and a polyisocyanate (B).
The polyol (A) contains: a long-chain crystalline polyester polyol (a 1); aliphatic polyester polyol (a 2) other than the long-chain crystalline polyester polyol (a 1) and starting from a diol having 2, 2-dimethyl-1, 3-propylene group; an aromatic polyester polyol (a 3).
The long-chain crystalline polyester polyol (a 1) is an essential component in terms of obtaining excellent adhesion due to its cohesive force, 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 the composition is based on JISK7121: in 2012, a peak of crystallization heat or melting heat was observed in the DSC (differential scanning calorimeter) measurement, and "amorphous" indicates that the peak was not observed.
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 glycerol. These compounds may be used alone or in combination of 2 or more. Among them, 1 or more selected from butanediol, hexanediol, octanediol and decanediol is preferably used from the viewpoint of improving crystallinity and obtaining 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. Among them, 1 or more selected from adipic acid, sebacic acid and dodecanedioic acid is preferably used from the viewpoint of obtaining more excellent adhesion.
The number average molecular weight of the long-chain crystalline polyester polyol (a 1) is preferably 500 to 10000, more preferably 1000 to 7000, from the point of obtaining more excellent adhesion. The number average molecular weight of the crystalline polyester polyol (a 1) is a value measured by a Gel Permeation Chromatography (GPC) method.
The amount of the long-chain crystalline polyester polyol (a 1) used is preferably 32 to 40% by mass, more preferably 33 to 37% by mass, based on the total amount of the polyol (a) and the polyisocyanate (B), from the point of obtaining more excellent adhesion.
The aliphatic polyester polyol (a 2) is an aliphatic polyester polyol which is obtained from a diol having a2, 2-dimethyl-1, 3-propylene group as a raw material, in addition to the long-chain crystalline polyester polyol (a 1).
In order to achieve both excellent initial adhesion to a substrate (particularly an aluminum substrate or a polyvinyl chloride substrate) and excellent adhesion, the aliphatic polyester polyol (a 2-1) having a number average molecular weight of 1000 to 3000 and the aliphatic polyester polyol (a 2-2) having a number average molecular weight of 5000 to 9000 are used in combination, and the mass ratio [ (a 2-1)/(a 2-2) ] of these components is 1 to 3.
The aliphatic polyester polyol (a 2) is an amorphous polyester polyol because it is prepared from a diol having a branched 2, 2-dimethyl-1, 3-propylene group, and has high molecular chain mobility, and can follow and interact with minute irregularities on aluminum-based substrates and PVC substrates, thereby exhibiting excellent adhesion. However, when the aliphatic polyester polyol (a 2) is used without design, the glass transition temperature is generally low, and the initial adhesion becomes poor. In the present invention, by providing the above-described configuration, the glass transition temperature and viscosity of the entire aliphatic polyester polyol become high, and therefore excellent adhesion and initial adhesion can be achieved at the same time.
The aliphatic polyester polyol (a 2-1) and the aliphatic polyester polyol (a 2-2) may each be a reaction product of a compound having a hydroxyl group containing a diol having 2, 2-dimethyl-1, 3-propylene as an essential component with a polybasic acid.
The diol having a 2, 2-dimethyl-1, 3-propylene group includes, for example, neopentyl glycol, its dimer and trimer. These compounds may be used alone or in combination of 2 or more. Among them, neopentyl glycol is preferable from the point of obtaining more excellent initial adhesiveness.
The amount of the diol having a2, 2-dimethyl-1, 3-propylene group is preferably 10% by mass or more, and more preferably 10 to 20% by mass based on the total amount of the compounds having a hydroxyl group.
Examples of the compounds having a hydroxyl group that can be used other than the diols having a2, 2-dimethyl-1, 3-propylene group include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, cyclohexanedimethanol, bisphenol A, bisphenol F, alkylene oxide adducts of these, triethylene glycol, trimethylolpropane, trimethylolethane, and glycerol.
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 aliphatic polyester polyol (a 2-1) is preferably 1500 to 2500 from the point of obtaining more excellent initial adhesiveness and adhesion, and the number average molecular weight of the aliphatic polyester polyol (a 2-2) is preferably 6000 to 8000. The number average molecular weight of the aliphatic polyester polyol (a 2-1) and the aliphatic polyester polyol (a 2-2) is a value measured by a Gel Permeation Chromatography (GPC) method.
The mass ratio [ (a 2-1)/(a 2-2) ] of the aliphatic polyester polyol (a 2-1) to the aliphatic polyester polyol (a 2-2) is preferably 1 to 2.5 in order to obtain more excellent initial adhesiveness and adhesion.
The total amount of the aliphatic polyester polyol (a 2) is preferably 15 to 38% by mass, more preferably 20 to 37% by mass, based on the total amount of the polyol (a) and the polyisocyanate (B), from the viewpoint of obtaining more excellent initial adhesiveness and adhesion.
As the aromatic polyester polyol (a 3), it is an essential component in terms of obtaining excellent adhesion by its cohesive force, and for example, it is possible to use: a reaction product of a compound having a hydroxyl group and a polyacid comprising an aromatic polyacid; reaction products of aromatic compounds having 2 or more hydroxyl groups with polybasic acids; and a reaction product of an aromatic compound having 2 or more hydroxyl groups and a polybasic acid containing an aromatic polybasic acid.
Examples of the compound having a hydroxyl group include aliphatic compounds such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1, 2-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, 2-methyl-1, 8-octanediol, 2, 4-diethyl-1, 5-pentanediol, trimethylolethane, trimethylolpropane, pentaerythritol and the like; alicyclic compounds such as cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol a, and alkylene oxide adducts thereof. These compounds may be used alone or in combination of 2 or more.
Examples of the aromatic compound having at least 2 hydroxyl groups include bisphenol a, bisphenol F, and adducts of these (ethylene oxide, propylene oxide, butylene oxide, etc.), and the like. These compounds may be used alone or in combination of 2 or more.
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, 1, 12-dodecanedioic acid, and the like. These polybasic acids may be used alone or in combination of 2 or more. The aromatic polybasic acid is a point of obtaining more excellent initial adhesion strength and flexibility.
Examples of the other 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.
The aromatic polyester polyol (a 3) preferably contains 1 or more kinds of phthalic acid compounds selected from phthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride as a raw material from the viewpoint of obtaining more excellent adhesion.
The number average molecular weight of the aromatic polyester polyol (a 3) is preferably 500 to 10000, more preferably 1000 to 5000, from the point of obtaining more excellent adhesion. The number average molecular weight of the aromatic polyester polyol (a 3) is a value measured by a Gel Permeation Chromatography (GPC) method.
The amount of the aromatic polyester polyol (a 3) used is preferably 15 to 35% by mass, more preferably 18 to 32% by mass, based on the total amount of the polyol (a) and the polyisocyanate (B), from the point of obtaining more excellent adhesion.
The polyol (a) contains the components (a 1) to (a 3) as essential polyol components, but may contain other polyols as required.
Examples of the other polyols include polyester polyols, polycarbonate polyols, polyacrylic polyols, polyether polyols, and the like, which are other than the components (a 1) to (a 3). These polyols may be used alone or in combination of 2 or more.
As the polyisocyanate (B), for example, there can be used: aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, xylylene diisocyanate, phenylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate; 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 them, aromatic polyisocyanates are preferable, and diphenylmethane diisocyanate is more preferable from the viewpoint of obtaining more excellent adhesion.
The urethane prepolymer (i) is obtained by reacting the polyol (a) with the polyisocyanate (B), and has isocyanate groups that can react with moisture present in the air in a substrate to which the moisture-curable polyurethane hot-melt resin composition is applied to form a crosslinked structure.
As a method for producing the urethane prepolymer (i), for example, the following method can be used: the polyisocyanate (B) is added to a reaction vessel containing the polyol (a) and allowed to react under a condition in which the isocyanate groups of the polyisocyanate (B) are excessive relative to the hydroxyl groups of the polyol (a).
The equivalent ratio [ NCO/OH ] of the isocyanate groups of the polyisocyanate (B) to the hydroxyl groups of the polyol (A) in the production of the urethane prepolymer (i) is preferably 1.5 to 4, more preferably 1.8 to 3.0, from the viewpoint of obtaining more excellent initial adhesiveness and adhesion.
The isocyanate group content (hereinafter abbreviated as "NCO%") of the urethane prepolymer (i) obtained by the above method is preferably 1 to 6% by mass, more preferably 2 to 4% by mass, from the point that more excellent initial adhesiveness and adhesion are obtained. The NCO% of the hot-melt urethane prepolymer (i) is represented by JISK1 603-1:2007 values determined by potentiometric titration.
The moisture-curable polyurethane hot-melt resin composition used in the present invention contains the urethane prepolymer (i) as an essential component, and other additives may be used as required.
As the aforementioned other additives, for example, it is possible to use: light-resistant stabilizers, curing catalysts, plasticizers, stabilizers, filler materials, dyes, pigments, carbon black, carriers, fluorescent whitening agents, silane coupling agents, waxes, thermoplastic resins, and the like. 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 initial adhesion to a substrate (particularly, an aluminum substrate and/or a PVC substrate) and adhesion. Therefore, the moisture-curable polyurethane hot-melt resin composition of the present invention can be suitably used as an adhesive for aluminum-based substrates and PVC substrates.
Next, the laminate of the present invention will be described.
The laminate comprises at least: a substrate, and a coating of an adhesive comprising the moisture-curable polyurethane hot-melt resin composition.
As the substrate, for example, a substrate obtained from: glass plates, metal plates of stainless steel (SUS), magnesium, aluminum, and the like, cycloolefin-based resins of norbornene, and the like, acrylic resins, urethane resins, silicone resins, epoxy resins, fluorine resins, polystyrene resins, polyester resins, polysulfone resins, polyarylate resins, polyvinyl chloride resins, polyvinylidene chloride, polyolefin resins, polyimide resins, alicyclic polyimide resins, polyamide resins, cellulose resins, polycarbonates (PC), polybutylene terephthalate (PBT), polyphenylene ether (modified PPE), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), lactic acid polymers, acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile-styrene copolymers (AS), aluminum-based (in-situ) and the like. The substrate may be subjected to corona treatment, plasma treatment, primer treatment, or the like, as required. The aluminum-based material means aluminum or an aluminum alloy.
Examples of the method of applying the adhesive to the base material include: and a method of applying the adhesive to the substrate by heating and melting the adhesive at 50 to 130 ℃. As the coating method, a roll coater, a spray coater, a T-die coater, a blade coater, a comma coater, or the like can be used.
After the application, a base material may be further placed on the adhesive surface and bonded. The thickness of the adhesive layer may be set according to the application, and may be set, for example, preferably in the range of 30 μm to 5 mm.
The curing conditions after the bonding can be suitably determined, for example, at a temperature of 20 to 80℃and a relative humidity of 50 to 90% RH for 0.5 to 5 days.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, was added: the reaction product of a long-chain crystalline polyester polyol (1, 6-hexanediol and dodecanedioic acid, the number average molecular weight: 3500, hereinafter abbreviated as "crystalline PEs (1)") 34 parts by mass, an aliphatic polyester polyol (diethylene glycol, neopentyl glycol and a reaction product of 1, 6-hexanediol and adipic acid, the number average molecular weight: 2000, the amount of the neopentyl glycol used in the total amount of all diols: 14 parts by mass, hereinafter abbreviated as "aliphatic PEs (1)") 10 parts by mass, an aliphatic polyester polyol (diethylene glycol, neopentyl glycol and a reaction product of 1, 6-hexanediol and adipic acid, the number average molecular weight: 7000, the amount of the neopentyl glycol used in the total amount of all diols: 14 parts by mass, hereinafter abbreviated as "aliphatic PEs (2)") 10 parts by mass, an aromatic polyester polyol (a reaction product of neopentyl glycol and phthalic acid, the number average molecular weight: 2000, hereinafter abbreviated as "aromatic PEs (1)") 30 parts by mass, and a dehydration flask, and a water content of the dehydration flask is reduced to 0.05% by mass. After cooling the flask to 90 ℃,16 parts by mass of 4,4' -diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") melted at 70 ℃ was added, and the mixture was reacted at 110 ℃ for about 2 hours under a nitrogen atmosphere until the NCO% became constant, thereby obtaining a moisture-curable polyurethane hot melt resin composition comprising the urethane prepolymer (i-1).
Example 2
To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, was added: 34 parts by mass of crystalline PEs (1), 20 parts by mass of aliphatic PEs (1), 10 parts by mass of aliphatic PEs (2), and 20 parts by mass of aromatic PEs (1) were heated at 100℃under reduced pressure, and dehydrated until the water content in the flask became 0.05% by mass. After cooling the flask to 90 ℃, 16 parts by mass of MDI melted at 70 ℃ was added, and reacted at 110 ℃ for about 2 hours under a nitrogen atmosphere until the nco% became constant, thereby obtaining a moisture-curable polyurethane hot melt resin composition containing a urethane prepolymer (i-2).
Example 3
To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, was added: 34 parts by mass of crystalline PEs (1), 20 parts by mass of aliphatic PEs (1), 15 parts by mass of aliphatic PEs (2) and 20 parts by mass of aromatic PEs (1) were heated at 100℃under reduced pressure, and dehydrated until the water content in the flask became 0.05% by mass. After cooling the flask to 90 ℃, 16 parts by mass of MDI melted at 70 ℃ was added, and reacted at 110 ℃ for about 2 hours under a nitrogen atmosphere until the nco% became constant, thereby obtaining a moisture-curable polyurethane hot melt resin composition containing a urethane prepolymer (i-3).
Comparative example 1
To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, was added: 35 parts by mass of crystalline PEs (1), 30 parts by mass of aliphatic PEs (2) and 20 parts by mass of aromatic PEs (1) were heated at 100℃under reduced pressure, and dehydrated until the water content in the flask became 0.05% by mass. After cooling the flask to 90 ℃, 15 parts by mass of MDI melted at 70 ℃ was added, and reacted at 110 ℃ for about 2 hours under a nitrogen atmosphere until nco% became constant, thereby obtaining a moisture-curable polyurethane hot melt resin composition containing a urethane prepolymer (iR-1).
Comparative example 2
To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, was added: 38 parts by mass of crystalline PEs (1), 10 parts by mass of aliphatic PEs (1) and 35 parts by mass of aromatic PEs (1) were heated at 100℃under reduced pressure, and dehydrated until the water content in the flask became 0.05% by mass. After cooling the flask to 90 ℃, 17 parts by mass of MDI melted at 70 ℃ was added, and reacted at 110 ℃ for about 2 hours under a nitrogen atmosphere until nco% became constant, thereby obtaining a moisture-curable polyurethane hot melt resin composition containing a urethane prepolymer (iR-2).
Comparative example 3
To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, was added: 35 parts by mass of crystalline PEs (1), 5 parts by mass of aliphatic PEs (1), 15 parts by mass of aliphatic PEs (2) and 30 parts by mass of aromatic PEs (1) were heated at 100℃under reduced pressure, and dehydrated until the water content in the flask became 0.05% by mass. After cooling the flask to 90 ℃, 15 parts by mass of MDI melted at 70 ℃ was added, and reacted at 110 ℃ for about 2 hours under a nitrogen atmosphere until nco% became constant, thereby obtaining a moisture-curable polyurethane hot melt resin composition containing a urethane prepolymer (iR-3).
[ Method for measuring number average molecular weight ]
The number average molecular weight of the polyols used in the examples and comparative examples is represented by: values measured by Gel Permeation Chromatography (GPC) under the following conditions.
Measurement device: high-speed GPC apparatus (HLC-8220 GPC, manufactured by Tosoh Co., ltd.)
Column: the following columns manufactured by Tosoh corporation were used 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
A detector: RI (differential refractometer)
Column temperature: 40 DEG C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100. Mu.L (tetrahydrofuran solution with sample concentration of 0.4% by mass)
Standard sample: standard curves were made using standard polystyrene as described below.
(Standard polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-5000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-1 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-2 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-4 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-10 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-20 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-40 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-80 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-128 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-288 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-550 manufactured by Tosoh Co., ltd "
[ Evaluation method of initial adhesion ]
The moisture curable polyurethane hot melt resin compositions obtained in examples and comparative examples were each melted at 120℃for 1 hour, and then coated on a polyethylene terephthalate sheet with a thickness of 0.1mm using an applicator, and an aluminum base material, a vinyl chloride base material, or a medium density fiberboard was placed on the coated surface, and bonded using a press roll. After applying a slit having a width of 25mm, a creep test was performed at a temperature of 35℃and a load of 150g for 3 minutes, and the peel distance after 15 minutes from the application of the load was measured and evaluated as follows.
"Good" is shown in the following description: the separation distance is 5mm or less with respect to each substrate.
"×": The above is not the case.
[ Method of evaluating adhesion ]
The moisture curable polyurethane hot melt resin compositions obtained in examples and comparative examples were melted at 120℃for 1 hour, and then coated on a polyethylene terephthalate sheet with a thickness of 0.1mm using an applicator, and an aluminum base material, a vinyl chloride base material or a medium density fiberboard was placed on the coated surface, respectively, and bonded using a press roll. A slit having a width of 25mm was applied, left to stand in an atmosphere of 23 ℃ C..times.50% humidity for 48 hours, then subjected to a creep test under conditions of a temperature of 60 ℃ and a load of 500g, and the peel distance after 60 minutes from the application of the load was measured, and evaluated as shown below.
"Good" is shown in the following description: the separation distance is 5mm or less with respect to each substrate.
"×": The above is not the case.
TABLE 1
TABLE 2
The numerals in tables 1 to 2 represent parts by mass.
The moisture-curable polyurethane hot melt resin composition of the present invention is known to have excellent initial adhesiveness and adhesion.
On the other hand, the initial adhesiveness of comparative example 1, which is a case where the aliphatic polyester polyol (a 2-1) was not used, was poor.
The adhesion was poor in comparative example 2, which was a case where the aliphatic polyester polyol (a 2-2) was not used.
The adhesion was poor in comparative example 3 in which the mass ratio of the aliphatic polyester polyol (a 2-1) to (a 2-2) was smaller than 1.

Claims (6)

1. A moisture-curable polyurethane hot-melt resin composition comprising a urethane prepolymer (i) having isocyanate groups as a reaction product of a polyol (A) and a polyisocyanate (B),
The polyol (A) contains:
a long-chain crystalline polyester polyol (a 1);
An aliphatic polyester polyol (a 2) other than the long-chain crystalline polyester polyol (a 1) starting from a diol having a2, 2-dimethyl-1, 3-propylene group; and
An aromatic polyester polyol (a 3),
The aliphatic polyester polyol (a 2) is used in combination with the aliphatic polyester polyol (a 2-1) having a number average molecular weight of 1000 to 3000 and the aliphatic polyester polyol (a 2-2) having a number average molecular weight of 5000 to 9000,
The mass ratio (a 2-1)/(a 2-2) of the aliphatic polyester polyol (a 2-1) having a number average molecular weight of 1000 to 3000 to the aliphatic polyester polyol (a 2-2) having a number average molecular weight of 5000 to 9000 is 1 to 3.
2. The moisture-curable polyurethane hot melt resin composition of claim 1, wherein the diol having 2, 2-dimethyl-1, 3-propylene is neopentyl glycol.
3. The moisture-curable polyurethane hot-melt resin composition according to claim 1, wherein, relative to the total amount of the polyol (A) and the polyisocyanate (B),
The amount of the long-chain crystalline polyester polyol (a 1) used is 32 to 40 parts by mass,
The total amount of the aliphatic polyester polyol (a 2) is 15 to 38 parts by mass,
The amount of the aromatic polyester polyol (a 3) used is 15 to 35 parts by mass.
4. An adhesive comprising the moisture-curable polyurethane hot-melt resin composition according to claim 1.
5. A laminate comprising a substrate and a coating of the adhesive according to claim 4.
6. The laminate according to claim 5, wherein the substrate is an aluminum-based substrate or a polyvinyl chloride substrate.
CN202280078327.3A 2022-03-22 2022-10-20 Moisture-curable polyurethane hot-melt resin composition, adhesive, and laminate Pending CN118302468A (en)

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JP5194518B2 (en) * 2007-03-30 2013-05-08 Ｄｉｃ株式会社 Moisture curable polyurethane hot melt adhesive and construction material using the same
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