CN116323198A - Urethane prepolymer, moisture-curable urethane hot-melt resin composition, and laminate - Google Patents

Urethane prepolymer, moisture-curable urethane hot-melt resin composition, and laminate Download PDF

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Publication number
CN116323198A
CN116323198A CN202180067588.0A CN202180067588A CN116323198A CN 116323198 A CN116323198 A CN 116323198A CN 202180067588 A CN202180067588 A CN 202180067588A CN 116323198 A CN116323198 A CN 116323198A
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polyol
urethane prepolymer
mass
moisture
difunctional
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CN116323198B (en
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奥泉宽女
河村亮
佐佐木一弥
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Dainichiseika Color and Chemicals Mfg Co Ltd
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Dainichiseika Color and Chemicals Mfg Co Ltd
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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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • 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)
  • Laminated Bodies (AREA)

Abstract

A urethane prepolymer which is a reactant of a polyol (A) and a polyisocyanate (B), wherein the reactant has an isocyanate group at the terminal, the polyol (A) contains at least a polycarbonate polyol (A-1) and an EO/PO copolymer polyol (A-2) as difunctional polyols, the polycarbonate polyol (A-1) contains a crystalline polycarbonate polyol (a) having at least a structural unit derived from an alkanediol having 6 or more carbon atoms, the content of the crystalline polycarbonate polyol (a) in the difunctional polyol is 20% by mass or more, the content of the polycarbonate polyol (A-1) in the difunctional polyol is 30% by mass or more, and the molar ratio [ EO/PO ] of the EO/PO copolymer polyol (A-2) is 25/75 to 80/20.

Description

Urethane prepolymer, moisture-curable urethane hot-melt resin composition, and laminate
Technical Field
The present invention relates to a urethane prepolymer, a moisture-curable urethane hot-melt resin composition, and a laminate.
Background
The moisture-permeable waterproof fabric has both high waterproof property against rain and moisture permeability for reducing uncomfortable feeling caused by sultry during sweating, and is therefore used not only for general rain gear but also for mountain climbing wear, far-foot wear, sportswear and the like.
As a method for producing a moisture-permeable waterproof fabric, a method of bonding a base fabric to a film-like material having moisture permeability via an adhesive has been mainly used. In this case, from the viewpoint of obtaining more excellent moisture permeability, it is desirable that the adhesive also have moisture permeability.
As a method for producing an adhesive having moisture permeability, for example, patent document 1 proposes a method in which moisture permeability is imparted by using a polyol composed of an oxyethylene group which is excellent in hydrophilicity, and adhesion is imparted by using a polyester polyol having high crystallinity.
In addition, patent document 2 proposes an adhesive having adhesion and durability using a highly crystalline polycarbonate polyol (for example, nippollan 980R) as a polyol component.
Prior art literature
Patent literature
Patent document 1: international publication No. 2017/104266,
patent document 2: japanese patent laid-open No. 2003-246830.
Disclosure of Invention
Problems to be solved by the invention
The conventional adhesive has moisture permeability, but has a problem that water resistance is impaired and durability against washing (hereinafter also referred to as "washing durability") is easily insufficient because of a high concentration of polyoxyethylene groups in the polyol.
In addition, the adhesive blended with the polyester polyol is degraded within 2 to 3 years from the beginning of use due to hydrolysis caused by rain, sweat, washing, etc., and is not suitable for long-term use.
In addition, from the viewpoint of improving the adhesiveness, there is a problem that the use of a highly crystalline polycarbonate polyol deteriorates the feel and deteriorates the wearing comfort.
The present invention has been made in view of the above-described conventional problems, and provides a urethane prepolymer which can form a laminate having excellent moisture permeability and also excellent adhesion, hydrolysis resistance, washing durability and hand. Further, a moisture-curable urethane hot-melt resin composition containing the urethane prepolymer and a laminate containing the cured product thereof are provided.
Means for solving the problems
Specifically, the gist of the present invention is the following [1] to [7].
[1] A urethane prepolymer having an isocyanate group at a terminal as a reactant of a polyol (a) and a polyisocyanate (B), wherein the polyol (a) contains at least the following components as a difunctional polyol: a polycarbonate polyol (A-1) which contains a crystalline polycarbonate polyol (a) having at least a structural unit derived from an alkanediol having 6 or more carbon atoms, and an EO/PO copolymer polyol (A-2);
the crystalline polycarbonate polyol (a) in the difunctional polyol is contained in an amount of 20 mass% or more, the polycarbonate polyol (A-1) in the difunctional polyol is contained in an amount of 30 mass% or more, and the EO/PO copolymer polyol (A-2) has a molar ratio [ EO/PO ] of 25/75 to 80/20.
[2] The urethane prepolymer according to [1], wherein the EO/PO copolymer polyol (A-2) in the difunctional polyol is contained in an amount of 50 to 70% by mass.
[3] The urethane prepolymer according to [1] or [2], wherein the polyisocyanate (B) contains an aliphatic polyisocyanate and an aromatic polyisocyanate.
[4] The urethane prepolymer according to any one of [1] to [3], wherein the crystalline polycarbonate polyol (a) in the difunctional polyol is contained in an amount of 20 to 50 mass%.
[5] The urethane prepolymer according to any one of [1] to [4], wherein an equivalent ratio [ NCO/OH ] of an isocyanate group of the polyisocyanate (B) to a hydroxyl group of the polyol (A) is 1.5 to 3.0.
[6] A moisture-curable urethane hot-melt resin composition comprising the urethane prepolymer according to any one of [1] to [5 ].
[7] A laminate comprising the cured product of the urethane prepolymer according to any one of [1] to [5] or the cured product of the moisture-curable urethane hot-melt resin composition according to [6 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a urethane prepolymer which can form a laminate having excellent moisture permeability and also excellent in adhesion, hydrolysis resistance, washing durability and hand can be provided. Further, a moisture-curable urethane hot-melt resin composition containing the urethane prepolymer and a laminate containing the cured product thereof can be provided.
Drawings
FIG. 1 is a schematic explanatory view illustrating the form of a sample used for evaluation in examples.
FIG. 2 is a diagram illustrating the form of a Ji Erre aging oven used for evaluation of examples.
Detailed Description
[1] Urethane prepolymers
The urethane prepolymer of the present invention is a urethane prepolymer having an isocyanate group at the terminal as a reactant of a polyol (A) and a polyisocyanate (B), and is characterized in that,
the polyol (A) contains at least the following components as difunctional polyols:
a polycarbonate polyol (A-1) which contains a crystalline polycarbonate polyol (a) having at least a structural unit derived from an alkanediol having 6 or more carbon atoms, and
EO/PO copolymer polyols (A-2);
the crystalline polycarbonate polyol (a) in the difunctional polyol is contained in an amount of 20 mass% or more and,
the content of the polycarbonate polyol (A-1) in the difunctional polyol is 30 mass% or more,
the molar ratio [ EO/PO ] of the EO/PO copolymer polyol (A-2) is 25/75 to 80/20.
The mode of the present invention will be described in detail below. In the present specification, "crystalline polycarbonate polyol (a) having at least a structural unit derived from an alkanediol having 6 or more carbon atoms" may be simply referred to as "crystalline polycarbonate polyol (a)".
[ polyol (A) ]
The polyol (a) used in the present invention contains at least the following components as difunctional polyols: a polycarbonate polyol (A-1) containing the above crystalline polycarbonate polyol (a), and an EO/PO copolymer polyol (A-2).
< difunctional polyol >
[ polycarbonate polyol (A-1) ]
The polycarbonate polyol (A-1) contains at least a crystalline polycarbonate polyol (a) having at least a structural unit derived from an alkanediol having 6 or more carbon atoms. Since the polycarbonate polyol (A-1) contains the crystalline polycarbonate polyol (a), both the adhesion and hydrolysis resistance are improved.
In the present invention, "crystallinity" means a peak of crystallization heat or heat of fusion that can be confirmed in DSC (differential scanning calorimeter) measurement according to JIS 7121-1987.
The crystalline polycarbonate polyol (a) has at least a structural unit derived from an alkanediol having 6 or more carbon atoms, and the carbon number of the alkanediol is preferably 6 to 16, more preferably 6 to 10, from the viewpoint of improving the adhesion and hydrolysis resistance. The alkanediol used for the crystalline polycarbonate polyol (a) is preferably a linear alkanediol.
Specific examples of the alkanediol having 6 or more carbon atoms include 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 11-undecanediol, and 1, 12-dodecanediol, and among these, 1, 6-hexanediol, 1, 9-nonanediol, and 1, 10-decanediol are preferable.
The crystalline polycarbonate polyol (a) may have a structural unit derived from a compound other than the alkanediol having 6 or more carbon atoms.
The compound constituting the other structural unit is preferably an alkanediol having an even number of linear carbon atoms, and examples thereof include ethylene glycol and 1, 4-butanediol.
If the structural unit described above contains "structural unit derived from an alkanediol having 6 or more carbon atoms" as an essential component, it may contain 1 kind of the structural unit alone or 2 kinds or more of the structural unit. That is, the polymer may be a homopolymer, or 2 or more kinds of copolymers, or 2 or more kinds of homopolymers may be mixed and used.
The content of the structural unit derived from the alkanediol having 6 or more carbon atoms is preferably 20mol% or more, more preferably 50mol% or more, and still more preferably 70mol% or more, based on the whole alkanediol in the crystalline polycarbonate polyol (a). When the content of the structural unit derived from the alkanediol having 6 or more carbon atoms is within the above range, both the adhesive property and the hydrolysis resistance can be improved.
The number average molecular weight of the crystalline polycarbonate polyol (a) is preferably 500 to 6,000, more preferably 700 to 5,000, and still more preferably 1,000 to 4,000. When the number average molecular weight is within the above range, the viscosity of the urethane prepolymer is not excessively high, and the handleability is improved.
In the present specification, the number average molecular weight refers to a value measured by gel permeation chromatography (GPC method) using polystyrene as a standard substance.
The content of the crystalline polycarbonate polyol (a) in the polycarbonate polyol (a-1) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and still more preferably 70 to 100% by mass. If the content of the crystalline polycarbonate polyol (a) in the polycarbonate polyol (a-1) is within the above range, particularly the water-resistant adhesive strength is improved.
The polycarbonate polyol (A-1) may contain a polycarbonate polyol other than the crystalline polycarbonate polyol (a). As the other polycarbonate polyol, an amorphous polycarbonate polyol is preferable.
Examples of the amorphous polycarbonate polyol include, but are not limited to, a polycarbonate polyol obtained by homopolymerizing 1, 2-propanediol, 1, 3-butanediol, 1, 5-pentanediol, neopentyl glycol, or copolymerizing with another alkanediol, in which a peak of crystallization heat or melting heat cannot be confirmed in DSC (differential scanning calorimeter) measurement according to JIS 7121-1987. In the present invention, the use of an amorphous polycarbonate polyol can improve the touch.
The alkanediol used for the amorphous polycarbonate polyol may be a linear alkanediol, a branched alkanediol, or an alicyclic alkanediol. Further, the alkanediol preferably contains both an alkanediol having an even number of carbon atoms and an alkanediol having an odd number of carbon atoms.
The number average molecular weight of the other polycarbonate polyol is preferably 500 to 6,000, more preferably 700 to 5,000, and still more preferably 1,000 to 4,000. When the number average molecular weight is within the above range, the viscosity of the urethane prepolymer is not excessively high, and the handleability is improved.
When the polycarbonate polyol (A-1) contains another polycarbonate polyol, the content thereof in the polycarbonate polyol (A-1) is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.
[ EO/PO copolymer polyol (A-2) ]
The EO/PO copolymer polyol (A-2) used in the present invention is a copolymer containing a unit derived from ethylene oxide and a unit derived from propylene oxide, and the molar ratio [ EO/PO ] of the ethylene oxide unit (EO) to the propylene oxide unit (PO) is 25/75 to 80/20.
By using the EO/PO copolymer polyol (A-2) in the present invention, it is possible to impart moisture permeability to the urethane prepolymer and also to improve the water-resistant adhesive strength, and thus to improve the washing durability.
In the above molar ratio, if the EO ratio is less than 25, the moisture permeability is lowered, which is not preferable. On the other hand, if it exceeds 80, the water-resistant adhesive strength is lowered, and the hand feeling is also lowered, which is not preferable.
The molar ratio [ EO/PO ] is preferably 30/70 to 80/20, more preferably 30/70 to 75/25, and even more preferably 50/50 to 75/25, from the viewpoint of improving the touch while simultaneously providing moisture permeability and water-resistant adhesive strength.
The copolymer containing a unit derived from ethylene oxide and a unit derived from propylene oxide may be any of a block copolymer, a random copolymer, and an alternating copolymer.
The number average molecular weight of the EO/PO copolymer polyol (A-2) is preferably 100 to 10,000, more preferably 300 to 9,000, still more preferably 500 to 5,000. When the number average molecular weight is within the above range, the viscosity of the urethane prepolymer is not excessively high, and the handleability is improved.
[ other difunctional polyol ]
Other difunctional polyols than those (A-1) and (A-2) described above may be used in the present invention.
Examples of the other difunctional polyols include polyethylene glycol, polypropylene glycol and polytetramethylene glycol, but polyester polyols are preferably not used in the present invention.
[ blending amount of each component in difunctional polyol ]
In the present invention, the content of the crystalline polycarbonate polyol (a) in the difunctional polyol is 20 mass% or more. If the content of the crystalline polycarbonate polyol (a) is less than 20 mass%, the adhesive strength, hydrolysis resistance, and washing durability (water-resistant adhesive strength) may not be sufficiently obtained. Therefore, from the viewpoint of improving these properties, the content of the crystalline polycarbonate polyol (a) in the difunctional polyol is preferably 20 to 80 mass%, more preferably 20 to 65 mass%, further preferably 20 to 50 mass%, and particularly preferably 30 to 50 mass%.
In the present invention, the content of the polycarbonate polyol (A-1) in the difunctional polyol is 30 mass% or more. When the content of the polycarbonate polyol (A-1) in the difunctional polyol is less than 30 mass%, hydrolysis resistance and the like are deteriorated. Therefore, the content of the polycarbonate polyol (a-1) in the difunctional polyol is preferably 30 to 70 mass%, more preferably 30 to 60 mass%, and even more preferably 30 to 55 mass% from the viewpoint of improving hydrolysis resistance and the like.
The EO/PO copolymer polyol (A-2) content in the above-mentioned difunctional polyol is preferably 50 to 70% by mass, more preferably 50 to 65% by mass, still more preferably 50 to 60% by mass. If the content of the EO/PO copolymer polyol (A-2) in the above-mentioned difunctional polyol is 50 mass% or more, the moisture permeability is improved, and if it is 70 mass% or less, the water-resistant adhesion is improved, and as a result, excellent washing durability is exhibited.
[ polyols other than difunctional polyol ]
In the present invention, polyols other than the above-mentioned difunctional polyols may be used, and examples thereof include polyols having a hydroxyl number of preferably 3 to 6, more preferably 3 to 4, and triols are preferred.
Examples of the triol include a triol type of polypropylene glycol, 1,2, 6-hexanetriol, 1,2, 3-butanetriol, pentanetriol, 1,2, 4-butanetriol, 1-trimethylol propane, triethanolamine, 1,2, 3-glycerol (glycerin), and a triol derived from castor oil, and among these, a triol type of polypropylene glycol is preferable.
The molecular weight of the polyol other than the difunctional polyol is preferably 100 to 1,000, more preferably 100 to 800. When the molecular weight is within the above range, the viscosity of the urethane prepolymer is not excessively high, and the handleability is improved.
The content of the difunctional polyol in the polyol (a) is preferably 90 mass% or more, more preferably 95 mass% or more.
On the other hand, the content of the polyol other than the difunctional polyol in the polyol (a) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less, relative to 100 parts by mass of the difunctional polyol. When the content of the polyol other than the difunctional polyol is not more than the above upper limit value, the amount of the difunctional polyol relatively increases, whereby a urethane prepolymer excellent in moisture permeability can be obtained.
< polyisocyanate (B) >
The polyisocyanate (B) may be a known aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate or the like.
Examples of the aromatic polyisocyanate include 1, 3-phenylene diisocyanate, 4' -diphenyl diisocyanate, 1, 4-phenylene diisocyanate, 4' -diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -toluidine diisocyanate, 2,4, 6-toluene triisocyanate, 1,3, 5-benzene triisocyanate, dianisidine diisocyanate, 4' -diphenyl ether diisocyanate, and 4,4',4 "-triphenylmethane triisocyanate.
Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, and 2, 4-trimethylhexamethylene diisocyanate.
Examples of the aromatic aliphatic polyisocyanate include ω, ω '-diisocyanate-1, 3-dimethylbenzene, ω' -diisocyanate-1, 4-diethylbenzene, 1, 4-tetramethylxylene diisocyanate, and 1, 3-tetramethylxylene diisocyanate.
Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3, 5-trimethylcyclohexyl isocyanate, 1, 3-cyclopentanediisocyanate, 1, 3-cyclohexanediisocyanate, 1, 4-cyclohexanediisocyanate, methyl-2, 6-cyclohexanediisocyanate, 4' -methylenebis (cyclohexylisocyanate), 1, 4-bis (isocyanatomethyl) cyclohexane, and 1, 4-bis (isocyanatomethyl) cyclohexane.
The polyisocyanate (B) may be used in combination with a trimethylolpropane adduct of the polyisocyanate (B), a water-reactive biuret, an isocyanurate ring-containing trimer, or the like.
In the present invention, the polyisocyanate (B) preferably contains an aliphatic polyisocyanate and an aromatic polyisocyanate. By containing the above 2 kinds, a laminate having excellent hand can be obtained. The mass ratio of the aromatic polyisocyanate (aromatic polyisocyanate/(aliphatic polyisocyanate and aromatic polyisocyanate) ×100) relative to the sum of the aliphatic polyisocyanate and the aromatic polyisocyanate is preferably 30 mass% or more, more preferably 40 mass% or more. The upper limit of the above mass ratio when the aliphatic polyisocyanate is contained is preferably 70 mass%, more preferably 60 mass%.
Among the above, preferred are 4,4' -diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanatomethyl-3, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), aliphatic polyisocyanate (HDI-type allophanate type polyisocyanate) and the like as the polyisocyanate (B) used in the present invention.
< additive >
The urethane prepolymer of the present invention may contain additives as required.
Examples of the additives include a light-resistant agent, an antioxidant, a slip agent, and a flame retardant. These additives may be used singly or in combination of 2 or more.
When the urethane prepolymer of the present invention contains an additive, the content thereof in the urethane prepolymer is preferably 20 mass% or less, more preferably 10 mass% or less, and still more preferably 5 mass% or less. If the content of the additive is within the above range, the effect of the additive can be obtained while the effect of the urethane prepolymer is obtained.
< method for producing urethane prepolymer >
The urethane prepolymer of the present invention can be obtained by reacting the polyol (a) with the polyisocyanate (B), and has isocyanate groups capable of reacting with moisture present in the air or in a substrate to which the urethane prepolymer is applied to form a crosslinked structure.
As a method for producing the urethane prepolymer of the present invention, for example, it can be produced by: the polyisocyanate (B) is placed in a reaction vessel so that the isocyanate groups are excessive relative to the hydroxyl groups of the polyol (A), and further, other necessary components are added thereto, followed by heating to react them.
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 is preferably 1.1 to 5.0, more preferably 1.4 to 5.0, still more preferably 1.5 to 5.0, and among these, preferably 1.5 to 4.0, more preferably 1.5 to 3.0, still more preferably 1.5 to 2.5, and still more preferably 1.5 to 2.0. When the equivalent ratio is within the above range, the peel strength when the urethane prepolymer is used as an adhesive is further improved, and a high tensile breaking strength and a heat softening temperature are easily obtained.
The isocyanate group content (hereinafter also referred to as "NCO%") of the urethane prepolymer of the present invention is preferably 1.7 to 5.5, more preferably 1.8 to 3.5.
When the NCO% is within the above range, the peel strength is further improved.
The NCO% of the urethane prepolymer mentioned above means that it is in accordance with JIS K1603-1:2007, values determined by potentiometric titration.
[2] Moisture-curable urethane hot-melt resin composition
The moisture-curable urethane hot-melt resin composition of the present invention is not particularly limited as long as it contains the urethane prepolymer of the present invention as an essential component, and may contain additives as needed.
As the above-mentioned additives, for example, curing catalysts, antioxidants, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent brighteners, silane coupling agents, waxes, thermoplastic resins, and the like can be used. These additives may be used singly or in combination of 2 or more.
When the moisture-curable urethane hot-melt resin composition of the present invention contains an additive, the content thereof is preferably 20 mass% or less, more preferably 10 mass% or less, and still more preferably 5 mass% or less. If the content of the additive is within the above range, the effect of the additive can be obtained while the effect of the urethane prepolymer is obtained.
[3] Laminate body
The laminate of the present invention is a laminate containing a cured product of the urethane prepolymer of the present invention or a cured product of the moisture-curable urethane hot-melt resin composition of the present invention. Specific examples of the laminate include a laminate having the following base fabric, the cured product, and the following moisture-permeable film in this order.
As described above, the urethane prepolymer and the moisture-curable urethane hot-melt resin composition of the present invention have excellent moisture permeability and also excellent adhesion, hydrolysis resistance, washing durability and hand feel, and therefore the obtained laminate represented by moisture-permeable waterproof fabric or synthetic leather can be suitably used for rain gear, mountain climbing clothing, far-foot clothing, sports wear and the like.
Examples of the base fabric constituting the laminate of the present invention include base fabrics using chemical fibers such as polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, and polylactic acid fibers, cotton, hemp, silk, wool, and blends thereof.
Examples of the moisture permeable film constituting the laminate of the present invention include:
(i) A moisture-permeable film obtained by coating a resin solution containing a thermoplastic resin having a hydrophilic group and an organic solvent on a release paper, and volatilizing the organic solvent;
(ii) A moisture-permeable film formed by molding thermoplastic resin pellets having a hydrophilic group;
(iii) A porous film having micropores formed by coating a resin solution containing a thermoplastic resin and an organic solvent on a release paper and volatilizing the organic solvent;
(iv) And a porous film having micropores formed by stretching a film obtained by melt-kneading and extruding a resin composition containing a thermoplastic resin and an inorganic filler having no compatibility with the thermoplastic resin to a predetermined magnification.
Examples of the method for producing the laminate of the present invention include the following methods: the urethane prepolymer or the moisture-curable urethane hot-melt resin composition of the present invention, which is preferably melted at 50 to 130 ℃, is coated on the moisture-permeable film, and then a base fabric is attached thereto, and then the urethane prepolymer or the moisture-curable urethane hot-melt resin composition is cured. According to this method, a laminate having a base fabric, the cured product, and a moisture-permeable film in this order can be easily obtained.
Examples of the method of applying the urethane prepolymer or the like to the moisture-permeable film include a method of intermittently applying the urethane prepolymer or the moisture-curable urethane hot-melt resin composition in the form of dots or meshes, and a method of applying the urethane prepolymer or the moisture-curable urethane hot-melt resin composition in the form of dots is preferable from the viewpoint of ease of production.
Examples of the intermittent coating method include gravure transfer coating using a engraved roll, screen coating, T-die coating, die coating with a gear pump, and fiber coating.
The thickness of the cured product of the urethane prepolymer in the laminate or the cured product of the moisture-curable urethane hot-melt resin composition is preferably 0.1 to 100. Mu.m, more preferably 1 to 50. Mu.m, still more preferably 5 to 30. Mu.m. When the thickness of each cured product is within the above range, the wearing comfort of the clothing using the laminate can be improved while maintaining the moisture permeability.
In the production of the laminate, the urethane prepolymer or the moisture-curable urethane hot-melt resin composition is preferably cured by drying and curing by a known method. The curing conditions are preferably such that the base fabric is pressure-bonded at 40 to 130℃and then cured at about 30℃and 65% RH for about 1 to 7 days.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1]
Nippollan 980R (number average molecular weight 2000, manufactured by Tosoh Co., ltd.) as crystalline polycarbonate polyol (a), BP-3025 (stable Polymer chemical Co., ltd., molar ratio [ EO/PO ] =30/70, number average molecular weight 2500), polyoxypropylene triol (T-700, number average molecular weight 700, manufactured by Sanchi chemical Co., ltd.), and 4,4' -diphenylmethane diisocyanate (MDI) as EO/PO copolymer polyol were charged into a glass reaction vessel provided with a stirrer, a thermometer, a gas inlet, etc., in blending amounts shown in Table 1, respectively.
Then, the inside of the reaction vessel was dehydrated by heating under reduced pressure, and then nitrogen gas was filled therein, followed by stirring at an internal temperature of 100℃for 120 minutes to react. Next, a light-resistant agent was added to obtain a polyurethane prepolymer. The urethane prepolymer obtained was evaluated as follows. The results are shown in table 1.
< examples 2 to 15, comparative examples 1 to 6>
Polyurethane prepolymers were produced in the same manner as in example 1, except that the proportions shown in table 1 and table 2 were changed. The urethane prepolymer obtained was evaluated as follows. The results are shown in tables 1 and 2.
[ evaluation method ]
< film Properties >
The urethane prepolymers obtained in examples and comparative examples were subjected to film physical properties measurement in accordance with the following points.
First, the urethane prepolymer thus obtained was melted at 100℃and coated on a release paper so that the film thickness after coating was 50 to 70. Mu.m. As a curing step, the film was obtained by standing at 30℃under an environment of 65% relative humidity for 4 days and further standing at room temperature (20 ℃) for 1 day. For the obtained film, the breaking strength and the heat softening temperature were measured as follows.
[ method for measuring breaking Strength ]
The obtained film was punched out of a dumbbell-shaped test piece in accordance with JIS3, and was stretched at a speed of 200mm/min under the conditions of 25℃and 30% RH or less using an automatic plotter AGS-J manufactured by Shimadzu corporation, and the tensile breaking strength was measured. In this evaluation, the higher the breaking strength, the higher the strength of the film.
[ method of measuring Heat softening temperature (Heat softening Point) ]
(1) Preparation of the sample
The film was peeled from the release paper to obtain a translucent film having a width of 1.5cm and a length of 6 cm. As shown in FIG. 1, clips 12 were attached to the upper and lower sides of the translucent film 10, the clips 12 were further fixed with Cellotage (registered trademark), and 450g/cm was applied while hanging on one clip 12 2 To produce a test specimen 16. The central portion of the film 10 was not covered with Cellotape (registered trademark) in the longitudinal direction of 2 cm.
(2) Measurement
As shown in fig. 2, the clips 12 without the weight 14 in the sample 16 of each example were mounted on the turntable 22 of the Ji Erre aging oven 20. Then, while rotating the turntable 22 at 5rpm, the temperature in the Ji Erre aging oven 20 was raised at a rate of 3 ℃/min from room temperature. The softening point is the temperature at which the film 10 is cut or stretched 2 times.
In the present evaluation, the higher the heat softening temperature (heat softening point) is, the higher the resistance (for example, resistance to hot melt tape adhesion or ironing) as a film is.
< production of moisture-permeable waterproof cloth for evaluation >
In order to measure the adhesive strength, moisture permeability, hydrolysis resistance, and water-resistant adhesive strength of the laminate, a moisture permeable waterproof cloth for evaluation was produced as follows.
(1) Production of skin (moisture permeable film)
The blend liquid was obtained by mixing 100 parts by mass of HI-MUREN Y-208-2 (manufactured by dai refinement industry co., ltd.), 10 parts by mass of a colorant [ seta DUT 4093White (manufactured by dai refinement industry co., ltd) ], 10 parts by mass of Dimethylformamide (DMF), and 5 parts by mass of Methyl Ethyl Ketone (MEK) as a solvent-based urethane resin. The above-mentioned blend was uniformly coated on a release paper in a wet coating amount of 50. Mu.m, using a gap coater. Then, the resultant was dried at 80℃for 2 minutes and further dried at 120℃for 3 minutes, whereby a skin (moisture permeable film) of a moisture permeable waterproof cloth having a film thickness of 10 to 15 μm was obtained.
(2) Bonding of skin to base fabric
The urethane prepolymers obtained in examples and comparative examples were melted at 100 ℃ and coated on the above skin (moisture permeable film). Then, the thickness of the urethane prepolymer was adjusted to 15 μm in the press treatment after the coating, and then the press-bonded base fabric (nylon silk) was processed at a lamination temperature of 100 ℃. As a curing step, the mixture was cured at a temperature of 30℃and a relative humidity of 65% for 4 days. The obtained laminate was used as a moisture-permeable waterproof cloth for evaluation, and the following evaluation was performed.
[ method for measuring adhesive Strength ]
The hot melt adhesive tape was laminated on the skin surface of the obtained moisture permeable waterproof cloth for evaluation, and the resultant was pressed by pressing an iron at 140℃for 1 minute to perform pressure bonding. After cooling at room temperature (20 ℃) for 1 hour, the base fabric and the skin adhered to the hot melt tape were peeled off, and the strength thereof was measured by an automatic plotter, whereby the adhesive strength was measured and evaluated according to the following criteria.
(Standard)
◎：≥1.3kg/inch
○：≥0.8kg/inch
×：＜0.8kg/inch
[ measurement of moisture permeability ]
According to JIS L1099: 2012, a-1 method (potassium chloride method), and the moisture permeability of the obtained moisture permeable waterproof cloth for evaluation was measured and evaluated according to the following criteria.
(Standard)
◎：≥5,000g/m 2 ·24h
○：≥3,000g/m 2 ·24h
[ hydrolysis resistance ]
The obtained moisture permeable waterproof cloth for evaluation was placed in a tank under 70 ℃/95% RH, and the adhesive strength before placement was compared with the adhesive strength after storage in the tank for a predetermined period of time, and the hydrolysis resistance was evaluated according to the following criteria. The retention ratio of the adhesive strength means a ratio of the adhesive strength after the storage in the tank for a predetermined time to the adhesive strength before the storage in the tank.
(Standard)
X: the retention of the adhesive strength after 5 weeks (5W) of storage was less than 70%
O: the retention rate of the adhesive strength after 5 weeks (5W) of storage is 70% or more
And (3) the following materials: the retention rate of the adhesive strength after 8 weeks (8W) of storage is 70% or more
[ Water-resistant adhesive Strength (washing durability test) ]
The obtained moisture-permeable waterproof cloth for evaluation was subjected to a total of 20 times of washing with a C-shaped standard washing machine (pulsator type) and drying with a C-drying method (flat drying) in accordance with JIS L-1930, and then the adhesive strength was measured. If the retention of the adhesive strength is 70% or more, it is judged that the adhesive has excellent water-resistant adhesive strength (o-evaluation), and if the retention is less than 70%, it is judged that the water-resistant adhesive strength is insufficient and the washing durability is insufficient (x-evaluation). The adhesive strength was measured by the same method as described above.
TABLE 1
TABLE 1
Figure BDA0004155744810000171
/>
Details of the components used in examples and comparative examples are as follows.
< crystalline polycarbonate polyol (a) >)
Nippollan 980R:1, 6-hexanediol homopolymer (number average molecular weight 2000, manufactured by Tosoh Co., ltd.)
Duranol G4672:1, 4-butanediol/1, 6-hexanediol (70 mol%/30 mol%) copolymer (number average molecular weight 2000, manufactured by Asahi chemical Co., ltd.)
BeneBioL NL2020DB:1, 4-butanediol/1, 10-decanediol (80 mol%/20 mol%) copolymer (number average molecular weight 2000, manufactured by Mitsubishi chemical Co., ltd.)
< amorphous polycarbonate polyol >
Duranol T5652:1, 5-pentanediol/1, 6-hexanediol (50 mol%/50 mol%) copolymer (number average molecular weight 2000, manufactured by Asahi chemical Co., ltd.)
< EO/PO copolymer polyol >
BP-3025: stable Polymer chemical Co., ltd., molar ratio [ EO/PO ] =30/70, number average molecular weight 2500
BP-2896: stable Polymer chemical Co., ltd., molar ratio [ EO/PO ] =28/72, number average molecular weight 960
BE-5028: stable Polymer chemical Co., ltd., molar ratio [ EO/PO ] =50/50, number average molecular weight 2800
DE-8735: stable Polymer chemical Co., ltd., molar ratio [ EO/PO ] =87/13, number average molecular weight 3500
DP-7530: stable Polymer chemical Co., ltd., molar ratio [ EO/PO ] =75/25, number average molecular weight 3000
< polyethylene glycol >
PEG2000: number average molecular weight 2000 manufactured by Sanyo chemical industry Co., ltd
< polyester polyol >
TEPE 85: number average molecular weight 2000 manufactured by Taiji chemical Co., ltd
< triol >
T-700: polyoxypropylene triol, manufactured by Mitsui chemical Co., ltd., number average molecular weight 700
< isocyanate >
MDI: dongcao, 4' -diphenylmethane diisocyanate
C-2770: dosoh, aliphatic polyisocyanate (HDI allophanate type polyisocyanate)
< additive >
Chesorb 770 (light fastness): double bond chemical bis (2, 6-tetramethyl-4-piperidinyl) sebacate
TABLE 2
TABLE 2
Figure BDA0004155744810000191
Figure BDA0004155744810000201
< examples 16 to 17>
A urethane prepolymer was produced in the same manner as in example 1, except that the ratio was changed to the one shown in table 3 and the reaction temperature was 110 ℃. The urethane prepolymer thus obtained was produced into a moisture-permeable waterproof cloth for evaluation by the above method, and the following hand feeling was evaluated in the same manner as in example 1 and example 8. The results are shown in table 3.
[ hand feel ]
The flexibility of the obtained moisture-permeable waterproof cloth for evaluation was compared with the touch feeling of rubbing by hand, and the evaluation was performed according to the following criteria. The standard moisture-permeable waterproof cloth was produced according to the following points.
[ Standard ]
And (3) the following materials: is softer than standard moisture permeable waterproof cloth
O: is as soft as standard moisture permeable waterproof cloth
Standard moisture-permeable waterproof cloth
As a raw material of the adhesive, 100 parts by mass of HI-MUREN Y-173 (polyurethane resin adhesive, manufactured by dai refining industry co., ltd.), 10 parts by mass of NE-crosslinking agent (isocyanate-based crosslinking agent, manufactured by dai refining industry co., ltd.), 20 parts by mass of Dimethylformamide (DMF), and 40 parts by mass of Methyl Ethyl Ketone (MEK) were mixed to prepare an adhesive blend liquid.
The obtained adhesive blend was applied to the skin (moisture permeable film) in a wet state of 50 μm using a gap coater, and dried at 80℃for 2 minutes to form an adhesive layer having a thickness of about 15. Mu.m.
Next, the base fabric (nylon silk) was laminated on the obtained adhesive layer, and the laminate was subjected to press bonding at a lamination temperature of 40 ℃. Then, a standard moisture-permeable waterproof cloth was manufactured by aging at 50 ℃ for 48 hours.
TABLE 3
TABLE 3 Table 3
Figure BDA0004155744810000211
From the above results, it is clear that the present invention can provide a urethane prepolymer which can form a laminate having excellent moisture permeability and also excellent adhesion, hydrolysis resistance, washing durability and hand.
Symbol description
10. Film and method for producing the same
12. Clip
14. Weight
16. Sample preparation
20. Ji Erre aging box
22. Turntable

Claims (7)

1. A urethane prepolymer having an isocyanate group at the terminal as a reactant of a polyol (A) and a polyisocyanate (B), characterized in that,
the polyol (A) contains at least the following components as difunctional polyol:
a polycarbonate polyol (A-1) which contains a crystalline polycarbonate polyol (a) having at least a structural unit derived from an alkanediol having 6 or more carbon atoms, and
EO/PO copolymer polyols (A-2);
the crystalline polycarbonate polyol (a) in the difunctional polyol is contained in an amount of 20 mass% or more and,
the content of the polycarbonate polyol (A-1) in the difunctional polyol is 30 mass% or more,
the molar ratio [ EO/PO ] of the EO/PO copolymer polyol (A-2) is 25/75 to 80/20.
2. The urethane prepolymer according to claim 1, wherein the EO/PO copolymer polyol (a-2) in the difunctional polyol is contained in an amount of 50 to 70 mass%.
3. The urethane prepolymer according to claim 1 or 2, wherein the polyisocyanate (B) contains an aliphatic polyisocyanate and an aromatic polyisocyanate.
4. The urethane prepolymer according to any one of claims 1 to 3, wherein the crystalline polycarbonate polyol (a) in the difunctional polyol is contained in an amount of 20 to 50 mass%.
5. The urethane prepolymer according to any one of claims 1 to 4, wherein the equivalent ratio [ NCO/OH ] of isocyanate groups of the polyisocyanate (B) to hydroxyl groups of the polyol (A) is 1.5 to 3.0.
6. A moisture-curable urethane hot-melt resin composition comprising the urethane prepolymer according to any one of claims 1 to 5.
7. A laminate comprising the cured product of the urethane prepolymer according to any one of claims 1 to 5 or the cured product of the moisture-curable urethane hot-melt resin composition according to claim 6.
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