WO2023090236A1 - ウレタン樹脂組成物、及び、積層体 - Google Patents

ウレタン樹脂組成物、及び、積層体 Download PDF

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Publication number
WO2023090236A1
WO2023090236A1 PCT/JP2022/041827 JP2022041827W WO2023090236A1 WO 2023090236 A1 WO2023090236 A1 WO 2023090236A1 JP 2022041827 W JP2022041827 W JP 2022041827W WO 2023090236 A1 WO2023090236 A1 WO 2023090236A1
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WO
WIPO (PCT)
Prior art keywords
urethane resin
resin composition
polyethylene glycol
manufactured
urethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/041827
Other languages
English (en)
French (fr)
Inventor
章恵 藤下
亮 前田
智博 鉄井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to KR1020247010936A priority Critical patent/KR20240097821A/ko
Priority to CN202280070710.4A priority patent/CN118541447A/zh
Priority to EP22895518.3A priority patent/EP4435054A4/en
Priority to JP2023561554A priority patent/JP7568136B2/ja
Publication of WO2023090236A1 publication Critical patent/WO2023090236A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3

Definitions

  • the present invention relates to a urethane resin composition containing water.
  • Urethane resin is widely used in the production of synthetic leather (including artificial leather) due to its mechanical strength and good texture.
  • solvent-based urethane resins containing N,N-dimethylformamide (DMF) have hitherto been the mainstream.
  • DMF N,N-dimethylformamide
  • urethane dispersion which is urethane resin dispersed in water, has begun to be considered as an alternative raw material for the intermediate porous layer formed by wet solidification of conventional solvent-based urethane resin.
  • PUD foams are being investigated in various ways.
  • the problem to be solved by the present invention is a water-containing urethane resin composition that can form a film having excellent crack resistance, texture, peel strength, and flexibility at low temperatures even when mechanically foamed. It is to provide things.
  • the present invention comprises a urethane resin (A) having a nonionic group, water (B), polyethylene glycol (c1), and/or polyethylene glycol (c2) having an alkoxy group having 11 or less carbon atoms.
  • a urethane resin composition characterized by containing a film auxiliary agent (C) is provided.
  • the present invention also provides a laminate comprising at least a substrate (i) and a foam layer (ii) formed from the urethane resin composition.
  • the urethane resin composition of the present invention contains water and is environmentally friendly.
  • the urethane resin composition of the present invention can form a film having excellent crack resistance, texture, peel strength, and low-temperature flexibility even when mechanically foamed. Therefore, the urethane resin composition of the present invention can be suitably used as a material for synthetic leather, and in particular can be suitably used as a foam layer of synthetic leather.
  • the urethane resin composition of the present invention contains a urethane resin (A) having a nonionic group, water (B), and a specific film forming aid (C).
  • the volatilization rate of water in the urethane resin composition can be made mild and uniform during drying, so cracks in the film can be suppressed, and the texture, It is presumed that a coating excellent in peel strength and the like was obtained.
  • the film forming aid (C) it is essential to use polyethylene glycol (c1) and/or polyethylene glycol (c2) having an alkoxy group with 11 or less carbon atoms.
  • the number of carbon atoms of the alkoxy group in the polyethylene glycol (c2) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3, from the viewpoint of obtaining even better crack resistance. is more preferred, and 1 (methoxy group) is particularly preferred. Further, the number of the alkoxy groups in one molecule of the polyethylene glycol (c2) ranges from 1 to 2, preferably 1.
  • the weight average molecular weights of the polyethylene glycol (c1) and the polyethylene glycol (c2) are preferably in the range of 100 to 4,000, more preferably in the range of 100 to 3,000, from the viewpoint of obtaining even better crack resistance. is more preferred, and a range of 400 to 2,000 is even more preferred.
  • the weight average molecular weights of the polyethylene glycol (c1) and the polyethylene glycol (c2) are values measured by gel permeation column chromatography (GPC).
  • the urethane resin (A) has a nonionic group, is dispersible in water, and does not require a cross-linking agent, so that excellent low-temperature flexibility can be obtained.
  • Examples of methods for obtaining the urethane resin having the nonionic group include a method using a compound having an oxyethylene structure as a raw material.
  • Examples of the compound having an oxyethylene structure include polyether polyols having an oxyethylene structure such as polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, and polyethylene glycol dimethyl ether. . These compounds may be used alone or in combination of two or more. Among these, it is preferable to use polyethylene glycol and/or polyethylene glycol dimethyl ether because the hydrophilicity can be controlled more easily.
  • the number average molecular weight of the compound having an oxyethylene structure is preferably in the range of 200 to 10,000, from the viewpoint of obtaining even better emulsifiability and water dispersion stability. A range of 300 to 2,000 is more preferred, and a range of 300 to 1,000 is particularly preferred. In addition, the number average molecular weight of the compound having the oxyethylene structure indicates a value measured by a gel permeation column chromatography (GPC) method.
  • GPC gel permeation column chromatography
  • urethane resin (A) specifically, for example, a reaction product of a chain extender (a1), a polyol (a2), a polyisocyanate (a3), and a compound having the oxyethylene structure can be used. can.
  • chain extender (a1) those having a molecular weight of less than 500 (preferably in the range of 50 to 450) can be used. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene can be used.
  • Glycol 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4 '-dihydroxydiphenyl ether, chain extender having a hydroxyl group such as trimethylolpropane; Cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine A chain extender having an amino group such as can be used. These chain extenders may be used alone or in combination of two or more.
  • the molecular weight of the chain extender (a1) indicates a value calculated from the
  • chain extender (a1) the chain can be easily extended even at a relatively low temperature of 30 ° C. or less, and the energy consumption during the reaction can be suppressed.
  • a chain extender having an amino group hereinafter referred to as abbreviated as "amine chain extender”. It is more preferable to use a range of amine-based chain extenders. When two or more types of chain extenders are used in combination, the molecular weight indicates the average value, and the average value may be included in the preferred molecular weight range.
  • the proportion of the chain extender (a1) used even better mechanical strength, film-forming properties, texture, peel strength, foam retention, emulsifiability, low-temperature flexibility, and water dispersion stability can be obtained.
  • the range of 0.1 to 30% by mass of the total mass of the raw materials constituting the urethane resin (X) is more preferable, and 0.5 to 30% by mass.
  • a range of 10% by weight is particularly preferred.
  • polyether polyol for example, polyether polyol, polyester polyol, polyacrylic polyol, polycarbonate polyol, polybutadiene polyol, etc.
  • polyacrylic polyol for example, polycarbonate polyol, polybutadiene polyol, etc.
  • polycarbonate polyol for example, polycarbonate polyol, polybutadiene polyol, etc.
  • polybutadiene polyol polystylene glycol
  • these polyols may be used alone or in combination of two or more.
  • polyol (a2) those other than the said compound which has the said oxyethylene structure which provides the said nonionic group are used.
  • the number average molecular weight of the polyol (a2) is preferably in the range of 500 to 100,000, more preferably in the range of 800 to 10,000, from the viewpoint of the mechanical strength of the resulting film.
  • the number average molecular weight of the polyol (a2) is the value measured by gel permeation column chromatography (GPC).
  • the ratio of the polyol (a2) to be used is more preferably in the range of 40 to 90% by mass in the total mass of the raw materials constituting the urethane resin (A), from the viewpoint of obtaining even better mechanical strength, and 50 to 90% by mass.
  • a range of 80% by weight is particularly preferred.
  • polyisocyanate (a3) examples include aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate; hexamethylene diisocyanate, Aliphatic polyisocyanates such as lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, or alicyclic polyisocyanates can be used. These polyisocyanates may be used alone or in combination of two or
  • the use ratio of the polyisocyanate (a3) is more preferably in the range of 5 to 40% by mass based on the total mass of the raw materials constituting the urethane resin (A) from the viewpoint of obtaining even better mechanical strength.
  • a range of up to 35% by weight is particularly preferred.
  • the urethane resin (A) is used from the viewpoint of obtaining even better foam retention, emulsifiability, water dispersion stability, low-temperature flexibility, and film-forming properties. It is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably in the range of 0.25 to 3% by mass, based on the total mass of the constituent raw materials.
  • the average particle size of the urethane resin (A) is in the range of 0.01 to 1 ⁇ m from the viewpoint of obtaining even better foam retention, surface smoothness, texture, low-temperature flexibility, and film-forming properties. preferably 0.05 to 0.9 ⁇ m. A method for measuring the average particle size of the urethane resin (A) will be described later in Examples.
  • the content of the urethane resin (A) in the urethane resin composition of the present invention is preferably 50-80% by mass, more preferably 50-70% by mass.
  • the so-called urethane resin (A) solid content in the aqueous dispersion is high, so even if the foam is mechanically foamed, the retention is even more excellent, and the drying property of the urethane resin composition is improved. / Or the crack resistance after drying is also excellent, and excellent texture and low-temperature flexibility can be obtained.
  • water (B) used in the present invention ion-exchanged water, distilled water, or the like can be used. These waters may be used alone or in combination of two or more.
  • the polyol (a2), the polyisocyanate (a3), and the compound having an oxyethylene structure are reacted in the absence of a solvent to obtain a compound having an isocyanate group.
  • a urethane prepolymer (i) is obtained (hereinafter abbreviated as the “prepolymer step”), then the urethane prepolymer (i) is dispersed in the water (hereinafter abbreviated as the “emulsification step”), and then , a step of reacting the chain extender (a1) to obtain a urethane resin (A) (hereinafter abbreviated as a “chain extend step”).
  • the prepolymer step is preferably carried out without a solvent.
  • the prepolymer process was generally carried out in an organic solvent such as methyl ethyl ketone or acetone. It took several production days on site. In addition, it is difficult to completely distill off the organic solvent in the solvent removal step, and there are many cases in which a small amount of the organic solvent remains, making it difficult to completely respond to environmental concerns.
  • the prepolymer in the absence of solvent, it is possible to obtain a urethane resin that is completely free of organic solvents and to save labor in the production process.
  • the molar ratio [isocyanate Group / (hydroxyl group and amino group)]
  • the molar ratio [isocyanate Group / (hydroxyl group and amino group)]
  • the molar ratio is preferably in the range of 1.1 to 3, more preferably in the range of 1.2 to 2.
  • reaction in the prepolymer step is carried out at 50 to 120°C for 1 to 10 hours.
  • the emulsification step includes, for example, a reactor equipped with stirring blades; Kneaders such as; Homomixer, Static Mixer, Filmix, Ebara Milder, Clearmix, Ultra Turrax, Cavitron, Biomixer, and other rotary dispersion mixers; Ultrasonic dispersion equipment; Instead, it can be performed by using a device or the like that can mix by the flow of the fluid itself.
  • Kneaders such as; Homomixer, Static Mixer, Filmix, Ebara Milder, Clearmix, Ultra Turrax, Cavitron, Biomixer, and other rotary dispersion mixers; Ultrasonic dispersion equipment; Instead, it can be performed by using a device or the like that can mix by the flow of the fluid itself.
  • the emulsification step is preferably performed at a temperature at which water does not evaporate, for example, a range of 10 to 90° C.
  • the emulsification step can be performed using the same equipment as the prepolymer step. .
  • the isocyanate group of the urethane prepolymer (i) reacts with the chain elongation agent (a1) to increase the molecular weight of the urethane prepolymer (i) to obtain the urethane resin (A). It is a process.
  • the temperature for the chain elongation step is preferably 50° C. or lower from the viewpoint of productivity.
  • the molar ratio of the isocyanate group of the urethane prepolymer (i) to the sum of the hydroxyl groups and amino groups of the chain extender (a1) [(hydroxyl group and amino group)/isocyanate group] is preferably in the range of 0.8 to 1.1, and 0.9 to 1 in terms of obtaining even better low-temperature flexibility, crack resistance, film-forming properties, and mechanical strength. A range is more preferred.
  • the chain elongation step can be performed using the same equipment as the prepolymer step.
  • the urethane resin composition of the present invention contains the urethane resin (A), water (B), and film-forming aid (C) as essential components, and may contain other additives as necessary. good too.
  • additives examples include surfactants, cross-linking agents, emulsifiers, neutralizers, thickeners, urethanization catalysts, fillers, pigments, dyes, flame retardants, leveling agents, antiblocking agents, and the like. be able to. These additives may be used alone or in combination of two or more.
  • organic solvent when producing the urethane resin (A), it is preferable that substantially no organic solvent is contained, but an organic solvent may be added as an additive.
  • a surfactant (D) having a hydrophobic portion having 10 or more carbon atoms is used in order to prevent bubbles generated by mechanical foaming from disappearing and to obtain more excellent crack resistance and texture. is preferably used.
  • surfactant (D) for example, a surfactant represented by the following formula (2); fatty acid salt, succinate, sulfosuccinate, octadecyl sulfosuccinate, sulfosuccinate, etc. can be used. These surfactants may be used alone or in combination of two or more.
  • R represents a linear or branched alkyl group having 10 to 20 carbon atoms
  • X represents Na, K, NH 4 , morpholine, ethanolamine, or triethanolamine.
  • the surfactant (D) among the surfactants described above, it is preferable to use a surfactant represented by the formula (2), which has 13 carbon atoms, from the viewpoint of obtaining even more excellent foam retention. More preferred are those exhibiting ⁇ 19 straight-chain alkyl groups, and the use of stearates is particularly preferred.
  • the laminate has at least a substrate (i) and a foam layer (ii) formed from the urethane resin composition.
  • Examples of the base material (i) include polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, glass fiber, carbon fiber, Fiber base materials such as non-woven fabrics, woven fabrics, and knitted fabrics made of blended fibers thereof, etc.; non-woven fabrics impregnated with resin such as polyurethane resin; non-woven fabrics further provided with a porous layer; thermoplastic urethane (TPU) etc. can be used.
  • (X) A method of foaming the urethane resin composition to obtain a foaming liquid, coating the foaming liquid on a release paper, drying it, and bonding it to the substrate (i);
  • (Y) A method of obtaining a foaming liquid by foaming the urethane resin composition, applying the foaming liquid onto a skin layer prepared on a release paper, drying the foaming liquid, and laminating the foaming liquid to the substrate (i).
  • (Z) The urethane resin composition is foamed to obtain a foaming liquid, the foaming liquid is applied onto the substrate (i), dried, and if necessary, a release paper is placed thereon.
  • a method of laminating the prepared skin layer (iii) may be used.
  • Examples of methods for obtaining a foamed liquid by foaming the urethane resin composition include manual stirring and mechanical foaming using a mixer such as a mechanical mixer. Among these methods, the method using a mixer is preferable because the foaming liquid can be easily obtained.
  • a mixer for example, a method of stirring at 500 to 3,000 rpm for 10 seconds to 10 minutes can be mentioned. At this time, from the viewpoint of obtaining a foamed layer (ii) with a good texture, it is preferable to increase the volume by 1.3 to 7 times, preferably 1.2 to 2 times, before and after foaming. is more preferred.
  • Examples of the method of applying the obtained foaming liquid to the substrate (i) and the like include methods using a roll coater, knife coater, comma coater, applicator, and the like.
  • Examples of the method for drying the coated material include a method of drying at a temperature of 60 to 130°C for 30 seconds to 10 minutes.
  • the thickness of the foam layer (ii) obtained by the above method is, for example, 5 to 300 ⁇ m.
  • the density of the foam layer (ii) is preferably from 200 to 1,000 kg/m 3 and more preferably from 400 to 800 kg/m 3 from the viewpoint of obtaining a more excellent feel.
  • the density of the foam layer (ii) is the value obtained by subtracting the weight of the base material (i) per 10 cm square from the weight of the laminate per 10 cm square, divided by the thickness of the foam layer (ii). indicates
  • the skin layer (iii) can be formed from a known material by a known method.
  • solvent-based urethane resin water-based urethane resin, silicone resin, polypropylene resin, polyester resin, etc.
  • Polycarbonate-based urethane resin is preferably used when emphasis is placed on soft texture, heat resistance, and hydrolysis resistance. Further, it is more preferable to use a water-based polycarbonate-based urethane resin in order to reduce DMF in an environmentally friendly manner.
  • a surface treatment layer (iv) may be further provided on the skin layer (iii), if necessary, for the purpose of improving scratch resistance and imparting glossiness.
  • the surface treatment layer (iv) can be formed by a known method using a known material.
  • the urethane resin composition of the present invention contains water and is environmentally friendly.
  • the urethane resin composition of the present invention can form a film having excellent crack resistance, texture, peel strength, and low-temperature flexibility even when mechanically foamed. Therefore, the urethane resin composition of the present invention can be suitably used as a material for synthetic leather, and in particular can be suitably used as a foam layer of synthetic leather.
  • the urethane prepolymer heated to 70° C., 65 parts by mass of a 20% aqueous solution of sodium dodecylbenzenesulfonate emulsifier (“Neogen S-20F” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 948 parts by mass of water were stirred and mixed in a homomixer. An emulsion was obtained. Immediately thereafter, a water-diluted solution of isophorone diamine (IPDA) having an amino group content equivalent to the NCO group and an equimolar amount was added to extend the chain, and finally the content of the urethane resin (A-1) was 58 mass. % of urethane resin (A-1) composition was obtained.
  • IPDA isophorone diamine
  • the urethane prepolymer heated to 70° C., 64 parts by mass of a 20% aqueous solution of sodium dodecylbenzenesulfonate emulsifier (“Neogen S-20F” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 811 parts by mass of water were stirred and mixed with a homomixer. An emulsion was obtained. Immediately thereafter, a water-diluted solution of IPDA having an amino group content equivalent to 95% of the NCO groups was added to extend the chain, and finally the urethane resin (A-2) content was 60% by mass. -2) A composition was obtained.
  • Example 1 100 g of the urethane resin (A-1) composition obtained in Synthesis Example 1, 2.0 g of thickener "Borch Gel ALA” (manufactured by Borchers), 2.0 g of ammonium stearate, methoxy polyethylene glycol (NOF Corporation manufactured by Uniox M-550, hereinafter abbreviated as “MPEG”.) 5.0 g was stirred with a mechanical mixer at 2,000 rpm, and air was added to make the volume 150% of the initial volume. It was adjusted. This was applied onto release paper and dried at 80° C. for 3 minutes to obtain a 300 ⁇ m-thick urethane foam layer, which was laminated to a non-woven fabric to obtain a synthetic leather.
  • MPEG methoxy polyethylene glycol
  • Example 2 100 g of the urethane resin (A-1) composition obtained in Synthesis Example 1, 2.0 g of a thickener "Borch Gel ALA” (manufactured by Borchers), 2.0 g of ammonium stearate, polyethylene col (manufactured by NOF Corporation) "PEG #400", number average molecular weight; 400, hereinafter abbreviated as "PEG”).
  • a compounded liquid was prepared. This was applied onto release paper and dried at 80° C. for 3 minutes to obtain a 300 ⁇ m-thick urethane foam layer, which was laminated to a non-woven fabric to obtain a synthetic leather.
  • Example 3 100 g of the urethane resin (A-2) composition obtained in Synthesis Example 2, 2.0 g of a thickening agent "Borch Gel ALA" (manufactured by Borchers), 2.0 g of ammonium stearate, and 5.0 g of MPEG were mixed in a mechanical mixer 2, A mixed liquid having a volume of 150% of the initial volume was prepared by stirring at 000 rpm and incorporating air. This was applied onto release paper and dried at 80° C. for 3 minutes to obtain a 300 ⁇ m-thick urethane foam layer, which was laminated to a non-woven fabric to obtain a synthetic leather.
  • a mixed liquid having a volume of 150% of the initial volume was prepared by stirring at 000 rpm and incorporating air. This was applied onto release paper and dried at 80° C. for 3 minutes to obtain a 300 ⁇ m-thick urethane foam layer, which was laminated to a non-woven fabric to obtain a synthetic leather.
  • the number-average molecular weights of polyols, film-forming aids, etc. used in Synthesis Examples and Comparative Synthesis Examples are values obtained by measurement under the following conditions by gel permeation column chromatography (GPC).
  • Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 Book “TSKgel G2000" (7.8 mm I.D.
  • Examples 1 to 3 which are the urethane resin compositions of the present invention, gave synthetic leathers with excellent crack resistance, texture, peel strength, and low-temperature flexibility.
  • Comparative Examples 1 and 2 are embodiments in which a urethane resin having an anionic group was used instead of the urethane resin (A) having a nonionic group, but the low-temperature flexibility was poor.
  • Comparative Example 3 is an embodiment in which the film-forming aid (C) is not used, but all of crack resistance, texture, peel strength, and low-temperature flexibility were poor.

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  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)
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Abstract

本発明は、ノニオン性基を有するウレタン樹脂（Ａ）、水（Ｂ）、並びに、ポリエチレングリコール（ｃ１）、及び／又は炭素原子数が１１以下のアルコキシ基を有するポリエチレングリコール（ｃ２）である成膜助剤（Ｃ）を含有することを特徴とするウレタン樹脂組成物を提供する。また、本発明は、少なくとも、基材（ｉ）、及び、前記ウレタン樹脂組成物により形成された発泡層（ｉｉ）を有することを特徴とする積層体を提供する。このウレタン樹脂組成物は、優れた耐クラック性、風合い、剥離強度、及び低温での屈曲性を有する皮膜を形成できる。

Description

ウレタン樹脂組成物、及び、積層体
　本発明は、水を含有するウレタン樹脂組成物に関する。
　ウレタン樹脂は、その機械的強度や風合いの良さから、合成皮革（人工皮革含む。）の製造に広く利用されている。この用途においては、これまでＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）を含有する溶剤系ウレタン樹脂が主流であった。しかしながら、欧州でのＤＭＦ規制、中国や台湾でのＶＯＣ排出規制の強化、大手アパレルメーカーによるＤＭＦ規制などを背景に、合成皮革を構成する各層用のウレタン樹脂組成物の脱ＤＭＦ化が求められている。
　このような環境下、ウレタン樹脂を水中に分散させたウレタンディスパージョン（ＰＵＤ）は、従来の溶剤系ウレタン樹脂を湿式凝固させて形成する中間多孔層の代替原料として検討され始めている。この代替には、湿式成膜品と同等の風合い等を付与するため、ＰＵＤの発泡体とする検討が種々行われている。
　前記ＰＵＤの発泡体を得る方法としては、例えば、マイクロカプセルを配合したり、二酸化炭素等の気体をＰＵＤ配合液に分散させる機械発泡などが検討されている（例えば、特許文献１を参照。）。しかしながら、マイクロカプセルを配合する方法では、得られる発泡体の風合いが不良となったり、マイクロカプセルの膨張による平滑性不良が問題となる。また、気体を分散させる方法では、発泡体を製造する過程で配合液にかませた気泡が消失等するため、泡サイズ等の制御が困難であり、風合いの良好な合成皮革を安定して得ることは困難であった。
　このような背景から、近年では簡便に発泡体を得る方法として、ＰＵＤを機械で撹拌して泡立てる機械発泡手法が検討されている。しかしながら、機械発泡方法では、ＰＵＤの水を乾燥している最中にウレタン皮膜に亀裂（クラック）が入ることにより、風合い、剥離強度、低温耐屈曲性等の物性発現が安定しない問題があった。
特開２００７－１９１８１０号公報
　本発明が解決しようとする課題は、機械発泡させても優れた耐クラック性、風合い、剥離強度、及び、低温での屈曲性を有する皮膜を形成することができる、水を含有するウレタン樹脂組成物を提供することである。
　本発明は、ノニオン性基を有するウレタン樹脂（Ａ）、水（Ｂ）、並びに、ポリエチレングリコール（ｃ１）、及び／又は炭素原子数が１１以下のアルコキシ基を有するポリエチレングリコール（ｃ２）である成膜助剤（Ｃ）を含有することを特徴とするウレタン樹脂組成物を提供するものである。また、本発明は、少なくとも、基材（ｉ）、及び、前記ウレタン樹脂組成物により形成された発泡層（ｉｉ）を有することを特徴とする積層体を提供するものである。
　本発明のウレタン樹脂組成物は、水を含有するものであり、環境対応型のものである。また、本発明のウレタン樹脂組成物は、機械発泡させても優れた耐クラック性、風合い、剥離強度、及び、低温屈曲性を有する皮膜を形成することができる。よって、本発明のウレタン樹脂組成物は、合成皮革の材料として好適に使用することができ、特に合成皮革の発泡層として好適に使用することができる。
　本発明のウレタン樹脂組成物は、ノニオン性基を有するウレタン樹脂（Ａ）、水（Ｂ）、及び、特定の成膜助剤（Ｃ）を含有するものである。
　本発明においては、前記特定の成膜助剤（Ｃ）を含有することが必須である。特定の成膜助剤（Ｃ）を用いることにより、ウレタン樹脂組成物中の水の乾燥時の、水の揮発速度をマイルドかつ均一にできるため、皮膜のクラックを抑制することができ、風合い、剥離強度等に優れる皮膜が得られたと推察される。
　前記成膜助剤（Ｃ）としては、ポリエチレングリコール（ｃ１）、及び／又は炭素原子数が１１以下のアルコキシ基を有するポリエチレングリコール（ｃ２）を用いることが必須である。
　前記ポリエチレングリコール（ｃ２）における前記アルコキシ基の炭素原子数としては、より一層優れた耐クラック性が得られる点から、１～５の範囲が好ましく、１～３の範囲がより好ましく、１～２の範囲が更に好ましく、１（メトキシ基）が特に好ましい。また、前記ポリエチレングリコール（ｃ２）１分子中における前記アルコキシ基の数は１～２個の範囲であり、好ましくは１個である。
　前記ポリエチレングリコール（ｃ１）及び前記ポリエチレングリコール（ｃ２）の重量平均分子量としては、より一層優れた耐クラック性が得られる点から、１００～４，０００の範囲が好ましく、１００～３，０００の範囲がより好ましく、４００～２，０００の範囲が更に好ましい。なお、前記ポリエチレングリコール（ｃ１）及び前記ポリエチレングリコール（ｃ２）の重量平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー（ＧＰＣ）法により測定した値を示す。
　前記成膜助剤（Ｃ）の使用量としては、後述するウレタン樹脂（Ａ）（＝固形分）１００質量部に対して、０．０５～５０質量部の範囲が好ましく、０．１～２０質量部の範囲が好ましい。
　前記ウレタン樹脂（Ａ）は、ノニオン性基を有するものであり、水に分散し得るものであり、また架橋剤を必要としないため、優れた低温屈曲性を得ることができる。
　前記ノニオン性基を有するウレタン樹脂を得る方法としては、例えば、オキシエチレン構造を有する化合物を原料として用いる方法が挙げられる。
　前記オキシエチレン構造を有する化合物としては、例えば、ポリエチレングリコール、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレンポリオキシテトラメチレングリコール、ポリエチレングリコールジメチルエーテル等のオキシエチレン構造を有するポリエーテルポリオールを用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。これらの中でも、より簡便に親水性を制御できる点から、ポリエチレングリコール、及び／又は、ポリエチレングリコールジメチルエーテルを用いることが好ましい。
　前記オキシエチレン構造を有する化合物の数平均分子量としては、より一層優れた乳化性、及び、水分散安定性が得られる点から、２００～１０，０００の範囲であることが好ましく、３００～３，０００の範囲がより好ましく、３００～２，０００の範囲であることがより好ましく、３００～１，０００の範囲が特に好ましい。なお、前記オキシエチレン構造を有する化合物の数平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー（ＧＰＣ）法により測定した値を示す。
　前記ウレタン樹脂（Ａ）としては、具体的には、例えば、鎖伸長剤（ａ１）、ポリオール（ａ２）、ポリイソシアネート（ａ３）、及び、前記オキシエチレン構造を有する化合物の反応物を用いることができる。
　前記鎖伸長剤（ａ１）としては、分子量が５００未満（好ましくは５０～４５０の範囲）のものを用いることができ、具体的には、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ヘキサメチレングリコール、サッカロース、メチレングリコール、グリセリン、ソルビトール、ビスフェノールＡ、４，４’－ジヒドロキシジフェニル、４，４’－ジヒドロキシジフェニルエーテル、トリメチロールプロパン等の水酸基を有する鎖伸長剤；エチレンジアミン、１，２－プロパンジアミン、１，６－ヘキサメチレンジアミン、ピペラジン、２，５－ジメチルピペラジン、イソホロンジアミン、１，２－シクロヘキサンジアミン、１，３－シクロヘキサンジアミン、１，４－シクロヘキサンジアミン、４，４’－ジシクロヘキシルメタンジアミン、３，３’－ジメチル－４，４’－ジシクロヘキシルメタンジアミン、１，４－シクロヘキサンジアミン、ヒドラジン等のアミノ基を有する鎖伸長剤などを用いることができる。これらの鎖伸長剤は単独で用いても２種以上を併用してもよい。なお、前記鎖伸長剤（ａ１）の分子量は、化学式から算出される値を示す。
　前記鎖伸長剤（ａ１）としては、３０℃以下の比較的低い温度下でも容易に鎖伸長でき、反応時のエネルギー消費を抑制できる点、及び、ウレア基導入によるより一層優れた機械的強度、造膜性、泡保持性、風合い、低温屈曲性、及び、剥離強度が得られる点、ウレタン樹脂（Ａ）の高固形分化がより一層容易となる点から、アミノ基を有する鎖伸長剤（以下「アミン系鎖伸長剤」と略記する。）が好ましく、より一層優れた泡保持性、乳化性、低温屈曲性、風合い、及び、水分散安定性が得られる点から、分子量が３０～２５０の範囲のアミン系鎖伸長剤を用いることがより好ましい。なお、前記鎖伸長剤として２種類以上を併用する場合には、前記分子量はその平均値を示し、平均値が前記好ましい分子量の範囲に包含されればよい。
　前記鎖伸長剤（ａ１）の使用割合としては、より一層優れた機械的強度、造膜性、風合い、剥離強度、泡保持性、乳化性、低温屈曲性、及び、水分散安定性が得られる点、ウレタン樹脂（Ａ）の高固形分化がより一層容易となる点から、ウレタン樹脂（Ｘ）を構成する原料の合計質量中０．１～３０質量％の範囲が更に好ましく、０．５～１０質量％の範囲が特に好ましい。
　前記ポリオール（ａ２）としては、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリアクリルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール等を用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。なお、前記ポリオール（ａ２）としては、前記ノニオン性基を付与する前記オキシエチレン構造を有する化合物以外のものを用いる。
　前記ポリオール（ａ２）の数平均分子量としては、得られる皮膜の機械的強度の点から、５００～１００，０００の範囲であることが好ましく、８００～１０，０００の範囲であることがより好ましい。なお、前記ポリオール（ａ２）の数平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー（ＧＰＣ）法により測定した値を示す。
　前記ポリオール（ａ２）の使用割合としては、より一層優れた機械的強度が得られる点から、ウレタン樹脂（Ａ）を構成する原料の合計質量中４０～９０質量％の範囲が更に好ましく、５０～８０質量％の範囲が特に好ましい。
　前記ポリイソシアネート（ａ３）としては、例えば、フェニレンジイソシアネート、トルエンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、ナフタレンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート、カルボジイミド化ジフェニルメタンポリイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、ダイマー酸ジイソシアネート、ノルボルネンジイソシアネート等の脂肪族ポリイソシアネート又は脂環式ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは、単独で用いても２種以上を併用してもよい。
　前記ポリイソシアネート（ａ３）の使用割合としては、より一層優れた機械的強度が得られる点から、ウレタン樹脂（Ａ）を構成する原料の合計質量中５～４０質量％の範囲が更に好ましく、１０～３５質量％の範囲が特に好ましい。
　前記オキシエチレン構造を有する化合物の使用割合としては、より一層優れた泡保持性、乳化性、水分散安定性、低温屈曲性、及び、造膜性が得られる点から、ウレタン樹脂（Ａ）を構成する原料の合計質量中５質量％以下であることが好ましく、３質量％以下がより好ましく、０．２５～３質量％の範囲が更に好ましい。
　前記ウレタン樹脂（Ａ）の平均粒子径としては、より一層優れた泡保持性、表面平滑性、風合い、低温屈曲性、及び、造膜性が得られる点から、０．０１～１μｍの範囲であることが好ましく、０．０５～０．９μｍの範囲がより好ましい。なお、前記ウレタン樹脂（Ａ）の平均粒子径の測定方法は、後述する実施例にて記載する。
　本発明のウレタン樹脂組成物における、前記ウレタン樹脂（Ａ）の含有率としては、５０～８０質量％が好ましく、５０～７０質量％がより好ましい。水分散体中のいわゆるウレタン樹脂（Ａ）固形分が高いことにより、機械発泡により泡をかませてもより一層保持性に優れ、かつウレタン樹脂組成物の乾燥性が向上するため、乾燥時及び／又は乾燥後における耐クラック性にも一掃優れ、また、優れた風合い、低温屈曲性を得ることができる。
　本発明で用いる水（Ｂ）としては、イオン交換水、蒸留水等を用いることができる。これらの水は単独で用いても２種以上を併用してもよい。
　次に、本発明で用いるウレタン樹脂（Ａ）の製造方法について説明する。
　本発明で用いるウレタン樹脂（Ａ）の製造方法としては、前記ポリオール（ａ２）、前記ポリイソシアネート（ａ３）、及び、前記オキシエチレン構造を有する化合物を無溶媒下で反応させて、イソシアネート基を有するウレタンプレポリマー（ｉ）を得（以下、「プレポリマー工程」と略記する。）、次いで、ウレタンプレポリマー（ｉ）を前記水に分散させ（以下、「乳化工程」と略記する。）、その後、前記鎖伸長剤（ａ１）を反応させてウレタン樹脂（Ａ）を得る工程（以下、「鎖伸長工程」と略記する。）を有するものである。
　前記プレポリマー工程は、無溶媒下で行うことが好ましい。従来技術では、プレポリマー工程の際に、メチルエチルケトン、アセトン等の有機溶媒中で行うことが一般的であったが、乳化工程後に前記有機溶剤を留去する脱溶剤工程が必要であり、実生産現場では数日の生産日数を要していた。また、前記脱溶剤工程で完全に有機溶剤を留去することも困難であり、若干の有機溶剤を残存しているケースが多く、環境対応に完全に対応することは困難であった。一方、無溶媒下でプレポリマーを製造することで、有機溶剤を完全に含まないウレタン樹脂が得られ、かつ、その生産工程も省力化することが可能である。
　前記プレポリマー工程における、前記ポリオール（ａ２）が有する水酸基、及び、前記オキシエチレン構造を有する化合物が有する水酸基及びアミノ基の合計と、前記ポリイソシアネート（ａ３）が有するイソシアネート基とのモル比［イソシアネート基／（水酸基及びアミノ基）］としては、より一層優れた泡保持性、低温屈曲性、耐クラック性、表面平滑性、造膜性、風合い、剥離強度、及び、機械的強度が得られる点から、１．１～３の範囲であることが好ましく、１．２～２の範囲がより好ましい。
　前記プレポリマー工程の反応は、例えば、５０～１２０℃で１～１０時間行うことが挙げられる。
　前記乳化工程は、例えば、撹拌翼を備えた反応釜；ニーダー、コンテイニアスニーダー、テーパーロール、単軸押出機、二軸押出機、三軸押出機、万能混合機、プラストミル、ボデーダ型混練機等の混練機；ホモミキサー、スタティックミキサー、フィルミックス、エバラマイルダー、クレアミックス、ウルトラターラックス、キャビトロン、バイオミキサー等の回転式分散混合機；超音波式分散装置；インラインミキサー等の可動部がなく、流体自身の流れによって混合できる装置などを使用することにより行うことができる。
　前記乳化工程は、水が蒸発しない温度下で行うことが好ましく、例えば、１０～９０℃の範囲が挙げられる、前記乳化工程は、前記プレポリマー工程と同様の設備を使用して行うことができる。
　前記鎖伸長工程は、前記ウレタンプレポリマー（ｉ）が有するイソシアネート基と、前記鎖伸長剤（ａ１）との反応により、ウレタンプレポリマー（ｉ）を高分子量化させ、ウレタン樹脂（Ａ）を得る工程である。前記鎖伸長工程の際の温度としては、生産性の点から、５０℃以下で行うことが好ましい。
　前記鎖伸長工程における、前記ウレタンプレポリマー（ｉ）が有するイソシアネート基と、前記鎖伸長剤（ａ１）が有する水酸基及びアミノ基の合計とのモル比［（水酸基及びアミノ基）／イソシアネート基］としては、より一層優れた低温屈曲性、耐クラック性、造膜性、及び、機械的強度が得られる点から、０．８～１．１の範囲であることが好ましく、０．９～１の範囲がより好ましい。
　前記鎖伸長工程は、前記プレポリマー工程と同様の設備を使用して行うことができる。
　本発明のウレタン樹脂組成物は、前記ウレタン樹脂（Ａ）、水（Ｂ）、及び、成膜助剤（Ｃ）を必須成分として含有するが、必要に応じてその他の添加剤を含有してもよい。
　前記その他の添加剤としては、例えば、界面活性剤、架橋剤、乳化剤、中和剤、増粘剤、ウレタン化触媒、充填剤、顔料、染料、難燃剤、レベリング剤、ブロッキング防止剤等を用いることができる。これらの添加剤は単独で用いても２種以上を併用してもよい。なお、前記ウレタン樹脂（Ａ）を製造する際には、実質的に有機溶剤を含まないことが好ましいが、添加剤として有機溶剤を添加してもよい。
　前記界面活性剤としては、機械発泡により生じた泡を消失から防止し、一層優れた耐クラック性および風合いが得られる点から、炭素原子数が１０以上の疎水部を有する界面活性剤（Ｄ）を用いることが好ましい。
　前記界面活性剤（Ｄ）としては、例えば、下記式（２）で示される界面活性剤；脂肪酸塩、コハク酸塩、スルホコハク酸塩、オクタデシルスルホコハク酸塩、スルホコハク酸エステル等を用いることができる。これらの界面活性剤は単独で用いても２種以上を併用しても良い。
Figure JPOXMLDOC01-appb-C000001
 （式（２）中、Ｒは炭素原子数１０～２０の直鎖又は分岐状のアルキル基を示し、ＸはＮａ、Ｋ、ＮＨ４、モルホリン、エタノールアミン、トリエタノールアミンを示す。）
　前記界面活性剤（Ｄ）としては、前記したものの中でも、より一層優れた泡保持性が得られる点から、前記式（２）で示される界面活性剤を用いることが好ましく、炭素原子数が１３～１９の直鎖のアルキル基を示すものがより好ましく、ステアリン酸塩を用いることが特に好ましい。
　前記界面活性剤（Ｄ）を用いる場合の使用量としては、より一層優れた泡保持性が得られる点から、前記ウレタン樹脂（Ａ）（＝固形分）１００質量に対して、０．０１～３０質量部の範囲であることが好ましく、０．１～２０質量部の範囲がより好ましい。
　次に、本発明の積層体について説明する。
　前記積層体は、少なくとも、基材（ｉ）、及び、前記ウレタン樹脂組成物により形成された発泡層（ｉｉ）を有するものである。
　前記基材（ｉ）としては、例えば、ポリエステル繊維、ポリエチレン繊維、ナイロン繊維、アクリル繊維、ポリウレタン繊維、アセテート繊維、レーヨン繊維、ポリ乳酸繊維、綿、麻、絹、羊毛、グラスファイバー、炭素繊維、それらの混紡繊維等による不織布、織布、編み物等の繊維基材；前記不織布にポリウレタン樹脂等の樹脂を含浸させたもの；前記不織布に更に多孔質層を設けたもの；熱可塑性ウレタン（ＴＰＵ）等の樹脂基材などを用いることができる。
　次に、本発明の積層体の製造方法について説明する。
　前記積層体の製造方法としては、例えば、
（Ｘ）前記ウレタン樹脂組成物を気泡させて起泡液を得、この起泡液を離型紙上に塗布し、乾燥させ、前記基材（ｉ）と貼り合わせる方法、
（Ｙ）前記ウレタン樹脂組成物を起泡させ起泡液を得、この起泡液を、離型紙上に作製した表皮層上に塗布し、乾燥させ、前記基材（ｉ）と貼り合わせる方法、
（Ｚ）前記ウレタン樹脂組成物を起泡させ起泡液を得、この起泡液を前記基材（ｉ）上に塗布し、乾燥させ、必要に応じて、その上に、離型紙上に作製した表皮層（ｉｉｉ）を貼り合わせる方法などが挙げられる。
　前記ウレタン樹脂組成物を起泡させ起泡液を得る方法としては、例えば、手による撹拌、メカニカルミキサー等のミキサーを使用する機械発泡などが挙げられる。これらの中でも、簡便に起泡液が得られる点から、ミキサーを使用する方法が好ましい。ミキサーを使用する場合には、例えば、５００～３，０００ｒｐｍにて１０秒～１０分間撹拌させる方法が挙げられる。この際、風合いの良好な発泡層（ｉｉ）が得られる点から、起泡させる前後にて、１．３～７倍の体積にすることが好ましく、１．２～２倍の体積にすることがより好ましい。
　得られた起泡液を基材（ｉ）等に塗布する方法としては、例えば、ロールコーター、ナイフコーター、コンマコーター、アプリケーター等を使用する方法が挙げられる。
　前記塗布物の乾燥方法としては、例えば、６０～１３０℃の温度で３０秒～１０分間乾燥させる方法が挙げられる。
　以上の方法により得られる発泡層（ｉｉ）の厚さとしては、例えば、５～３００μｍである。
　前記発泡層（ｉｉ）の密度としては、より一層優れた風合いが得られる点から、２００～１，０００ｋｇ／ｍ３であることが好ましく、４００～８００ｋｇ／ｍ３の範囲がより好ましい。なお、前記発泡層（ｉｉ）の密度は、１０ｃｍ四方あたりの積層体の重量から１０ｃｍ四方あたりの基材（ｉ）の重量を減じた値を、発泡層（ｉｉ）の厚さで除した値を示す。
　前記表皮層（ｉｉｉ）としては、公知の材料により公知の方法で形成することができ、例えば、溶剤系ウレタン樹脂、水系ウレタン樹脂、シリコーン樹脂、ポリプロピレン樹脂、ポリエステル樹脂等を用いることができる。柔軟な風合い、及び耐熱性、耐加水分解性を重視する場合は、ポリカーボネート系ウレタン樹脂を用いることが好ましい。また、環境対応でのＤＭＦ低減化のためには、水系ポリカーボネート系ウレタン樹脂を用いることがより好ましい。
　前記表皮層（ｉｉｉ）上には、必要に応じて、耐擦傷性向上やグロス性付与等を目的に表面処理層（ｉｖ）を更に設けてもよい。前記表面処理層（ｉｖ）としては、公知の材料により公知の方法で形成することができる。
　以上、本発明のウレタン樹脂組成物は、水を含有するものであり、環境対応型のものである。また、本発明のウレタン樹脂組成物は、機械発泡させても優れた耐クラック性、風合い、剥離強度、及び、低温屈曲性を有する皮膜を形成することができる。よって、本発明のウレタン樹脂組成物は、合成皮革の材料として好適に使用することができ、特に合成皮革の発泡層として好適に使用することができる。
　以下、実施例を用いて、本発明をより詳細に説明する。
［合成例１］ウレタン樹脂（Ａ－１）組成物の調製
　オクチル酸第一錫０．１質量部の存在下、ポリエーテルポリオール（三菱化学株式会社製「ＰＴＭＧ２０００」、数平均分子量；２，０００）１，０００質量部と、ポリエチレングリコール（日油株式会社製「ＰＥＧ６００」、数平均分子量；６００）３８質量部と、ジシクロヘキシルメタンジイソシアネート（ＨＭＤＩ）２６２質量部とをＮＣＯ％が２．８％に達するまで１００℃で反応させてウレタンプレポリマーを得た。
　７０℃に加熱した前記ウレタンプレポリマーと乳化剤ドデシルベンゼンスルホン酸Ｎａ２０％水溶液（第一工業製薬株式会社製「ネオゲンＳ－２０Ｆ」）６５質量部、水９４８質量部をホモミキサーで攪拌、混合して乳化液を得た。その後、直ちにＮＣＯ基と等モル量に相当するアミノ基含量のイソホロンジアミン（ＩＰＤＡ）の水希釈液を添加して鎖伸長させ、最終的にウレタン樹脂（Ａ－１）の含有率が、５８質量％のウレタン樹脂（Ａ－１）組成物を得た。
［合成例２］ウレタン樹脂（Ａ－２）組成物の調製
　オクチル酸第一錫０．１質量部の存在下、ポリカーボネートポリオール（１，６－ヘキサンジオールを原料とするもの、数平均分子量；２，０００）を１，０００質量部と、ＰＥＧ６００を１８質量部と、ＨＭＤＩ２６２質量部とをＮＣＯ％が３．１質量％に達するまで１００℃で反応させてウレタンプレポリマーを得た。
　７０℃に加熱した前記ウレタンプレポリマーと乳化剤ドデシルベンゼンスルホン酸Ｎａ２０％水溶液（第一工業製薬株式会社製「ネオゲンＳ－２０Ｆ」）６４質量部、水８１１質量部をホモミキサーで攪拌、混合して乳化液を得た。その後、直ちにＮＣＯ基の９５％に相当するアミノ基含量のＩＰＤＡの水希釈液を添加して鎖伸長させ、最終的にウレタン樹脂（Ａ－２）の含有率が６０質量％のウレタン樹脂（Ａ－２）組成物を得た。
［実施例１］
　合成例１で得られたウレタン樹脂（Ａ－１）組成物１００ｇ、増粘剤「Ｂｏｒｃｈ　Ｇｅｌ　ＡＬＡ」（Ｂｏｒｃｈｅｒｓ社製）２．０ｇ、ステアリン酸アンモニウム２．０ｇ、メトキシポリエチレングリコール（日油株式会社製「ユニオックスＭ－５５０」、以下「ＭＰＥＧ」と略記する。） ５．０ｇをメカニカルミキサー２，０００ｒｐｍにて撹拌し、空気を含ませることで初期体積に対し１５０％体積にした配合液を調整した。
　これを離型紙上に塗工し、８０℃で３分間乾燥させることで、厚さ３００μｍのウレタン発泡層を得、これを不織布に貼り合わせることで合成皮革を得た。
［実施例２］
　合成例１で得られたウレタン樹脂（Ａ－１）組成物１００ｇと増粘剤「Ｂｏｒｃｈ　Ｇｅｌ　ＡＬＡ」（Ｂｏｒｃｈｅｒｓ社製）２．０ｇ、ステアリン酸アンモニウム２．０ｇ、ポリエチレンコール（日油株式会社製「ＰＥＧ＃４００」、数平均分子量；４００、以下「ＰＥＧ」と略記する。）５．０ｇをメカニカルミキサー２，０００ｒｐｍにて撹拌し、空気を含ませることで初期体積に対し１５０％体積にした配合液を調整した。
　これを離型紙上に塗工し、８０℃で３分間乾燥させることで、厚さ３００μｍのウレタン発泡層を得、これを不織布に貼り合わせることで合成皮革を得た。
［実施例３］
　合成例２で得られたウレタン樹脂（Ａ－２）組成物１００ｇと増粘剤「Ｂｏｒｃｈ　Ｇｅｌ　ＡＬＡ」（Ｂｏｒｃｈｅｒｓ社製）２．０ｇ、ステアリン酸アンモニウム２．０ｇ、ＭＰＥＧ５．０ｇをメカニカルミキサー２，０００ｒｐｍにて撹拌し、空気を含ませることで初期体積に対し１５０％体積にした配合液を調整した。
　これを離型紙上に塗工し、８０℃で３分間乾燥させることで、厚さ３００μｍのウレタン発泡層を得、これを不織布に貼り合わせることで合成皮革を得た。
［比較例１］
　アニオン性水性ウレタン樹脂（ＤＩＣ株式会社製「ハイドランＷＬＳ－１２０ＡＲ」）１００ｇ増粘剤「Ｂｏｒｃｈ　Ｇｅｌ　ＡＬＡ」（Ｂｏｒｃｈｅｒｓ社製）２．０ｇ、ステアリン酸アンモニウム２．０ｇ、ＭＰＥＧ５．０ｇ、架橋剤（日清紡ケミカル株式会社製「カルボジライトＳＶ－０２」）４．０ｇをメカニカルミキサー２，０００ｒｐｍにて撹拌し、空気を含ませることで初期体積に対し１５０％体積にした配合液を調整した。
　これを離型紙上に塗工し、８０℃で３分間乾燥させることで、厚さ３００μｍのウレタン発泡層を得、これを不織布に貼り合わせることで合成皮革を得た。
［比較例２］
　アニオン性水性ウレタン樹脂（ＤＩＣ株式会社製「ハイドランＷＬＳ－１２０ＡＲ」）１００ｇ増粘剤「Ｂｏｒｃｈ　Ｇｅｌ　ＡＬＡ」（Ｂｏｒｃｈｅｒｓ社製）２．０ｇ、ステアリン酸アンモニウム２．０ｇ、ＰＥＧ５．０ｇ、架橋剤（日清紡ケミカル株式会社製「カルボジライトＳＶ－０２」）４．０ｇをメカニカルミキサー２，０００ｒｐｍにて撹拌し、空気を含ませることで初期体積に対し１５０％体積にした配合液を調整した。
　これを離型紙上に塗工し、８０℃で３分間乾燥させることで、厚さ３００μｍのウレタン発泡層を得、これを不織布に貼り合わせることで合成皮革を得た。
［比較例３］
　合成例１で得られたウレタン樹脂（Ａ－１）組成物１００ｇと増粘剤「Ｂｏｒｃｈ　Ｇｅｌ　ＡＬＡ」（Ｂｏｒｃｈｅｒｓ社製）２．０ｇ、ステアリン酸アンモニウム３．０ｇをメカニカルミキサー２，０００ｒｐｍにて撹拌し、空気を含ませることで初期体積に対し150%体積にした配合液を調整した。
　これを離型紙上に塗工し、８０℃で３分間乾燥させることで、厚さ３００μｍのウレタン発泡層を得、これを不織布に貼り合わせることで合成皮革を得た。
［数平均分子量等の測定方法］
　合成例及び比較合成例で用いたポリオール、成膜助剤等の数平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー（ＧＰＣ）法により、下記の条件で測定し得られた値を示す。
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
　「ＴＳＫｇｅｌ　Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。
（標準ポリスチレン）
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－１０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－２５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－８０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１２８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２８８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－５５０」
［ウレタン樹脂（Ａ）の平均粒子径の測定方法］
　実施例及び比較例で得られたウレタン樹脂組成物をレーザー回折／散乱式粒度分布測定装置（株式会社堀場製作所製「ＬＡ－９１０」）を使用して、分散液として水を使用し、相対屈折率＝１．１０、粒子径基準が面積の時の平均粒子径を測定した。
［耐クラック性の評価方法］
　実施例及び比較例で得られた合成皮革の外観を観察し、クラックの有無を確認した。クラックがないものを「〇」、クラックが確認されたものを「×」と評価した。
［風合いの評価方法］
　実施例及び比較例で得られた合成皮革を手で触り、以下のように評価した。
　「〇」：柔軟性と弾力がある
　「×」：柔軟性が劣り、硬い。
［剥離強度の評価方法］
　２.５ｃｍ幅のホットメルトテープ（サン化成株式会社製「ＢＷ－２」）を、実施例及び比較例で得られた合成皮革のウレタン発泡層側に置いて１５０℃で３０秒加熱し、ホットメルトテープを接着した。ホットメルトテープの幅に沿って試料を切断した。この試料の一部を剥離し、基材とホットメルトテープをチャックで挟み、オートグラフ（島津製作所製）で剥離強度を測定し、以下の様に評価した。得られたデータの平均値を求め、１ｃｍ幅に換算した。
　「〇」；３ｋｇｆ／ｃｍ以上
　「×」；３ｋｇｆ／ｃｍ未満
［低温屈曲性の測定方法］
　実施例及び比較例で得られた合成皮革をフレキソメーター（株式会社安田精機製作所製「低温槽付フレキシオメーター」）での屈曲性試験（－３５℃、１００回／毎分）を行い、合成皮革の表面に割れが生じるまでの回数を測定し、以下のように評価した。
　「○」：１０，０００回以上
　「×」：１０，０００回未満
Figure JPOXMLDOC01-appb-T000002
　本発明のウレタン樹脂組成物である実施例１～３は、優れた耐クラック性、風合い、剥離強度、及び、低温屈曲性を有する合成皮革が得られることが分かった。
　一方、比較例１～２は、ノニオン性基を有するウレタン樹脂（Ａ）の代わりに、アニオン性基を有するウレタン樹脂を用いた態様であるが、低温屈曲性が不良であった。
　比較例３は、成膜助剤（Ｃ）を使用しない態様であるが、耐クラック性、風合い、剥離強度、低温屈曲性いずれも不良であった。

Claims (7)

  1. ノニオン性基を有するウレタン樹脂（Ａ）、水（Ｂ）、並びに、ポリエチレングリコール（ｃ１）、及び／又は炭素原子数が１１以下のアルコキシ基を有するポリエチレングリコール（ｃ２）である成膜助剤（Ｃ）を含有することを特徴とするウレタン樹脂組成物。
  2. 前記ポリエチレングリコール（ｃ１）及び前記ポリエチレングリコール（ｃ２）の重量平均分子量が、１００～４，０００の範囲である請求項１記載のウレタン樹脂組成物。
  3. 前記ウレタン樹脂（Ａ）のノニオン性基が、オキシエチレン構造を有する化合物により形成されたものである請求項１又は２記載のウレタン樹脂組成物。
  4. 更に、炭素原子数が１０以上の疎水部を有する界面活性剤（Ｄ）を含有するものである請求項１～３のいずれか１項記載のウレタン樹脂組成物。
  5. 前記界面活性剤（Ｄ）が、ステアリン酸塩である請求項４記載のウレタン樹脂組成物。
  6. 少なくとも、基材（ｉ）、及び、請求項１～５のいずれか１項記載のウレタン樹脂組成物により形成された発泡層（ｉｉ）を有することを特徴とする積層体。
  7. 前記発泡層（ｉｉ）が、前記ウレタン樹脂組成物を機械発泡することにより形成されたものである請求項６記載の積層体。
PCT/JP2022/041827 2021-11-18 2022-11-10 ウレタン樹脂組成物、及び、積層体 Ceased WO2023090236A1 (ja)

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