WO2019098039A1 - 発泡ウレタンシート、及び、合成皮革 - Google Patents

発泡ウレタンシート、及び、合成皮革 Download PDF

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Publication number
WO2019098039A1
WO2019098039A1 PCT/JP2018/040669 JP2018040669W WO2019098039A1 WO 2019098039 A1 WO2019098039 A1 WO 2019098039A1 JP 2018040669 W JP2018040669 W JP 2018040669W WO 2019098039 A1 WO2019098039 A1 WO 2019098039A1
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WIPO (PCT)
Prior art keywords
mass
urethane resin
parts
urethane
synthetic leather
Prior art date
Application number
PCT/JP2018/040669
Other languages
English (en)
French (fr)
Inventor
智博 鉄井
Original Assignee
Dic株式会社
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株式会社 filed Critical Dic株式会社
Priority to CN201880064067.8A priority Critical patent/CN111164141B/zh
Priority to KR1020207009582A priority patent/KR102409657B1/ko
Priority to JP2019507957A priority patent/JP6521349B1/ja
Priority to EP18877423.6A priority patent/EP3712203A4/en
Priority to US16/761,684 priority patent/US20210164157A1/en
Publication of WO2019098039A1 publication Critical patent/WO2019098039A1/ja

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0047—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by incorporating air, i.e. froth
    • C—CHEMISTRY; METALLURGY
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/56—After-treatment of articles, e.g. for altering the shape
    • B29C44/5627—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching
    • B29C44/5654—Subdividing foamed articles to obtain particular surface properties, e.g. on multiple modules
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Definitions

  • the present invention relates to a foamed urethane sheet.
  • Polyurethane resins have been used in various applications such as coatings and adhesives because of their excellent mechanical strength and flexibility.
  • solvent-based urethane resins containing dimethylformamide (DMF) have been widely used until now, but the legal restrictions on DMF have become stricter every year, and it has become weak solvents, water systems, no solvents, etc. The development of environmentally friendly products is urgently needed.
  • DMF dimethylformamide
  • aqueous urethane in which a urethane resin is dispersed in water is most actively studied.
  • PUD aqueous urethane
  • this water-based urethane for various applications, there are also many needs to be molded as a foam for the purpose of improving the texture and the like.
  • mechanical foaming in which microcapsules are compounded or a gas such as carbon dioxide is dispersed in a PUD-blended solution has been studied (see, for example, Patent Document 1).
  • the texture of the resulting foam may be poor, and the smoothness may be poor due to the expansion of the microcapsules.
  • the method of dispersing the gas since the bubbles which are entangled in the mixed solution disappear in the process of producing the foam, it is difficult to control the bubble size etc. and stably obtain the foam with good texture. It was difficult.
  • the problem to be solved by the present invention is to provide a foamed urethane sheet excellent in texture and tensile strength using a water-containing urethane resin composition.
  • the present invention is formed of a urethane resin composition containing a urethane resin (A), water (B), and a surfactant (C) having 10 or more carbon atoms, and has a density of 200 to 1, 1
  • the present invention provides a foamed urethane sheet characterized by having a weight of 000 kg / m 3 .
  • this invention is a synthetic leather which has a base material (i) and a polyurethane layer (ii), Comprising: That the said polyurethane layer (ii) was formed by the said foaming urethane sheet It provides a synthetic leather characterized by the above.
  • the foamed urethane sheet of the present invention is excellent in feeling and tensile strength.
  • foamed urethane sheet when the foamed urethane sheet is applied to synthetic leather, it is possible to uniformly produce an embossing having excellent peel strength and excellent in design on the surface thereof.
  • the urethane foam sheet of the present invention contains urethane resin (A), water (B), and urethane containing surfactant (C) having no aromatic ring and having a hydrophobic portion having 10 or more carbon atoms. It is formed of a resin composition and has a density of 200 to 1,000 kg / m 3 .
  • the urethane resin (A) can be dispersed in water (B) described later, and, for example, a urethane resin having a hydrophilic group such as an anionic group, a cationic group or a nonionic group; forced by an emulsifier It is possible to use a urethane resin or the like dispersed in water (B). These urethane resins (A) may be used alone or in combination of two or more. Among these, in view of production stability, it is preferable to use a urethane resin having a hydrophilic group, and an aqueous urethane resin having an anionic group is more preferable.
  • the method of using 1 or more types of compounds selected from the group which consists of a glycol compound which has a carboxyl group, and a compound which has a sulfonyl group as a raw material is mentioned, for example.
  • glycol compound having a carboxyl group examples include, for example, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol butyric acid, 2,2-dimethylol propionic acid, and 2,2- Valeric acid etc. can be used. These compounds may be used alone or in combination of two or more.
  • Examples of the compound having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N- (2-aminoethyl)- It is possible to use 2-aminoethylsulfonic acid or the like. These compounds may be used alone or in combination of two or more.
  • the amount of use in the case of using the raw material used to produce the urethane resin having an anionic group is 0% of the total mass of the raw material of the urethane resin (A), from the viewpoint that much more excellent water dispersion stability is obtained. It is preferably in the range of 1 to 4.8% by mass, more preferably in the range of 0.5 to 4% by mass, and still more preferably in the range of 1 to 3% by mass.
  • the carboxyl group and the sulfonyl group may be partially or entirely neutralized to a basic compound in the urethane resin composition.
  • the basic compound include organic amines such as ammonia, triethylamine, pyridine and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; and metal base compounds containing sodium, potassium, lithium, calcium and the like. Can.
  • the method of using 1 type, or 2 or more types of a compound which has an amino group as a raw material is mentioned, for example.
  • Examples of the compound having an amino group include compounds having a primary and secondary amino group such as triethylenetetramine and diethylenetriamine; N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine; and N-methyl Compounds having a tertiary amino group such as N-alkyldiaminoalkylamine such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.
  • urethane resin (A) for example, polyisocyanate (a1), polyol (a2), and a reactant of a raw material used to produce the above-described aqueous urethane resin having a hydrophilic group are used. be able to.
  • polyisocyanate (a1) examples include aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidated diphenylmethane polyisocyanate, etc .; hexamethylene diisocyanate, Aliphatic or alicyclic polyisocyanates such as lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate and the like can be used. These polyisocyanates may be used alone or in combination of two or
  • the amount of the polyisocyanate (a1) used is in the range of 5 to 40% by mass based on the total mass of the raw material of the urethane resin (A) from the viewpoint of production stability and mechanical properties of the obtained film. Preferably, it is in the range of 10 to 30% by mass.
  • polyether polyol As said polyol (a2), a polyether polyol, polyester polyol, a polyacryl polyol, a polycarbonate polyol, a polybutadiene polyol etc. can be used, for example. These polyols may be used alone or in combination of two or more.
  • the number average molecular weight of the polyol (a2) is preferably in the range of 500 to 8,000, and more preferably in the range of 800 to 4,000, from the viewpoint of the mechanical strength of the obtained film.
  • the number average molecular weight of the polyol (a2) is a value measured by gel permeation column chromatography (GPC).
  • a chain extender (a2 ') having a number average molecular weight of 50 to 450 may be used in combination with the polyol (a2), if necessary.
  • Examples of the chain extender (a2 ′) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol and 1,4-butanediol.
  • a chain extender having a hydroxyl group such as hexamethylene glycol, sucrose, methylene glycol, glycerin, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, trimethylolpropane, etc .; -Propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cycle Using chain extenders having an amino group such as hexane diamine, 4,4'-dicyclohexyl methane diamine, 3,3'-dimethyl-4,4'- dicyclohexyl methane diamine, 1,4-cyclohexane diamine, hydrazine etc. it can. These chain extenders may be used alone or in combination of two or more.
  • urethane resin (A) It is preferably in the range of 0.8 to 4.3% by mass, more preferably in the range of 1 to 3.5% by mass, and in the range of 1.5 to 3.2% by mass in the total mass of the raw materials of It is further preferred that
  • the urethane resin (A) for example, the polyol (a2), a raw material used to produce the urethane resin having the hydrophilic group, the chain extender (a2 ′), and the polyisocyanate ( There is a method in which a1) is charged in one batch and reacted. These reactions may be carried out, for example, at 50 to 100 ° C. for 3 to 10 hours.
  • the molar ratio [isocyanate group / (hydroxy group and amino group)] of the sum of hydroxyl group and amino group possessed by ') and isocyanate group possessed by the polyisocyanate (a1) is in the range of 0.8 to 1.2. It is preferably present, and more preferably in the range of 0.9 to 1.1.
  • the isocyanate group which remains in the said urethane resin (A).
  • an alcohol having one hydroxyl group such as methanol.
  • the amount of the alcohol used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A).
  • the organic solvent examples include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetic acid ester compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; and dimethylformamide, N-methylpyrrolidone and the like An amide compound etc. can be used.
  • These organic solvents may be used alone or in combination of two or more. The organic solvent is preferably removed by distillation or the like when the final urethane resin composition is obtained.
  • the foam generated in the foaming step to be described later is stably held (particularly in the drying step), and the density of the urethane foam sheet is stably 200 to 1,000 kg /
  • the temperature is preferably 80 ° C. or higher, and more preferably in the range of 80 to 220 ° C. in that it can be in the range of m 3 .
  • polystyrene resin As a method of adjusting the flow start temperature high, for example, using a polyol with high crystallinity such as polycarbonate polyol as the polyol (a2), increasing the amount of use of the chain extender (a2 ′), polyisocyanate As (a1), use is made of polyisocyanate having high crystallinity such as dicyclohexylmethane diisocyanate and 4,4′-diphenylmethane diisocyanate.
  • polysocyanate having high crystallinity such as dicyclohexylmethane diisocyanate and 4,4′-diphenylmethane diisocyanate.
  • the flow start temperature of the said urethane resin (A) can be adjusted by selecting these methods suitably.
  • the measuring method of the flow start temperature of the said urethane resin (A) is described in the Example mentioned later.
  • urethane resin having an anionic group When a urethane resin having an anionic group is used as the urethane resin (A), it is easy to adjust the flow initiation temperature, and from the viewpoint of further excellent bubble retention, texture, and tensile strength, 4,4 '-Diphenylmethane diisocyanate, toluene diisocyanate, cyclohexylmethane diisocyanate, and isophorone diisocyanate, at least one polyisocyanate selected from the group consisting of: polyol (a2), glycol compound having a carboxyl group, chain extender having a hydroxyl group ( It is preferable to use a urethane resin (A-A-1) having an anionic group which is a reactant of a chain extender containing a2 ′).
  • water (B) for example, ion exchange water, distilled water or the like can be used. These waters may be used alone or in combination of two or more.
  • the mass ratio [(A) / (B)] of the urethane resin (A) to the water (B) is in the range of 10/80 to 70/30 from the viewpoint of water dispersion stability and workability. It is preferable that the ratio be in the range of 20/80 to 60/40.
  • the surfactant (C) it is essential to use one having no aromatic ring and having a hydrophobic part having 10 or more carbon atoms in order to prevent the foam generated by foaming from disappearing. .
  • surfactant (C) for example, a surfactant represented by the following general formula (1); fatty acid salt, succinate, sulfosuccinate, octadecylsulfosuccinate, sulfosuccinate, etc. may be used it can. These surfactants may be used alone or in combination of two or more.
  • R represents an alkyl group having a linear or branched structure having 10 to 20 carbon atoms
  • X represents Na, K, NH 4 , morpholine, ethanolamine, or triethanolamine.
  • the surfactant represented by the above-mentioned general formula (1) is preferably used because it has further excellent foam retention among the above-mentioned surfactants, and the number of carbon atoms is preferably It is more preferable to use one showing a linear alkyl group of 13 to 19, and a stearate is more preferable.
  • the said urethane resin composition contains the said urethane resin (A), water (B), and surfactant (C) as an essential component, you may contain another additive as needed.
  • a crosslinking agent As said other additive, a crosslinking agent, a neutralizing agent, a thickener, a urethanization catalyst, a filler, a pigment, a dye, a flame retardant, a leveling agent, an antiblocking agent etc. can be used, for example.
  • These additives may be used alone or in combination of two or more.
  • crosslinking agent it is used for the purpose of the improvement of the mechanical strength of a foaming urethane sheet etc.
  • a polyisocyanate crosslinking agent an epoxy crosslinking agent, a melamine crosslinking agent, an oxazoline crosslinking agent etc.
  • crosslinking agents may be used alone or in combination of two or more.
  • the range of ⁇ 50 parts by mass is more preferable, the range of 0.5 ⁇ 30 parts by mass is further preferable, and 1 ⁇ 10 parts by mass is particularly preferable.
  • the foamed urethane sheet is produced by foaming the urethane resin composition to obtain a foaming liquid, applying the foaming liquid to a substrate and drying it to obtain a density of 200 to 1,000 kg / m 3. Be done.
  • the method of using mixers such as stirring by a hand and a mechanical mixer, is mentioned, for example.
  • a mixer for example, a method of stirring at 500 to 3,000 rpm for 10 seconds to 3 minutes can be mentioned.
  • the volume of the foamed urethane sheet is preferably adjusted to 1.3 to 7 times before and after foaming, from the viewpoint of easily adjusting the density of the foamed urethane sheet within the range defined in the present invention. It is more preferable to use a volume, and it is further preferable to use a volume of 1.3 to 1.7 times.
  • Examples of the method of 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 urethane foam sheet obtained by the above method is, for example, 5 to 200 ⁇ m.
  • the density of the foamed urethane sheet is 200 to 1,000 kg / m 3 . If the said density is this range, it will become the sheet
  • the density is preferably in the range from the point it is available in a variety of applications of 300 ⁇ 900kg / m 3 as foamed urethane sheet, more preferably in the range of 400 ⁇ 800kg / m 3.
  • the density of the urethane foam sheet is a value calculated by dividing the mass of the urethane foam sheet by the volume.
  • the synthetic leather of the present invention is a synthetic leather having at least a substrate (i) and a polyurethane layer (ii), wherein the polyurethane layer (ii) is formed of the foamed urethane sheet.
  • (X) A method of foaming the urethane resin composition to obtain a foam, applying the foam on a release paper, drying it, and bonding it to the substrate (i).
  • (Y) A method of foaming the urethane resin composition to obtain a foaming liquid, and applying the foaming liquid on a skin layer prepared on a release paper, drying it, and bonding it to the substrate (i) ,
  • (Z) The urethane resin composition is foamed to obtain a foaming liquid, which is applied onto the substrate (i), dried, and, if necessary, on the release paper.
  • epidermis layer (iii), etc. are mentioned.
  • Examples of the substrate (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 substrates of non-woven fabric, woven fabric, knitted fabric, etc. by their blended fibers etc .; said non-woven fabric impregnated with resin such as polyurethane resin; said non-woven fabric further provided with porous layer; thermoplastic urethane (TPU) And the like can be used.
  • 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 substrates of non-woven fabric, woven fabric, knitted fabric, etc. by their blended fibers etc .
  • said non-woven fabric impregnated with resin such as polyurethane resin
  • said non-woven fabric further provided with porous layer
  • thermoplastic urethane (TPU) And the like can be
  • the polyurethane layer (ii) is formed of the foam sheet, and the density thereof is 300 to 900 kg / kg, from the viewpoint of being able to obtain a synthetic leather having a more excellent feel and peel strength.
  • the range of m 3 is preferable, and the range of 400 to 800 kg / m 3 is more preferable.
  • the density of the polyurethane layer (ii) is obtained by dividing the weight of the synthetic leather per 10 cm square by the weight of the base material (i) per 10 cm square, by the thickness of the polyurethane layer (ii). Indicates In addition, the density of the said polyurethane layer (ii) can be adjusted with the foaming condition of the said urethane resin composition.
  • the skin layer (iii) can be formed of a known material by a known method, and for example, a solvent-based urethane resin, a water-based urethane resin, a silicone resin, a polypropylene resin, a polyester resin, etc. can be used.
  • a solvent-based urethane resin a water-based urethane resin
  • a silicone resin a silicone resin
  • a polypropylene resin a polyester resin, etc.
  • a polyester resin etc.
  • water-based polycarbonate type urethane resin for DMF reduction by environmental response.
  • a surface treatment layer (iv) may be provided on the surface layer (iii) for the purpose of improving scratch resistance and the like.
  • the surface treatment layer (iv) can be formed of a known material by a known method.
  • the synthetic leather of the present invention is capable of uniformly producing an embossing having excellent peel strength and excellent design on the surface by using the above-described foamed urethane sheet having excellent feeling and tensile strength. It is.
  • a release paper provided with a design such as a concavo-convex pattern is placed on the polyurethane layer (ii) of synthetic leather, and heat is applied by a preheated roll or the like.
  • a method of pressing; a method of heat pressing using a roll coater provided with design properties such as a concavo-convex pattern etc. may be mentioned.
  • the roll can be heated at 50 to 200.degree.
  • a methyl ethyl ketone solution of a urethane resin After mixing 70 parts by mass of polyoxyethylene distyrenated phenyl ether (Hydrophile-Lipophile Balance (hereinafter abbreviated as "HLB"); 14) and 13 parts by mass of triethylamine in this urethane resin solution, deionized water 800 is prepared. An emulsion liquid in which the urethane resin (A-1) was dispersed in water was obtained by adding a mass part and performing phase inversion emulsification. Subsequently, methyl ethyl ketone was distilled away from the emulsion to obtain a urethane resin composition containing 50% by mass of the urethane resin (A-1).
  • HLB Hydroethylene distyrenated phenyl ether
  • a methyl ethyl ketone solution of a urethane resin was added to stop the reaction to obtain a methyl ethyl ketone solution of a urethane resin.
  • the urethane resin solution is mixed with 70 parts by mass of polyoxyethylene distyrenated phenyl ether (HLB; 14) and 13 parts by mass of triethylamine, and then 800 parts by mass of ion exchange water is added to cause phase inversion emulsification.
  • An emulsion was obtained in which the resin (A-2) was dispersed in water.
  • methyl ethyl ketone was distilled away from the emulsion to obtain a urethane resin composition containing 50% by mass of the urethane resin (A-2).
  • the urethane resin solution is mixed with 70 parts by mass of polyoxyethylene distyrenated phenyl ether (HLB; 14) and 13 parts by mass of triethylamine, and then 800 parts by mass of ion exchange water is added to cause phase inversion emulsification.
  • An emulsion was obtained in which the resin (A-3) was dispersed in water.
  • methyl ethyl ketone was distilled away from the emulsion to obtain a urethane resin composition containing 50% by mass of the urethane resin (A-3).
  • HLB Hydrophile-Lipophile Balance
  • a urethane resin composition was obtained by mixing 21 parts by mass of ethylene diamine and 189 parts of ion-exchanged water with the obtained emulsion and conducting chain elongation reaction. Subsequently, methyl ethyl ketone and water were distilled away from the urethane resin composition to obtain a urethane resin composition containing 50% by mass of the urethane resin (A-4).
  • HLB Hydrophile-Lipophile Balance
  • ion-exchanged water 2 By adding 650 parts by mass, phase inversion emulsification was carried out to obtain an emulsion in which the urethane prepolymer was dispersed in water.
  • a urethane resin composition was obtained by mixing 21 parts by mass of ethylene diamine and 189 parts of ion-exchanged water with the obtained emulsion and conducting chain elongation reaction. Subsequently, methyl ethyl ketone and water were distilled away from the urethane resin composition to obtain a urethane resin composition containing 50% by mass of the urethane resin (A-5).
  • HLB Hydrophile-Lipophile Balance
  • a urethane resin composition was obtained by mixing 21 parts by mass of ethylene diamine and 189 parts of ion-exchanged water with the obtained emulsion and conducting chain elongation reaction. Subsequently, methyl ethyl ketone and water were distilled away from the urethane resin composition to obtain a urethane resin composition containing 50% by mass of the urethane resin (A-6).
  • Example 1 To 100 parts by mass of the urethane resin composition obtained in Synthesis Example 1, 2 parts by mass of a thickener (“Borchi Gel ALA” manufactured by Borchers), 0.5 parts by mass of ammonium stearate, a crosslinking agent (manufactured by Nippon Shokubai Co., Ltd.) 4 parts by mass of “Epocross WS-700” was added, and the mixture was stirred at 2,000 rpm for 1 minute using a mechanical mixer to foam, and a 1.5-fold volume of a foaming liquid was obtained. This was applied to a release paper and dried at 80 ° C. for 3 minutes, and further dried at 120 ° C. for 2 minutes to produce a foamed urethane sheet.
  • a thickener (“Borchi Gel ALA” manufactured by Borchers)
  • a crosslinking agent manufactured by Nippon Shokubai Co., Ltd.
  • Examples 2 to 8 A foamed urethane sheet was obtained in the same manner as in Example 1 except that the type of the aqueous urethane resin composition used and the amount of ammonium stearate used were changed as shown in Tables 1 to 3.
  • Comparative Example 1 To 100 parts by mass of the urethane resin composition obtained in Synthesis Example 1, 2 parts by mass of a thickener (“Borchi Gel ALA” manufactured by Borchers), 1.5 parts by mass of sodium dodecylbenzene sulfonate, a crosslinking agent Four parts by mass of “Epocross WS-700” (manufactured by Company) were added, and the mixture was stirred at 2,000 rpm for 1 minute using a mechanical mixer to foam, and a volume of 1.5 times the volume was obtained. This was applied to a release paper and dried at 80 ° C. for 3 minutes, and further dried at 120 ° C. for 2 minutes to produce a sheet.
  • a thickener (“Borchi Gel ALA” manufactured by Borchers)
  • sodium dodecylbenzene sulfonate 1.5 parts by mass of sodium dodecylbenzene sulfonate
  • a crosslinking agent Four parts by mass of “Epocross WS-700
  • the number average molecular weight of the polyol etc. used in the synthesis example was measured by gel permeation column chromatography (GPC) under the following conditions.
  • Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used in series connection. "TSKgel G5000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 4000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 3000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 This "TSKgel G2000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • Examples 1 to 8 which are the foamed urethane sheets of the present invention, have excellent texture and tensile strength.
  • Comparative Example 1 is an embodiment using sodium dodecylbenzene sulfonate having an aromatic ring instead of the surfactant (C), but the foam retention is poor, and the texture of the sheet is hard and poor.
  • C surfactant
  • Comparative Example 2 is an embodiment in which the surfactant (C) is not used, but the foam retention is poor, and the texture of the sheet is hard and poor.
  • Comparative Example 3 is an embodiment in which the expansion ratio is excessive and the density is less than the range specified in the present invention, but the tensile strength is poor.
  • Example 9 To 100 parts by mass of the urethane resin composition obtained in Synthesis Example 1, 2 parts by mass of a thickener ("Borch Gel ALA" manufactured by Borchers), 1.5 parts by mass of ammonium stearate, a crosslinking agent (manufactured by Nippon Shokubai Co., Ltd.) 4 parts by mass of “Epocross WS-700” was added, and the mixture was stirred at 2,000 rpm for 1 minute using a mechanical mixer to foam, and a 1.5-fold volume of a foaming liquid was obtained. This was applied to a polyester fiber non-woven fabric and dried at 80 ° C. for 3 minutes and further at 120 ° C. for 2 minutes to form a polyurethane layer. Subsequently, the release paper to which the uneven
  • a thickener (“Borch Gel ALA” manufactured by
  • Example 10 to 12 A synthetic leather was obtained in the same manner as in Example 9, except that the type of urethane resin composition used and the amount of ammonium stearate used were changed as shown in Table 4.
  • Examples 9 to 12 which are synthetic leathers of the present invention, were found to have excellent feel, peel strength, and embossing.

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Abstract

本発明は、ウレタン樹脂（Ａ）、水性媒体（Ｂ）、及び、炭素原子数が１０以上の界面活性剤（Ｃ）を含有する水性ウレタン樹脂組成物により形成されたであり、密度が２００～１，０００ｋｇ／ｍ３であることを特徴とする発泡ウレタンシートを提供する。また、本発明は、前記少なくとも、基材（ｉ）、及び、ポリウレタン層（ｉｉ）を有する合成皮革であって、前記ポリウレタン層（ｉｉ）が、請求項１～４のいずれか１項記載の発泡ウレタンシートにより形成されているものであることを特徴とする合成皮革を提供するものである。前記ポリウレタン層（ｉｉ）は、エンボス加工されているものであってもよい。前記界面活性剤（Ｃ）は、ステアリン酸塩であることが好ましく、前記ウレタン樹脂（Ａ）は、アニオン性基を有するものであり、流動開始温度が８０℃以上であるものを用いることが好ましい。

Description

発泡ウレタンシート、及び、合成皮革
　本発明は、発泡ウレタンシートに関する。
　ポリウレタン樹脂は、優れた機械的強度、及び柔軟性を有することから、これまでコーティング剤、接着剤等の様々な用途で使用されている。その中で、これまでは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広く利用されてきたが、ＤＭＦの法的規制は年々厳しくなっており、弱溶剤化、水系化、無溶剤化等に環境対応製品の開発が急務となっている。
　その中で、ウレタン樹脂を水中に分散させた水系ウレタン（ＰＵＤ）は最も盛んに研究がなされている。この水系ウレタンを様々な用途に利用する際には、風合い等の向上を目的に発泡体として成型するニーズも多い。水系ウレタンにより発泡体を成型する方法としては、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、風合いの良好な発泡体を安定して得ることは困難であった。
特開２００７－１９１８１０号公報
　本発明が解決しようとする課題は、水を含有するウレタン樹脂組成物を使用して、風合い、及び引張強度に優れる発泡ウレタンシートを提供することである。
　本発明は、ウレタン樹脂（Ａ）、水（Ｂ）、及び、炭素原子数が１０以上の界面活性剤（Ｃ）を含有するウレタン樹脂組成物により形成されたであり、密度が２００～１，０００ｋｇ／ｍ３であることを特徴とする発泡ウレタンシート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、ポリウレタン層（ｉｉ）を有する合成皮革であって、前記ポリウレタン層（ｉｉ）が、前記発泡ウレタンシートにより形成されたものであることを特徴とする合成皮革を提供するものである。
　本発明の発泡ウレタンシートは、風合い、及び、引張強度に優れるものである。
　また、前記発泡ウレタンシートを合成皮革に応用した際には、更に、剥離強度にも優れ、かつ、その表面上に意匠性に優れるエンボス加工を均一に作製できるものである。
　本発明の発泡ウレタンシートは、ウレタン樹脂（Ａ）、水（Ｂ）、及び、芳香環を有さず、かつ炭素原子数が１０以上の疎水部を有する界面活性剤（Ｃ）を含有するウレタン樹脂組成物により形成されたであり、密度が２００～１，０００ｋｇ／ｍ３であるものである。
　前記ウレタン樹脂（Ａ）は、後述する水（Ｂ）中に分散等し得るものであり、例えば、アニオン性基、カチオン性基、ノニオン性基等の親水性基を有するウレタン樹脂；乳化剤で強制的に水（Ｂ）中に分散したウレタン樹脂などを用いることができる。これらのウレタン樹脂（Ａ）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、製造安定性の点から、親水性基を有するウレタン樹脂を用いることが好ましく、アニオン性基を有する水性ウレタン樹脂がより好ましい。
　前記ア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、カルボキシル基を有するグリコール化合物、及び、スルホニル基を有する化合物からなる群より選ばれる１種以上の化合物を原料として用いる方法が挙げられる。
　前記カルボキシル基を有するグリコール化合物としては、例えば、２，２－ジメチロールプロピオン酸、２，２－ジメチロールブタン酸、２，２－ジメチロール酪酸、２，２－ジメチロールプロピオン酸、２，２－吉草酸等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。
　前記スルホニル基を有する化合物としては、例えば、３，４－ジアミノブタンスルホン酸、３，６－ジアミノ－２－トルエンスルホン酸、２，６－ジアミノベンゼンスルホン酸、Ｎ－（２－アミノエチル）－２－アミノエチルスルホン酸等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。
　前記アニオン性基を有するウレタン樹脂を製造するために用いる原料を用いる場合の使用量としては、より一層優れた水分散安定性が得られる点から、ウレタン樹脂（Ａ）の原料の合計質量中０．１～４．８質量％の範囲であることが好ましく、０．５～４質量％の範囲であることがより好ましく、１～３質量％の範囲であることが更に好ましい。
　前記カルボキシル基及びスルホニル基は、ウレタン樹脂組成物中で、一部又は全部が塩基性化合物に中和されていてもよい。前記塩基性化合物としては、例えば、アンモニア、トリエチルアミン、ピリジン、モルホリン等の有機アミン；モノエタノールアミン、ジメチルエタノールアミン等のアルカノールアミン；ナトリウム、カリウム、リチウム、カルシウム等を含む金属塩基化合物などを用いることができる。
　前記カチ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、アミノ基を有する化合物の１種又は２種以上を原料として用いる方法が挙げられる。
　前記アミノ基を有する化合物としては、例えば、トリエチレンテトラミン、ジエチレントリアミン等の１級及び２級アミノ基を有する化合物；Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン等のＮ－アルキルジアルカノールアミン、Ｎ－メチルジアミノエチルアミン、Ｎ－エチルジアミノエチルアミン等のＮ－アルキルジアミノアルキルアミンなどの３級アミノ基を有する化合物など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。
　前記ウレタン樹脂（Ａ）としては、具体的には、例えば、ポリイソシアネート（ａ１）、ポリオール（ａ２）、及び前記した親水性基を有する水性ウレタン樹脂を製造するために用いる原料の反応物を用いることができる。
　前記ポリイソシアネート（ａ１）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（ａ１）の使用量としては、製造安定性、及び得られる皮膜の機械物性の点から、前記ウレタン樹脂（Ａ）の原料の合計質量中５～４０質量％の範囲であることが好ましく、１０～３０質量％の範囲であることがより好ましい。
　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。
　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、５００～８，０００の範囲であることが好ましく、８００～４，０００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）には、必要に応じて、数平均分子量が５０～４５０の鎖伸長剤（ａ２’）を併用しても良い。前記鎖伸長剤（ａ２’）としては、例えば、エチレングリコール、ジエチレンリコール、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。
　前記鎖伸長剤（ａ２’）を用いる場合の使用量としては、得られるウレタン樹脂（Ａ）の流動開始温度を調整しやすく、より一層優れた引張強度が得られる点から、ウレタン樹脂（Ａ）の原料の合計質量中０．８～４．３質量％の範囲であることが好ましく、１～３．５質量％の範囲であることがより好ましく、１．５～３．２質量％の範囲であることが更に好ましい。
　前記ウレタン樹脂（Ａ）の製造方法としては、例えば、前記ポリオール（ａ２）、前記親水性基を有するウレタン樹脂を製造するために用いる原料、前記鎖伸長剤（ａ２’）、及び前記ポリイソシアネート（ａ１）を一括に仕込み反応させる方法が挙げられる。これらの反応は、例えば５０～１００℃で３～１０時間行うことが挙げられる。
　前記ウレタン樹脂（Ａ）を製造する際の、前記ポリオール（ａ２）が有する水酸基、前記親水性基を有するウレタン樹脂を製造するために用いる原料が有する水酸基及びアミノ基、並びに前記鎖伸長剤（ａ２’）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（ａ１）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、０．８～１．２の範囲であることが好ましく、０．９～１．１の範囲であることがより好ましい。
　前記ウレタン樹脂（Ａ）を製造する際には、前記ウレタン樹脂（Ａ）に残存するイソシアネート基を失活させることが好ましい。前記イソシアネート基を失活させる場合には、メタノール等の水酸基を１個有するアルコールを用いることが好ましい。前記アルコールの使用量としては、ウレタン樹脂（Ａ）１００質量部に対し、０．００１～１０質量部の範囲であることが好ましい。
　また、前記ウレタン樹脂（Ａ）を製造する際には、有機溶剤を用いてもよい。前記有機溶剤としては、例えば、アセトン、メチルエチルケトン等のケトン化合物；テトラヒドロフラン、ジオキサン等のエーテル化合物；酢酸エチル、酢酸ブチル等の酢酸エステル化合物；アセトニトリル等のニトリル化合物；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド化合物などを用いることができる。これらの有機溶媒は単独で用いても２種以上を併用してもよい。なお、前記有機溶剤は、最終のウレタン樹脂組成物を得る際には蒸留法等によって除去されることが好ましい。
　前記ウレタン樹脂（Ａ）の流動開始温度としては、後述する起泡工程により発生した泡を安定的に保持し（特に乾燥工程において）、安定的に発泡ウレタンシートの密度を２００～１，０００ｋｇ／ｍ３の範囲にすることができる点で、８０℃以上であることが好ましく、８０～２２０℃の範囲であることより好ましい。
　前記ウレタン樹脂（Ａ）の流動開始温度を調整する方法としては、主に後述するウレタン樹脂（Ａ）の原料であるポリオール（ａ２）の種類、鎖伸長剤（ａ２’）の使用量、及びポリイソシアネート（ａ１）の種類により調整する方法が挙げられる。前記流動開始温度を高く調整する方法としては、例えば、ポリオール（ａ２）としてポリカーボネートポリオールのように結晶性の高いポリオールを用いること、鎖伸長剤（ａ２’）の使用量を多くすること、ポリイソシアネート（ａ１）として、ジシクロヘキシルメタンジイソシアネートや４，４’－ジフェニルメタンジイソシアネートのように結晶性の高いポリイソシアネートを用いることなどが挙げられる。また、前記流動開始温度を低く調整する方法としては、例えば、ポリオール（ａ２）としてポリオキシプロピレングリコールのように結晶性の低いポリオールを用いること、鎖伸長剤（ａ２’）の使用量を少なくすること、ポリイソシアネート（ａ１）として、イソホロンジイソシアネートやトルエンジイソシアネートのように結晶性の低いポリイソシアネートを用いることなどが挙げられる。よって、これらの方法を適宜選択することによって、前記ウレタン樹脂（Ａ）の流動開始温度を調整することができる。なお、前記ウレタン樹脂（Ａ）の流動開始温度の測定方法は、後述する実施例にて記載する。
　前記ウレタン樹脂（Ａ）としてアニオン性基を有するウレタン樹脂を用いる場合には、流動開始温度を調整しやすく、より一層優れた泡保持性、風合い、及び引張強度が得られる点から、４，４’－ジフェニルメタンジイソシアネート、トルエンジイソシアネート、シクロヘキシルメタンジイソシアネート、及びイソホロンジイソシアネートからなる群より選ばれる１種以上のポリイソシアネートと、ポリオール（ａ２）と、カルボキシル基を有するグリコール化合物と、水酸基を有する鎖伸長剤（ａ２’）を含む鎖伸長剤の反応物であるアニオン性基を有するウレタン樹脂（Ａ－Ａ－１）を用いることが好ましい。
　前記水（Ｂ）としては、例えば、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種以上を用いてもよい。
　前記ウレタン樹脂（Ａ）と前記水（Ｂ）との質量比［（Ａ）／（Ｂ）］としては、水分散安定性、及び作業性の点から、１０／８０～７０／３０の範囲であることが好ましく、２０／８０～６０／４０の範囲であることがより好ましい。
　前記界面活性剤（Ｃ）は、起泡により生じた泡を消失から防止するために、芳香環を有さず、かつ炭素原子数が１０以上の疎水部を有するものを用いることが必須である。
　前記界面活性剤（Ｃ）としては、例えば、下記一般式（１）で表される界面活性剤；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-I000001
（式（１）中、Ｒは炭素原子数が１０～２０の直鎖又は分岐構造を有するアルキル基を示し、ＸはＮａ、Ｋ、ＮＨ４、モルホリン、エタノールアミン、又はトリエタノールアミンを示す。）
　前記界面活性剤（Ｃ）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を有することから、前記一般式（１）で表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を用いることがより好ましく、ステアリン酸塩が更に好ましい。
　前記界面活性剤（Ｃ）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質量部に対して、０．０１～１０質量部の範囲であることが好ましく、０．１～５質量部の範囲がより好ましい。
　前記ウレタン樹脂組成物は、前記ウレタン樹脂（Ａ）、水（Ｂ）、及び界面活性剤（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、架橋剤、中和剤、増粘剤、ウレタン化触媒、充填剤、顔料、染料、難燃剤、レべリング剤、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。
　前記架橋剤としては、発泡ウレタンシートの機械的強度の向上等の目的で用いられるものであり、例えば、ポリイソシアネート架橋剤、エポキシ架橋剤、メラミン架橋剤、オキサゾリン架橋剤等を用いることができる。これらの架橋剤は単独で用いても２種以上を併用してもよい。前記架橋剤を用いる場合の使用量としては、例えば、前記ウレタン樹脂（Ａ）（＝固形分）１００質量部に対して、０．０１～１００質量部の範囲であることが好ましく、０．１～５０質量部の範囲がより好ましく、０．５～３０質量部の範囲が更に好ましく、１～１０質量部が特に好ましい。
　次に、本発明の発泡ウレタンシートの製造方法について説明する。
　前記発泡ウレタンシートは、前記ウレタン樹脂組成物を起泡させ起泡液を得、この起泡液を基材に塗布し、乾燥させ、２００～１，０００ｋｇ／ｍ３の密度を得ることにより製造される。
　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、手による撹拌や、メカニカルミキサー等のミキサーを使用する方法が挙げられる。ミキサーを使用する場合には、例えば、５００～３，０００ｒｐｍにて１０秒～３分間撹拌させる方法が挙げられる。この際、発泡ウレタンシートの密度を本発明で規定する範囲に調整しやすい点から、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く、１．３～１．７倍の体積にすることが更に好ましい。
　得られた起泡液を離型紙等の基材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ウレタンシートの厚さとしては、例えば、５～２００μｍである。
　前記発泡ウレタンシートの密度は、２００～１，０００ｋｇ／ｍ３であることが必須である。前記密度がこの範囲であれば、優れた風合いと引張強度とを両立したシートとなる。前記密度としては、発泡ウレタンシートとして様々な用途に利用可能である点から３００～９００ｋｇ／ｍ３の範囲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、前記発泡ウレタンシートの密度は、発泡ウレタンシートの質量を体積で割ることにより算出した値を示す。
　次に、本発明の合成皮革について説明する。
　本発明の合成皮革は、少なくとも、基材（ｉ）、及び、ポリウレタン層（ｉｉ）を有する合成皮革であって、前記ポリウレタン層（ｉｉ）が、前記発泡ウレタンシートにより形成されたものである。
　前記合成皮革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起泡させ起泡液を得、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。
　前記ポリウレタン層（ｉｉ）は、前記発泡シートにより形成されたものであり、その密度としては、より一層優れた風合いと剥離強度とを両立した合成皮革を得ることができる点から、３００～９００ｋｇ／ｍ３の範囲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、前記ポリウレタン層（ｉｉ）の密度は、１０ｃｍ四方あたりの合成皮革の重量から１０ｃｍ四方あたりの基材（ｉ）の重量を減じた値を、ポリウレタン層（ｉｉ）の厚さで除した値を示す。なお、前記ポリウレタン層（ｉｉ）の密度は、前記ウレタン樹脂組成物を起泡具合により調整することができる。
　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、耐擦傷性向上等を目的に表面処理層（ｉｖ）を設けても良い。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、本発明の合成皮革は、前記した風合い及び引張強度に優れる発泡ウレタンシートを用いることにより、更に剥離強度にも優れ、かつ、その表面上に意匠性に優れるエンボス加工を均一に作製できるものである。
　前記ポリウレタン層（ｉｉ）上にエンボス加工する方法としては、例えば、合成皮革のポリウレタン層（ｉｉ）上に、凹凸模様等の意匠性を施した離型紙を載置し、予熱したロール等で熱プレスする方法；凹凸模様等の意匠性を施したロールコーターを使用して、熱プレスする方法が挙げられる。前記熱プレス時には、例えば５０～２００℃でロールを加熱することができる。
　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）の調製
　メチルエチルケトン３，２８１質量部及びオクチル酸第一錫０．１質量部の存在下、ポリカーボネートポリオール（「ニッポラン９８０Ｒ」日本ポリウレタン株式会社製、数平均分子量；２，０００）１，０００質量部と、２，２－ジメチロールプロピオン酸１７質量部と、エチレングリコール４７質量部と、ジフェニルメタンジイソシアネート（以下、「ＭＤＩ」と略記する。）３４４質量部とを溶液粘度が２０，０００ｍＰａ・ｓに達するまで７０℃で反応させた後、メタノール３質量部を加えて反応を停止させてウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル（Ｈｙｄｒｏｐｈｉｌｅ－Ｌｉｐｏｐｈｉｌｅ　Ｂａｌａｎｃｅ（以下、「ＨＬＢ」と略記する）；１４）７０質量部と、トリエチルアミン１３質量部を混合させた後に、イオン交換水８００質量部を加えて転相乳化させることで前記ウレタン樹脂（Ａ－１）が水に分散した乳化液を得た。
　次いで、前記乳化液からメチルエチルケトンを留去することによって、ウレタン樹脂（Ａ－１）５０質量％を含むウレタン樹脂組成物を得た。
［合成例２］ウレタン樹脂（Ａ－２）の調製
　メチルエチルケトン３，２８１質量部及びオクチル酸第一錫０．１質量部の存在下、ポリエーテルポリオール（「ＰＴＭＧ２０００」三菱化型株式会社製、数平均分子量；２，０００）１，０００質量部と、２，２－ジメチロールプロピオン酸１７質量部と、エチレングリコール４７質量部と、ＭＤＩを３４４質量部とを溶液粘度が２０，０００ｍＰａ・ｓに達するまで７０℃で反応させた後、メタノール３質量部を加えて反応を停止させてウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル（ＨＬＢ；１４）７０質量部と、トリエチルアミン１３質量部を混合させた後に、イオン交換水８００質量部を加えて転相乳化させることで前記ウレタン樹脂（Ａ－２）が水に分散した乳化液を得た。
　次いで、前記乳化液からメチルエチルケトンを留去することによって、ウレタン樹脂（Ａ－２）５０質量％を含むウレタン樹脂組成物を得た。
［合成例３］ウレタン樹脂（Ａ－３）の調製
　メチルエチルケトン３，２８１質量部及びオクチル酸第一錫０．１質量部の存在下、ポリエステルポリオール（「プラクセル２２０」株式会社ダイセル製、数平均分子量；２，０００）１，０００質量部と、２，２－ジメチロールプロピオン酸１７質量部と、エチレングリコール４７質量部と、ＭＤＩを３４４質量部とを溶液粘度が２０，０００ｍＰａ・ｓに達するまで７０℃で反応させた後、メタノール３質量部を加えて反応を停止させてウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル（ＨＬＢ；１４）７０質量部と、トリエチルアミン１３質量部を混合させた後に、イオン交換水８００質量部を加えて転相乳化させることで前記ウレタン樹脂（Ａ－３）が水に分散した乳化液を得た。
　次いで、前記乳化液からメチルエチルケトンを留去することによって、ウレタン樹脂（Ａ－３）５０質量％を含むウレタン樹脂組成物を得た。
［合成例４］ウレタン樹脂（Ａ－４）の調製
　メチルエチルケトン１，２７９質量部及びオクチル酸第一錫０．１質量部の存在下、ポリカーボネートポリオール（「ニッポラン９８０Ｒ」日本ポリウレタン株式会社製、数平均分子量；２，０００）１，０００質量部と、２，２－ジメチロールプロピオン酸１７質量部と、ジシクロヘキシルメタンジイソシアネート（以下、「Ｈ１２ＭＤＩ」と略記する。）２６２質量部とを、イソシアネート濃度が１．２質量％に達するまで７０℃で反応させてウレタンプレポリマーのメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル（Ｈｙｄｒｏｐｈｉｌｅ－Ｌｉｐｏｐｈｉｌｅ　Ｂａｌａｎｃｅ（以下、「ＨＬＢ」と略記する）；１４）６４質量部と、トリエチルアミン２８質量部を混合させた後に、イオン交換水２，６５０質量部を加えて転相乳化させることで前記ウレタンプレポリマーが水に分散した乳化液を得た。得られた乳化液にエチレンジアミン２１質量部とイオン交換水１８９部を混合し鎖伸長反応することによってウレタン樹脂組成物を得た。
　次いで、ウレタン樹脂組成物からメチルエチルケトンと水分を留去することによって、ウレタン樹脂（Ａ－４）５０質量％を含むウレタン樹脂組成物を得た。
［合成例５］ウレタン樹脂（Ａ－５）の調製
　メチルエチルケトン１，２７９質量部及びオクチル酸第一錫０．１質量部の存在下、ポリエーテルポリオール（「ＰＴＭＧ２０００」三菱化型株式会社製、数平均分子量；２，０００）１，０００質量部と、２，２－ジメチロールプロピオン酸１７質量部と、Ｈ１２ＭＤＩ　２６２質量部とを、イソシアネート濃度が１．２質量％に達するまで７０℃で反応させてウレタン樹脂プレポリマー（Ａ‘－２）のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル（Ｈｙｄｒｏｐｈｉｌｅ－Ｌｉｐｏｐｈｉｌｅ　Ｂａｌａｎｃｅ（以下、「ＨＬＢ」と略記する）；１４）６４質量部と、トリエチルアミン２８質量部を混合させた後に、イオン交換水２，６５０質量部を加えて転相乳化させることで前記ウレタンプレポリマーが水に分散した乳化液を得た。得られた乳化液にエチレンジアミン２１質量部とイオン交換水１８９部を混合し鎖伸長反応することによってウレタン樹脂組成物を得た。
　次いで、ウレタン樹脂組成物からメチルエチルケトンと水分を留去することによって、ウレタン樹脂（Ａ－５）５０質量％を含むウレタン樹脂組成物を得た。
［合成例６］ウレタン樹脂（Ａ－６）の調製
　メチルエチルケトン１，２７９質量部及びオクチル酸第一錫０．１質量部の存在下、ポリエステルポリオール（「プラクセル２２０」株式会社ダイセル製、数平均分子量；２，０００）１，０００質量部と、２，２－ジメチロールプロピオン酸１７質量部と、Ｈ１２ＭＤＩ　２６２質量部とを、イソシアネート濃度が１．２質量％に達するまで７０℃で反応させてウレタン樹脂プレポリマーのメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル（Ｈｙｄｒｏｐｈｉｌｅ－Ｌｉｐｏｐｈｉｌｅ　Ｂａｌａｎｃｅ（以下、「ＨＬＢ」と略記する）；１４）６４質量部と、トリエチルアミン２８質量部を混合させた後に、イオン交換水２，６５０質量部を加えて転相乳化させることで前記ウレタンプレポリマーが水に分散した乳化液を得た。得られた乳化液にエチレンジアミン２１質量部とイオン交換水１８９部を混合し鎖伸長反応することによってウレタン樹脂組成物を得た。
　次いで、ウレタン樹脂組成物からメチルエチルケトンと水分を留去することによって、ウレタン樹脂（Ａ－６）５０質量％を含むウレタン樹脂組成物を得た。
［実施例１］
　合成例１で得られたウレタン樹脂組成物１００質量部に、増粘剤（Ｂｏｒｃｈｅｒｓ社製「Ｂｏｒｃｈｉ　Ｇｅｌ　ＡＬＡ」）２質量部、ステアリン酸アンモニウム０．５質量部、架橋剤（日本触媒株式会社製「エポクロスＷＳ－７００」）４質量部を加え、メカニカルミキサーを使用して２，０００ｒｐｍで１分間撹拌し、起泡させ、１．５倍の体積にした起泡液を得た。
　これを離型紙に塗布し、８０℃で３分間、さらに１２０℃で２分間乾燥させることで、発泡ウレタンシートを製造した。
［実施例２～８］
　用いる水性ウレタン樹脂組成物の種類、及び、ステアリン酸アンモニウムの使用量を表１～３に示す通りに変更した以外は、実施例１と同様にして発泡ウレタンシートを得た。
［比較例１］
　合成例１で得られたウレタン樹脂組成物１００質量部に、増粘剤（Ｂｏｒｃｈｅｒｓ社製「Ｂｏｒｃｈｉ　Ｇｅｌ　ＡＬＡ」）２質量部、ドデシルベンゼンスルホン酸ナトリウム１．５質量部、架橋剤（日本触媒株式会社製「エポクロスＷＳ－７００」）４質量部を加え、メカニカルミキサーを使用して２，０００ｒｐｍで１分間撹拌し、起泡させ、１．５倍の体積にした起泡液を得た。
　これを離型紙に塗布し、８０℃で３分間、さらに１２０℃で２分間乾燥させることで、シートを製造した。
［比較例２］
　合成例１で得られたウレタン樹脂組成物１００質量部に、増粘剤（Ｂｏｒｃｈｅｒｓ社製「Ｂｏｒｃｈｉ　Ｇｅｌ　ＡＬＡ」）２質量部、架橋剤（日本触媒株式会社製「エポクロスＷＳ－７００」）４質量部を加え、メカニカルミキサーを使用して２，０００ｒｐｍで１分間撹拌し、起泡させ、１．５倍の体積にした起泡液を得た。
　これを離型紙に塗布し、８０℃で３分間、さらに１２０℃で２分間乾燥させたところ、乾燥工程にて泡が消失したため、ほぼ無孔のシートを形成した
［比較例３］
　合成例１で得られたウレタン樹脂組成物１００質量部に、増粘剤（Ｂｏｒｃｈｅｒｓ社製「Ｂｏｒｃｈｉ　Ｇｅｌ　ＡＬＡ」）２質量部、ドデシルベンゼンスルホン酸ナトリウム１．５質量部、ステアリン酸アンモニウム１質量部、架橋剤（日本触媒株式会社製「エポクロスＷＳ－７００」）４質量部を加え、メカニカルミキサーを使用して２，０００ｒｐｍで１分間撹拌し、起泡させ、７倍の体積にした起泡液を得た。
　これを離型紙に塗布し、８０℃で３分間、さらに１２０℃で２分間乾燥させることで、シートを製造した。
［数平均分子量の測定方法］
　合成例で用いたポリオール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た。
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）の流動開始温度の測定方法］
　合成例で得られた水性ウレタン樹脂組成物を離型紙に塗布し（塗布厚さ１５０μｍ）、熱風乾燥機にて７０℃、４分間、次いで１２０℃で２分間乾燥することで乾燥物を得た。この乾燥物を、株式会社島津製作所製フローテスター「ＣＦＴ－５００Ａ」（口径１ｍｍ、長さ１ｍｍのダイスを使用、荷重９８Ｎ、昇温速度３℃／分）を使用して、流動開始温度を測定した。
［風合いの評価方法］
　得られた発泡ウレタンシートを手で触り、以下のように評価した。
　「Ａ」：柔軟性に富む。
　「Ｂ」：やや柔軟性がある。
　「Ｃ」：柔軟性が劣る。
　「Ｄ」：硬い。
［引張強度の測定方法］
　得られたウレタンシートを幅１０ｍｍ、長さ６０ｍｍに裁断したものを試験片とした。この試験片の両端をチャックで挟み、引張試験機「オートグラフＡＧ－Ｉ」（株式会社島津製作所製）を使用して、温度２３℃、湿度６０％の雰囲気下で、クロスヘッドスピード３００ｍｍ／分で引張り、１００％伸長時における引張強度を測定し、以下のように評価した。
　「Ｔ」：１０Ｎ／ｃｍ２以上
　「Ｆ」：１０Ｎ／ｃｍ２未満
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
　本発明の発泡ウレタンシートである実施例１～８は、優れた風合い、及び引張強度を有することが分かった。
　一方、比較例１は、界面活性剤（Ｃ）の代わりに、芳香環を有するドデシルベンゼンスルホン酸ナトリウムを用いた態様であるが、泡保持性が不良であり、シートの風合いが硬く不良であった。
　比較例２は、界面活性剤（Ｃ）を使用しない態様であるが、泡保持性が不良であり、シートの風合いが硬く不良であった。
　比較例３は、発泡倍率を過剰にし、密度が本発明で規定する範囲を下回る態様であるが、引張強度が不良であった。
［実施例９］
　合成例１で得られたウレタン樹脂組成物１００質量部に、増粘剤（Ｂｏｒｃｈｅｒｓ社製「Ｂｏｒｃｈ　Ｇｅｌ　ＡＬＡ」）２質量部、ステアリン酸アンモニウム１．５質量部、架橋剤（日本触媒株式会社製「エポクロスＷＳ－７００」）４質量部を加え、メカニカルミキサーを使用して２，０００ｒｐｍで１分間撹拌し、起泡させ、１．５倍の体積にした起泡液を得た。
　これをポリエステル繊維不織布に塗布し、８０℃で３分間、さらに１２０℃で２分間乾燥させることで、ポリウレタン層を形成した。次いで、得られたポリウレタン層上に、凹凸パターンが施された離型紙を載置し、１８０℃で予熱したロールプレスを施すことでエンボス加工された合成皮革を得た。
［実施例１０～１２］
　用いるウレタン樹脂組成物の種類、及び、ステアリン酸アンモニウムの使用量を表４に示す通りに変更した以外は、実施例９と同様にして合成皮革を得た。
［風合いの評価方法］
　得られた合成皮革を手で触り、以下のように評価した。
　「Ａ」：柔軟性に富む。
　「Ｂ」：やや柔軟性がある。
　「Ｃ」：柔軟性が劣る。
　「Ｄ」：硬い。
［剥離強度の測定方法］
　実施例及び比較例で得られた合成皮革を、島津オートグラフ「ＡＧ－１」（株式会社島津製作所製）を使用して、フルスケール５ｋｇ、ヘッドスピード２０ｍｍ／分の条件にて剥離強度を測定し、以下のように評価した。
　「Ａ」：０．１５ＭＰａ以上
　「Ｂ」：０．１ＭＰａ以上０．１５ＭＰａ未満
　「Ｃ」：０．１ＭＰａ未満
［エンボス加工性の評価方法］
　実施例及び比較例で得られた合成皮革を目視で観察し、以下のように評価した。
　「Ｔ」：エンボス加工により形成された表面上のシワが均一に作製できている。
　「Ｆ」：エンボス加工により形成された表面上のシワが均一でない。
Figure JPOXMLDOC01-appb-T000005
　本発明の合成皮革である実施例９～１２は、優れた風合い、剥離強度、及び、エンボス加工性を有することが分かった。

Claims (6)

  1. ウレタン樹脂（Ａ）、水（Ｂ）、及び、芳香環を有さず、かつ炭素原子数が１０以上の疎水部を有する界面活性剤（Ｃ）を含有するウレタン樹脂組成物により形成された、密度が２００～１，０００ｋｇ／ｍ３であることを特徴とする発泡ウレタンシート。
  2. 前記界面活性剤（Ｃ）が、ステアリン酸塩である請求項１記載の発泡ウレタンシート。
  3. 前記ウレタン樹脂（Ａ）が、アニオン性基を有するものである請求項１又は２記載の発泡ウレタンシート。
  4. 前記ウレタン樹脂（Ａ）の流動開始温度が、８０℃以上である請求項１～３のいずれか１項記載の発泡ウレタンシート。
  5. 少なくとも、基材（ｉ）、及び、ポリウレタン層（ｉｉ）を有する合成皮革であって、
    前記ポリウレタン層（ｉｉ）が、請求項１～４のいずれか１項記載の発泡ウレタンシートにより形成されているものであることを特徴とする合成皮革。
  6. 前記ポリウレタン層（ｉｉ）が、エンボス加工されているものである請求項５記載の合成皮革。
PCT/JP2018/040669 2017-11-15 2018-11-01 発泡ウレタンシート、及び、合成皮革 WO2019098039A1 (ja)

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