WO2020003779A1 - Urethane resin composition, surface treatment agent, and article - Google Patents

Urethane resin composition, surface treatment agent, and article Download PDF

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Publication number
WO2020003779A1
WO2020003779A1 PCT/JP2019/019055 JP2019019055W WO2020003779A1 WO 2020003779 A1 WO2020003779 A1 WO 2020003779A1 JP 2019019055 W JP2019019055 W JP 2019019055W WO 2020003779 A1 WO2020003779 A1 WO 2020003779A1
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Prior art keywords
mass
urethane resin
parts
resin composition
range
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PCT/JP2019/019055
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French (fr)
Japanese (ja)
Inventor
竹村　潔
宏之 千々和
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Dic株式会社
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Priority to CN201980041730.7A priority Critical patent/CN112313285B/en
Priority to JP2020527264A priority patent/JP7298608B2/en
Publication of WO2020003779A1 publication Critical patent/WO2020003779A1/en

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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents

Definitions

  • the present invention relates to a urethane resin composition, a surface treatment agent, and an article having a layer formed by the surface treatment agent.
  • the surface is finished with a surface treatment agent from the viewpoint of imparting chemical resistance and design.
  • the material used for the conventional surface treatment agent is mainly a solvent-based resin composition containing an organic solvent.
  • an aqueous surface treatment agent substantially containing no organic solvent has been developed. Development is underway.
  • aqueous surface treating agent for example, a polyurethane having specific mechanical properties, a carbodiimide crosslinking agent, and an aqueous surface treating agent containing a filler are disclosed (for example, see Patent Document 1).
  • a polyurethane having specific mechanical properties for example, a carbodiimide crosslinking agent, and an aqueous surface treating agent containing a filler are disclosed (for example, see Patent Document 1).
  • Patent Document 1 As the aqueous surface treating agent, for example, a polyurethane having specific mechanical properties, a carbodiimide crosslinking agent, and an aqueous surface treating agent containing a filler are disclosed (for example, see Patent Document 1).
  • the conventional solvent-based resin composition is converted to an aqueous system, there is a problem in that the abrasion resistance is reduced.
  • the aqueous surface treating agent also has a high surface friction coefficient, and further improvement in abrasion resistance has been demanded.
  • the problem to be solved by the present invention is to provide a urethane resin composition which can provide a film having excellent wear resistance in a water-containing urethane resin composition.
  • the present invention provides a urethane resin composition containing a urethane resin (A), water (B), and a silicone compound (C) having a number average molecular weight of 150,000 or more and less than 330,000. It is.
  • the present invention also provides a surface treatment agent containing the urethane resin composition, and an article having a layer formed by the surface treatment agent.
  • the urethane resin composition of the present invention can provide a film having excellent chemical resistance. Therefore, the urethane resin composition of the present invention can be suitably used as a surface treatment agent for various articles.
  • the urethane resin composition of the present invention contains a urethane resin (A), water (B), and a silicone compound (C) having a specific number average molecular weight.
  • the urethane resin (A) can be dispersed in water (B), and is, for example, a urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group; A urethane resin dispersed in B) can be used. These urethane resins (A) may be used alone or in combination of two or more.
  • a method for obtaining the urethane resin having an anionic group for example, a method using one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group as a raw material may be mentioned.
  • Examples of the compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, and Herbic acid or the like 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, and N- (2-aminoethyl)- 2-aminoethylsulfonic acid and the like can be used. These compounds may be used alone or in combination of two or more.
  • the carboxyl group and the sulfonyl group may be partially or entirely neutralized by a basic compound in the 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 including sodium, potassium, lithium, and calcium. Can be.
  • a method for obtaining the urethane resin having a cationic group for example, a method using one or more compounds having an amino group as a raw material may be mentioned.
  • 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; 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.
  • a method for obtaining the urethane resin having a nonionic group for example, a method using one or more compounds having an oxyethylene structure as a raw material may be mentioned.
  • polyether polyol having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol can be used. These compounds may be used alone or in combination of two or more.
  • the amount of the raw material used for producing the urethane resin having the above hydrophilic group is such that urethane is more excellent in chemical resistance, abrasion resistance, weather resistance, and hydrolysis resistance. It is preferably in the range of 0.1 to 15% by mass, more preferably in the range of 1 to 10% by mass, and even more preferably in the range of 1.5 to 7% by mass of the raw material of the resin (A).
  • Examples of the emulsifier that can be used for obtaining the urethane resin that is forcibly dispersed in water (B) include, for example, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene Nonionic emulsifiers such as ethylene sorbitol tetraoleate and polyoxyethylene / polyoxypropylene copolymers; fatty acid salts such as sodium oleate; alkyl sulfates; alkyl benzene sulfonates; alkyl sulfosuccinates; naphthalene sulfonates; Anionic emulsifiers such as polyoxyethylene alkyl sulfate, sodium alkane sulfonate, sodium salt of alkyl diphenyl ether sulfonate; alkyl amine salt, alkyl trimethyl ammonium Arm salts,
  • urethane resin (A) specifically, for example, a raw material used for producing the above-mentioned urethane resin having a hydrophilic group, polyisocyanate (a1), polyol (a2), and a chain extender ( The reactants of a3) can be used. For these reactions, known urethanation reactions can be used.
  • polyisocyanate (a1) examples include aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidated diphenylmethane polyisocyanate; hexamethylene diisocyanate And aliphatic or alicyclic polyisocyanates such as lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, dimer acid diisocyanate and norbornene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.
  • the polyisocyanate (a1) it is preferable to use an alicyclic polyisocyanate from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance, and at least the nitrogen atom of the isocyanate group is cyclohexane. It is more preferable to use a polyisocyanate having one or more structures directly connected to a ring, and it is more preferable to use isophorone diisocyanate and / or dicyclohexylmethane diisocyanate. Further, the amount of the alicyclic polyisocyanate used is preferably 30% by mass or more in the polyisocyanate (a1) from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. , 40% by mass or more, more preferably 50% by mass or more.
  • the alicyclic polyisocyanate and the aliphatic polyisocyanate may be used as the polyisocyanate (a1). It is preferable to use an isocyanate in combination, and it is preferable to use hexamethylene diisocyanate as the aliphatic polyisocyanate.
  • the content of the alicyclic polyisocyanate in the polyisocyanate (a1) is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more.
  • the amount of the polyisocyanate (a1) used is in the range of 5 to 50% by mass in the raw material of the urethane resin (A) from the viewpoint that more excellent chemical resistance, abrasion resistance and weather resistance are obtained. It is preferably in the range of 15 to 40% by mass, more preferably in the range of 20 to 37% by mass.
  • polyether polyol for example, polyether polyol, polyester polyol, polyacryl polyol, polycarbonate polyol, polybutadiene polyol and the like can be used. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use a polycarbonate polyol from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance.
  • polycarbonate polyol for example, a reaction product of a carbonate ester and / or phosgene and a compound having two or more hydroxyl groups can be used.
  • Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl 1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,10-decanediol, 1,12-dodecanediol 1,4-cyclohexanedimethanol, 1,3-cyclohexane
  • 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-propanediol, 1,6-pentanediol and 1,6-propanediol are more excellent in chemical resistance, abrasion resistance, and weather resistance. It is preferable to use one or more compounds selected from the group consisting of -hexanediol, 1,4-cyclohexanedimethanol, 3-methylpentanediol, and 1,10-decanediol. More preferred.
  • the amount of the polycarbonate polyol used is preferably 85% by mass or more in the polyol (a2), and more preferably 90% by mass or more from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. Is more preferable, and 95 mass% or more is still more preferable.
  • the number average molecular weight of the polycarbonate polyol is preferably in the range of 100 to 100,000 from the viewpoint of obtaining more excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance. It is more preferably in the range of ⁇ 10,000, further preferably in the range of 2002002,500.
  • the number average molecular weight of the polycarbonate polyol indicates a value measured by a gel permeation column chromatography (GPC) method.
  • the number average molecular weight of the polyol (a2) other than the polycarbonate polyol is preferably in the range of 500 to 100,000, and more preferably in the range of 700 to 50,000, from the viewpoint that more excellent weather resistance is obtained. Preferably, the range is 800 to 10,000.
  • the number average molecular weight of the polyol (a2) indicates a value measured by a gel permeation column chromatography (GPC) method.
  • the amount of the polyol (a2) used is preferably in the range of 30 to 80% by mass, more preferably in the range of 40 to 75% by mass, and more preferably in the range of 50 to 70% by mass in the raw material of the urethane resin (A). Is more preferred.
  • Examples of the chain extender (a3) include those having a number average molecular weight in the range of 50 to 450 (excluding the polycarbonate polyol), and specifically include ethylenediamine, 1,2-propanediamine, 6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3,
  • a chain extender having an amino group such as 3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, , 3- Lopandiol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sac
  • chain extender (a3) among those described above, a chain extender having an amino group is used, because more excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance are obtained. Is preferable, and piperazine and / or hydrazine are more preferable.
  • the total amount of piperazine and hydrazine is preferably 30% by mass or more in the chain extender (a3), more preferably 50% by mass or more, and 60% by mass. The above is more preferable, and the amount is particularly preferably 80% by mass or more.
  • the chain extender (a3) preferably has an average number of functional groups of less than 3, more preferably less than 2.5. Also,
  • the method for producing the urethane resin (A) includes, for example, reacting the polyisocyanate (a1), the polyol (a2), and a raw material used for producing the urethane resin having a hydrophilic group, thereby obtaining an isocyanate group.
  • the urethane resin (A) it is preferable to deactivate the isocyanate groups remaining in the urethane resin (A).
  • an alcohol having one hydroxyl group such as methanol.
  • the amount of the alcohol to be 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).
  • an organic solvent when producing the urethane resin (A), an organic solvent may be used.
  • the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; dimethylformamide and N-methylpyrrolidone.
  • An amide compound or the like can be used.
  • These organic solvents may be used alone or in combination of two or more. Preferably, the organic solvent is finally removed by a distillation method or the like.
  • the content of the urethane bond in the urethane resin (A) is preferably in the range of 980 to 4,000 mmol / kg, from the viewpoint that more excellent chemical resistance, wear resistance, and weather resistance can be obtained.
  • the range is more preferably from 2,000 to 3,500 mmol / kg, further preferably from 1,100 to 3,000 mmol / kg, and more preferably from 1,150 to 2,500 mmol / kg.
  • the content of the urethane bond in the urethane resin (A) is determined by the following: the polyisocyanate (a1), the polyol (a2), the raw material used for producing the urethane resin having a hydrophilic group, and the chain extender (a3). ) Indicates a value calculated from the charged amount.
  • the content of the urea bond in the urethane resin (A) is preferably in the range of 315 to 850 mmol / kg from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance, The range is more preferably from 350 to 830 mmol / kg, still more preferably from 400 to 800 mmol / kg, even more preferably from 410 to 770 mmol / kg.
  • the content of the urea bond of the urethane resin (A) is based on the polyisocyanate (a1), the polyol (a2), the raw material used for producing the urethane resin having a hydrophilic group, and the chain extender. A value calculated from the charged amount of (a3) is shown.
  • the content of the urethane resin (A) is preferably in the range of 3 to 50% by mass, and more preferably 5 to 30% by mass in the urethane resin composition from the viewpoint of coating properties, workability and storage stability. The range is more preferable.
  • the water (B) ion-exchanged water, distilled water or the like can be used.
  • the content of the water (B) is preferably in the range of 30 to 95% by mass in the urethane resin composition, from the viewpoint of coatability, workability and storage stability of the urethane resin composition, A range of 90% by mass is more preferable.
  • the silicone compound (C) it is essential to use a compound having a number average molecular weight of 150,000 or more and less than 330,000 in order to obtain excellent wear resistance.
  • a silicone compound having a relatively high molecular weight By using a silicone compound having a relatively high molecular weight, a coating film having a high surface strength and a small coefficient of friction is formed, and excellent wear resistance can be obtained.
  • the number average molecular weight of the silicone compound (C) is preferably in the range of 200,000 to 300,000, more preferably 220,000 to 270,000, from the viewpoint of obtaining more excellent abrasion resistance.
  • the number average molecular weight of the silicone compound (C) indicates a value measured by a gel permeation chromatography (GPC) method, and specifically, the measuring method is described in Examples.
  • silicone compound (C) examples include polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, and polymethylphenylhydrogensiloxane; modified products thereof; these silicone compounds and acryl. And the like can be used. These silicone compounds may be used alone or in combination of two or more. Among these, it is preferable to use polydimethylsiloxane from the viewpoint that more excellent wear resistance can be obtained.
  • the silicone compound (C) is preferably in the form of an emulsion dispersed in water (B) from the viewpoint of affinity with water (B).
  • a known surfactant may be contained.
  • the urethane resin composition of the present invention contains the urethane resin (A), water (B), and silicone compound (C) as essential components, but may use other additives as necessary.
  • Examples of the other additives include a filler (D), a crosslinking agent (E), an emulsifier, an antifoaming agent, a leveling agent, a thickener, a viscoelasticity adjusting agent, an antifoaming agent, a wetting agent, a dispersant, and a preservative.
  • Agents, plasticizers, penetrants, fragrances, bactericides, acaricides, fungicides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (e.g., titanium white, redwood, phthalocyanine, carbon Black, permanent yellow, etc.) can be used.
  • These additives may be used alone or in combination of two or more.
  • a filler (D) for imparting a matte feeling to the coating film, and mechanical properties of the coating film It is preferable to include a crosslinking agent (E) in order to improve the strength.
  • Examples of the filler (D) include silica particles, organic beads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, and alumina silicate. Can be used. These fillers may be used alone or in combination of two or more.
  • silica particles for example, dry silica, wet silica and the like can be used. Of these, dry silica is preferred because of its high scattering effect and wide adjustment range of gloss value.
  • the average particle size of these silica particles is preferably in the range of 2 to 14 ⁇ m, and more preferably in the range of 3 to 12 ⁇ m.
  • the average particle size of the silica particles indicates the particle size (the particle size at D50 in the particle size distribution) when the integrated amount occupies 50% in the integrated particle amount curve of the particle size distribution measurement result.
  • organic beads for example, acrylic beads, urethane beads, silicon beads, olefin beads and the like can be used.
  • the amount of the filler (D) to be used can be appropriately determined according to the matt feeling to be imparted.
  • the amount is 1 to 30 parts by mass with respect to 100 parts by mass of the urethane resin (A).
  • the range is 3 to 10 parts by mass.
  • crosslinking agent (E) for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a carbodiimide crosslinking agent, an oxazolidine crosslinking agent, an oxazoline crosslinking agent, a melamine crosslinking agent and the like can be used. These crosslinking agents may be used alone or in combination of two or more.
  • the urethane resin composition of the present invention can provide a film having excellent chemical resistance. Therefore, the urethane resin composition of the present invention is suitably used as a surface treatment agent for various articles such as synthetic leather, polyvinyl chloride (PVC) leather, thermoplastic olefin resin (TPO) leather, dashboard, and instrument panel. be able to.
  • PVC polyvinyl chloride
  • TPO thermoplastic olefin resin
  • the article of the present invention has a layer formed by the surface treatment agent.
  • the article include, for example, synthetic leather, artificial leather, natural leather, automobile interior seats using polyvinyl chloride (PVC) leather, sports shoes, clothing, furniture, thermoplastic olefin (TPO) leather, and dashboard. , Instrument panels and the like.
  • PVC polyvinyl chloride
  • TPO thermoplastic olefin
  • the thickness of the layer made of the surface treatment agent is, for example, in the range of 0.1 to 100 ⁇ m.
  • urethane prepolymer solution in methyl ethyl ketone 6.8 parts by mass of hydrazine and 15 parts by mass of triethylamine were mixed with the methyl ethyl ketone solution of the urethane prepolymer, and then 820 parts by mass of ion-exchanged water was added to disperse the urethane resin (A-1) in water. A liquid was obtained. Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain an aqueous dispersion of a urethane resin (A-1) having a nonvolatile content of 30% by mass.
  • urethane resin (A-3) having a nonvolatile content of 30% by mass.
  • the urethane resin (A-3) obtained had a urethane bond content of 1,747 mmol / kg, a urea bond content of 576 mmol / kg, and an alicyclic structure content of 2,341 mmol / kg.
  • Example 1 35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc.), and a filler (manufactured by Evonik Degussa) ACEMATT TS 100, 2 parts by mass of silica particles produced by a dry method, average particle size: 10 ⁇ m, water dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 25.5) By mixing 3 parts by mass of water and 57 parts by mass of water, a urethane resin composition was obtained.
  • a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc.)
  • a filler manufactured by Evonik Degussa) ACEMATT
  • Example 2 35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc.), and a filler (manufactured by Evonik Degussa) ACEMATT TS 100, 2 parts by mass of silica particles produced by a dry method, average particle size: 10 ⁇ m, water dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 25.5) A urethane resin composition was obtained by mixing 6 parts by mass of water and 54 parts by mass of water.
  • a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc.)
  • a filler manufactured by Evonik Degussa) ACEMATT TS 100
  • Example 3 35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc.), and a filler (manufactured by Evonik Degussa) ACEMATT TS 100, 2 parts by mass of silica particles produced by a dry method, average particle size: 10 ⁇ m, water dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 25.5) Urethane resin composition was obtained by mixing 0.5 parts by mass of 50000 parts by mass and 59.5 parts by mass of water.
  • a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc.)
  • a filler manufactured by Evonik Degussa) ACE
  • Example 1 A urethane resin composition was obtained in the same manner as in Example 1 except that the aqueous dispersion of polydimethylsiloxane was omitted.
  • a carbodiimide cross-linking agent “Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc.
  • a filler (“ACEMATT” manufactured by Evonik Degussa
  • the number average molecular weight of the polyol used in the synthesis example is a value 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 connected in series and used. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 Book “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.
  • the number average molecular weight of the silicone compound (C) is a value measured by GPC (gel permeation chromatography) 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 connected in series and used. "TSKgel GMHXL” (7.8 mm ID x 30 cm) x 4 detectors: RI (differential refractometer) Column temperature: 40 ° C Eluent: tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 ⁇ L Concentration: Analytical sample: 4 mg / mL tetrahydrofuran solution standard: 1 mg / mL tetrahydrofuran solution standard: A calibration curve was prepared using the following polyethylene oxide / polyethylene glycol.
  • the urethane resin composition of the present invention has excellent abrasion resistance.
  • Comparative Example 1 was an embodiment in which no silicone compound (C) was used, but the abrasion resistance was insufficient.
  • Comparative Example 2 is an embodiment in which a silicone compound having a number average molecular weight below the range specified in the present invention was used instead of the silicone compound (C), but the abrasion resistance was insufficient.
  • Comparative Example 3 is an embodiment in which a silicone compound having a number average molecular weight exceeding the range specified in the present invention is used instead of the silicone compound (C). It was difficult to use as.

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Abstract

The present invention provides a urethane resin composition characterized by containing a urethane resin (A), water (B), and a silicone compound (C) having a number-average molecular weight of not less than 150,000 but less than 330,000. The present invention also provides: a surface treatment agent characterized by containing the urethane resin composition; and an article having a layer formed of the surface treatment agent. The contained amount of the silicone compound (C) is preferably in the range of 0.01-10 mass%. The silicone compound (C) is preferably polydimethylsiloxane. The silicone compound (C) is preferably polydimethylsiloxane. The surface treatment agent preferably further contains a filler (D).

Description

ウレタン樹脂組成物、表面処理剤、及び、物品Urethane resin composition, surface treatment agent, and article
　本発明は、ウレタン樹脂組成物、表面処理剤、及び、表面処理剤による層を有する物品に関する。 The present invention relates to a urethane resin composition, a surface treatment agent, and an article having a layer formed by the surface treatment agent.
　自動車内装レザー用シートの製造工程においては、その表面に耐薬品性および意匠性付与の観点から、表面処理剤により仕上げがなされている。従来の表面処理剤に用いられる材料は、有機溶剤を含んだ溶剤系樹脂組成物が主流であったが、近年の環境規制の高まりを受け、有機溶剤を実質的に含まない水性表面処理剤の開発が進められている。 In the manufacturing process of automotive interior leather seats, the surface is finished with a surface treatment agent from the viewpoint of imparting chemical resistance and design. The material used for the conventional surface treatment agent is mainly a solvent-based resin composition containing an organic solvent. However, due to the recent increase in environmental regulations, an aqueous surface treatment agent substantially containing no organic solvent has been developed. Development is underway.
　前記水性表面処理剤としては、例えば、特定の機械物性を有するポリウレタン、カルボジイミド架橋剤、及び、フィラーを含有する水性表面処理剤が開示されている（例えば、特許文献１を参照。）。しかしながら、従来の溶剤系樹脂組成物を水系化すると耐摩耗性が低下する問題があり、前記水性表面処理剤についても表面の摩擦係数が高く、更なる耐摩耗性の改善が求められていた。 水性 As the aqueous surface treating agent, for example, a polyurethane having specific mechanical properties, a carbodiimide crosslinking agent, and an aqueous surface treating agent containing a filler are disclosed (for example, see Patent Document 1). However, when the conventional solvent-based resin composition is converted to an aqueous system, there is a problem in that the abrasion resistance is reduced. The aqueous surface treating agent also has a high surface friction coefficient, and further improvement in abrasion resistance has been demanded.
国際公開第２０１５／１０７９３３号公報International Publication No. WO 2015/107933
　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において、耐摩耗性に優れる皮膜が得られるウレタン樹脂組成物を提供することである。 課題 The problem to be solved by the present invention is to provide a urethane resin composition which can provide a film having excellent wear resistance in a water-containing urethane resin composition.
　本発明は、ウレタン樹脂（Ａ）、水（Ｂ）、及び、数平均分子量が１５万以上３３万未満であるシリコーン化合物（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。 The present invention provides a urethane resin composition containing a urethane resin (A), water (B), and a silicone compound (C) having a number average molecular weight of 150,000 or more and less than 330,000. It is.
　また、本発明は、前記ウレタン樹脂組成物を含有することを特徴とする表面処理剤、及び、その表面処理剤により形成された層を有することを特徴とする物品を提供するものである。 The present invention also provides a surface treatment agent containing the urethane resin composition, and an article having a layer formed by the surface treatment agent.
　本発明のウレタン樹脂組成物は、耐薬品性に優れる皮膜を得ることができる。よって、本発明のウレタン樹脂組成物は、各種物品の表面処理剤として好適に用いることができる。 は The urethane resin composition of the present invention can provide a film having excellent chemical resistance. Therefore, the urethane resin composition of the present invention can be suitably used as a surface treatment agent for various articles.
　本発明のウレタン樹脂組成物は、ウレタン樹脂（Ａ）、水（Ｂ）、及び、特定の数平均分子量を有するシリコーン化合物（Ｃ）を含有するものである。 ウ The urethane resin composition of the present invention contains a urethane resin (A), water (B), and a silicone compound (C) having a specific number average molecular weight.
　前記ウレタン樹脂（Ａ）は、水（Ｂ）に分散し得るものであり、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。 The urethane resin (A) can be dispersed in water (B), and is, for example, a urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group; A urethane resin dispersed in B) can be used. These urethane resins (A) may be used alone or in combination of two or more.
　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。 As a method for obtaining the urethane resin having an anionic group, for example, a method using one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group as a raw material may be mentioned.
　前記カルボキシル基を有する化合物としては、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。 Examples of the compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, and Herbic acid or the like can be used. These compounds may be used alone or in combination of two or more.
　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。 Examples of the compound having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, and N- (2-aminoethyl)- 2-aminoethylsulfonic acid and the like can be used. These compounds may be used alone or in combination of two or more.
　前記カルボキシル基及びスルホニル基は、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。 The carboxyl group and the sulfonyl group may be partially or entirely neutralized by a basic compound in the resin composition. Examples of the basic compound include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; and metal base compounds including sodium, potassium, lithium, and calcium. Can be.
　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。 方法 As a method for obtaining the urethane resin having a cationic group, for example, a method using one or more compounds having an amino group as a raw material may be mentioned.
　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。 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; 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.
　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。 方法 As a method for obtaining the urethane resin having a nonionic group, for example, a method using one or more compounds having an oxyethylene structure as a raw material may be mentioned.
　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、ポリオキシ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。 As the compound having an oxyethylene structure, for example, polyether polyol having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol can be used. These compounds may be used alone or in combination of two or more.
　以上の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の使用量としては、より一層優れた耐薬品性、耐摩耗性、耐候性、及び、耐加水分解性が得られる点から、ウレタン樹脂（Ａ）の原料中０．１～１５質量％の範囲であることが好ましく、１～１０質量％の範囲がより好ましく、１．５～７質量％の範囲が更に好ましい。 The amount of the raw material used for producing the urethane resin having the above hydrophilic group is such that urethane is more excellent in chemical resistance, abrasion resistance, weather resistance, and hydrolysis resistance. It is preferably in the range of 0.1 to 15% by mass, more preferably in the range of 1 to 10% by mass, and even more preferably in the range of 1.5 to 7% by mass of the raw material of the resin (A).
　前記強制的に水（Ｂ）中に分散するウレタン樹脂を得る際に用いることができる乳化剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビトールテトラオレエート、ポリオキシエチレン・ポリオキシプロピレン共重合体等のノニオン性乳化剤；オレイン酸ナトリウム等の脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルフォン酸塩、アルキルスルホコハク酸塩、ナフタレンスルフォン酸塩、ポリオキシエチレンアルキル硫酸塩、アルカンスルフォネートナトリウム塩、アルキルジフェニルエーテルスルフォン酸ナトリウム塩等のアニオン性乳化剤；アルキルアミン塩、アルキルトリメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩等のカチオン性乳化剤などを用いることができる。これらの乳化剤は単独で用いても２種以上を併用してもよい。 Examples of the emulsifier that can be used for obtaining the urethane resin that is forcibly dispersed in water (B) include, for example, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene Nonionic emulsifiers such as ethylene sorbitol tetraoleate and polyoxyethylene / polyoxypropylene copolymers; fatty acid salts such as sodium oleate; alkyl sulfates; alkyl benzene sulfonates; alkyl sulfosuccinates; naphthalene sulfonates; Anionic emulsifiers such as polyoxyethylene alkyl sulfate, sodium alkane sulfonate, sodium salt of alkyl diphenyl ether sulfonate; alkyl amine salt, alkyl trimethyl ammonium Arm salts, cationic emulsifiers such as alkyl dimethyl benzyl ammonium salts can be used. These emulsifiers may be used alone or in combination of two or more.
　前記ウレタン樹脂（Ａ）としては、具体的には、例えば、前記した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、ポリイソシアネート（ａ１）、ポリオール（ａ２）、及び、鎖伸長剤（ａ３）の反応物を用いることができる。これらの反応は公知のウレタン化反応を用いることができる。 As the urethane resin (A), specifically, for example, a raw material used for producing the above-mentioned urethane resin having a hydrophilic group, polyisocyanate (a1), polyol (a2), and a chain extender ( The reactants of a3) can be used. For these reactions, known urethanation reactions can be used.
　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、トリレ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また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。 Examples of the polyisocyanate (a1) include aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidated diphenylmethane polyisocyanate; hexamethylene diisocyanate And aliphatic or alicyclic polyisocyanates such as lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, dimer acid diisocyanate and norbornene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.
　前記ポリイソシアネート（ａ１）としては、より一層優れた耐薬品性、耐摩耗性、及び、耐候性が得られる点から、脂環式ポリイソシアネートを用いることが好ましく、少なくともイソシアネート基の窒素原子がシクロヘキサン環と直接連結した構造を１つ以上有するポリイソシアネートを用いることがより好ましく、イソホロンジイソシアネート及び／又はジシクロヘキシルメタンジイソシアネートを用いることが更に好ましい。また、脂環式ポリイソシアネートの使用量としては、より一層優れた耐薬品性、耐摩耗性、及び、耐候性が得られる点から、ポリイソシアネート（ａ１）中３０質量％以上であることが好ましく、４０質量％以上がより好ましく、５０質量％以上が更に好ましい。 As the polyisocyanate (a1), it is preferable to use an alicyclic polyisocyanate from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance, and at least the nitrogen atom of the isocyanate group is cyclohexane. It is more preferable to use a polyisocyanate having one or more structures directly connected to a ring, and it is more preferable to use isophorone diisocyanate and / or dicyclohexylmethane diisocyanate. Further, the amount of the alicyclic polyisocyanate used is preferably 30% by mass or more in the polyisocyanate (a1) from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. , 40% by mass or more, more preferably 50% by mass or more.
　また、本発明のウレタン樹脂組成物が表面処理剤として使用される際に、より一層の耐光性が求められる場合には、前記ポリイソシアネート（ａ１）として、前記脂環式ポリイソシアネートと脂肪族ポリイソシアネートとを併用することが好ましく、前記脂肪族ポリイソシアネートとしては、ヘキサメチレンジイソシアネートを用いることが好ましい。この際のポリイソシアネート（ａ１）中の前記脂環式ポリイソシアネートの含有量としては、３０質量％以上であることが好ましく、４０質量％以上がより好ましく、５０質量％以上が更に好ましい。 In the case where the urethane resin composition of the present invention is used as a surface treatment agent and further light resistance is required, as the polyisocyanate (a1), the alicyclic polyisocyanate and the aliphatic polyisocyanate may be used. It is preferable to use an isocyanate in combination, and it is preferable to use hexamethylene diisocyanate as the aliphatic polyisocyanate. At this time, the content of the alicyclic polyisocyanate in the polyisocyanate (a1) is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more.
　前記ポリイソシアネート（ａ１）の使用量としては、より一層優れた耐薬品性、耐摩耗性、及び、耐候性が得られる点から、ウレタン樹脂（Ａ）の原料中５～５０質量％の範囲であることが好ましく、１５～４０質量％の範囲がより好ましく、２０～３７質量％の範囲が更に好ましい。 The amount of the polyisocyanate (a1) used is in the range of 5 to 50% by mass in the raw material of the urethane resin (A) from the viewpoint that more excellent chemical resistance, abrasion resistance and weather resistance are obtained. It is preferably in the range of 15 to 40% by mass, more preferably in the range of 20 to 37% by mass.
　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。これらの中でも、より一層優れた耐薬品性、耐摩耗性、及び、耐候性が得られる点から、ポリカーボネートポリオールを用いることが好ましい。 ポ リ オ ー ル As the polyol (a2), for example, polyether polyol, polyester polyol, polyacryl polyol, polycarbonate polyol, polybutadiene polyol and the like can be used. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use a polycarbonate polyol from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance.
　前記ポリカーボネートポリオールとしては、例えば、炭酸エステル及び／又はホスゲンと、水酸基を２個以上有する化合物との反応物を用いることができる。 反 応 As the polycarbonate polyol, for example, a reaction product of a carbonate ester and / or phosgene and a compound having two or more hydroxyl groups can be used.
　前記炭酸エステルとしては、例えば、ジメチルカーボネート、ジエチルカーボネート、ジフェニルカーボネート、エチレンカーボネート、プロピレンカーボネート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。 炭 酸 As the carbonate ester, for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like can be used. These compounds may be used alone or in combination of two or more.
　前記水酸基を２個以上有する化合物としては、例えば、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，３－ブタンジオール、１，２－ブタンジオール、２－メチル－１，３－プロパンジオール、１，５－ペンタンジオール、ネオペンチルグリコール、１，６－ヘキサンジオール、１，５－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，８－ノナンジオール、２－エチル－２－ブチル－１，３－プロパンジオール、１，１０－デカンジオール、１，１２－ドデカンジオール、１，４－シクロヘキサンジメタノール、１，３－シクロヘキサンジメタノール、トリメチロールプロパン、３－メチルペンタンジオール、ネオペンチルグリコール、トリメチロールエタン、グリセリン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。これらの中でも、より一層優れた耐薬品性、耐摩耗性、及び、耐候性が得られる点から、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，４－シクロヘキサンジメタノール、３－メチルペンタンジオール、及び、１，１０－デカンジオールからなる群から選ばれる１種以上の化合物を用いることが好ましく、１，６－ヘキサンジオールがより好ましい。 Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl 1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,10-decanediol, 1,12-dodecanediol 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane , 3-methyl pentanediol, neopentyl glycol, trimethylol ethane, can be used glycerin. These compounds may be used alone or in combination of two or more. Among these, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-propanediol, 1,6-pentanediol and 1,6-propanediol are more excellent in chemical resistance, abrasion resistance, and weather resistance. It is preferable to use one or more compounds selected from the group consisting of -hexanediol, 1,4-cyclohexanedimethanol, 3-methylpentanediol, and 1,10-decanediol. More preferred.
　前記ポリカーボネートポリオールの使用量としては、より一層優れた耐薬品性、耐摩耗性、及び、耐候性が得られる点から、ポリオール（ａ２）中８５質量％以上であることが好ましく、９０質量％以上がより好ましく、９５質量％以上が更に好ましい。 The amount of the polycarbonate polyol used is preferably 85% by mass or more in the polyol (a2), and more preferably 90% by mass or more from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. Is more preferable, and 95 mass% or more is still more preferable.
　前記ポリカーボネートポリオールの数平均分子量としては、より一層優れた耐薬品性、機械的強度、耐摩耗性、及び、耐候性が得られる点から、１００～１００，０００の範囲であることが好ましく、１５０～１０，０００の範囲より好ましく、２００～２，５００の範囲が更に好ましい。なお、前記ポリカーボネートポリオールの数平均分子量は、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。 The number average molecular weight of the polycarbonate polyol is preferably in the range of 100 to 100,000 from the viewpoint of obtaining more excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance. It is more preferably in the range of ～ 10,000, further preferably in the range of 200２００2,500. In addition, the number average molecular weight of the polycarbonate polyol indicates a value measured by a gel permeation column chromatography (GPC) method.
　前記ポリカーボネートポリオール以外の前記ポリオール（ａ２）の数平均分子量としては、より一層優れた耐候性が得られる点から、５００～１００，０００の範囲であることが好ましく、７００～５０，０００の範囲より好ましく、８００～１０，０００の範囲が更に好ましい。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。 The number average molecular weight of the polyol (a2) other than the polycarbonate polyol is preferably in the range of 500 to 100,000, and more preferably in the range of 700 to 50,000, from the viewpoint that more excellent weather resistance is obtained. Preferably, the range is 800 to 10,000. In addition, the number average molecular weight of the polyol (a2) indicates a value measured by a gel permeation column chromatography (GPC) method.
　前記ポリオール（ａ２）の使用量としては、ウレタン樹脂（Ａ）の原料中３０～８０質量％の範囲であることが好ましく、４０～７５質量％の範囲がより好ましく、５０～７０質量％の範囲が更に好ましい。 The amount of the polyol (a2) used is preferably in the range of 30 to 80% by mass, more preferably in the range of 40 to 75% by mass, and more preferably in the range of 50 to 70% by mass in the raw material of the urethane resin (A). Is more preferred.
　前記鎖伸長剤（ａ３）としては、例えば、数平均分子量が５０～４５０の範囲のもの（前記ポリカーボネートポリオールを除く。）であり、具体的には、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；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。 Examples of the chain extender (a3) include those having a number average molecular weight in the range of 50 to 450 (excluding the polycarbonate polyol), and specifically include ethylenediamine, 1,2-propanediamine, 6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3, A chain extender having an amino group such as 3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, , 3- Lopandiol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, trimethylol A chain extender having a hydroxyl group such as propane can be used. These chain extenders may be used alone or in combination of two or more.
　前記鎖伸長剤（ａ３）としては、前記した中でも、より一層優れた耐薬品性、機械的強度、耐摩耗性、及び、耐候性が得られる点から、アミノ基を有する鎖伸長剤を用いることが好ましく、ピペラジン及び／又はヒドラジンがより好ましく、ピペラジン及びヒドラジンの合計量としては、前記鎖伸長剤（ａ３）中３０質量％以上であることが好ましく、５０質量％以上がより好ましく、６０質量％以上が更に好ましく、８０質量％以上が特に好ましい。また、前記鎖伸長剤（ａ３）としては、平均官能基数が３未満であること好ましく、２．５未満がより好ましい。また、 As the chain extender (a3), among those described above, a chain extender having an amino group is used, because more excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance are obtained. Is preferable, and piperazine and / or hydrazine are more preferable. The total amount of piperazine and hydrazine is preferably 30% by mass or more in the chain extender (a3), more preferably 50% by mass or more, and 60% by mass. The above is more preferable, and the amount is particularly preferably 80% by mass or more. The chain extender (a3) preferably has an average number of functional groups of less than 3, more preferably less than 2.5. Also,
　前記鎖伸長剤（ａ３）の使用量としては、より一層優れた耐薬品性、機械的強度、耐摩耗性、及び、耐候性が得られる点から、ウレタン樹脂（Ａ）の原料中０．５～１０質量％の範囲であることが好ましく、０．７～５質量％の範囲がより好ましく、０．９～２．３の範囲が更に好ましい。 The amount of the chain extender (a3) used is 0.5% in the raw material of the urethane resin (A) from the viewpoint that even more excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance are obtained. The range is preferably from 10 to 10% by mass, more preferably from 0.7 to 5% by mass, and even more preferably from 0.9 to 2.3.
　前記ウレタン樹脂（Ａ）の製造方法としては、例えば、前記ポリイソシアネート（ａ１）と前記ポリオール（ａ２）と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を反応させることによって、イソシアネート基を有するウレタンプレポリマーを製造し、次いで、前記ウレタンプレポリマーと、前記鎖伸長剤（ａ３）とを反応させることによって製造する方法；前記ポリイソシアネート（ａ１）、前記ポリオール（ａ２）、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、及び、前記鎖伸長剤（ａ３）を一括に仕込み反応させる方法等が挙げられる。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。 The method for producing the urethane resin (A) includes, for example, reacting the polyisocyanate (a1), the polyol (a2), and a raw material used for producing the urethane resin having a hydrophilic group, thereby obtaining an isocyanate group. A method of producing a urethane prepolymer having the following formula: and then reacting the urethane prepolymer with the chain extender (a3); the polyisocyanate (a1), the polyol (a2), and a hydrophilic group. And a method in which the chain extender (a3) is charged and reacted at once. These reactions can be carried out, for example, at 50 to 100 ° C. for 3 to 10 hours.
　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、前記ポリオール（ａ２）が有する水酸基、及び、前記鎖伸長剤（ａ３）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。 The total of the hydroxyl group of the raw material used for producing the urethane resin having the hydrophilic group, the hydroxyl group of the polyol (a2), and the hydroxyl group and amino group of the chain extender (a3), and the polyisocyanate The molar ratio [(isocyanate group) / (hydroxyl group and amino group)] to the isocyanate group of (a1) is preferably in the range of 0.8 to 1.2, and is preferably in the range of 0.9 to 1.1. More preferably, it is within the range.
　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。 製造 When producing the urethane resin (A), it is preferable to deactivate the isocyanate groups remaining in the urethane resin (A). When deactivating the isocyanate group, it is preferable to use an alcohol having one hydroxyl group such as methanol. The amount of the alcohol to be 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).
　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、蒸留法等によって最終的には除去されることが好ましい。 有機 Further, when producing the urethane resin (A), an organic solvent may be used. Examples of the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; dimethylformamide and N-methylpyrrolidone. An amide compound or the like can be used. These organic solvents may be used alone or in combination of two or more. Preferably, the organic solvent is finally removed by a distillation method or the like.
　前記ウレタン樹脂（Ａ）のウレタン結合の含有量としては、より一層優れた耐薬品性、耐摩耗性、及び、耐候性が得られる点から、９８０～４，０００ｍｍｏｌ／ｋｇの範囲が好ましく、１，０００～３，５００ｍｍｏｌ／ｋｇの範囲がより好ましく、１，１００～３，０００ｍｍｏｌ／ｋｇの範囲が更に好ましく、１，１５０～２，５００ｍｍｏｌ／ｋｇの範囲が。なお、前記ウレタン樹脂（Ａ）のウレタン結合の含有量は、前記ポリイソシアネート（ａ１）、ポリオール（ａ２）、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、および、鎖伸長剤（ａ３）の仕込み量から算出される値を示す。 The content of the urethane bond in the urethane resin (A) is preferably in the range of 980 to 4,000 mmol / kg, from the viewpoint that more excellent chemical resistance, wear resistance, and weather resistance can be obtained. The range is more preferably from 2,000 to 3,500 mmol / kg, further preferably from 1,100 to 3,000 mmol / kg, and more preferably from 1,150 to 2,500 mmol / kg. The content of the urethane bond in the urethane resin (A) is determined by the following: the polyisocyanate (a1), the polyol (a2), the raw material used for producing the urethane resin having a hydrophilic group, and the chain extender (a3). ) Indicates a value calculated from the charged amount.
　前記ウレタン樹脂（Ａ）のウレア結合の含有量としては、より一層優れた耐薬品性、耐摩耗性、及び、耐候性が得られる点から、３１５～８５０ｍｍｏｌ／ｋｇの範囲であることが好ましく、３５０～８３０ｍｍｏｌ／ｋｇの範囲がより好ましく、４００～８００ｍｍｏｌ／ｋｇの範囲が更に好ましく、４１０～７７０ｍｍｏｌ／ｋｇの範囲が更に好ましい。なお、なお、前記ウレタン樹脂（Ａ）のウレア結合の含有量は、前記ポリイソシアネート（ａ１）、ポリオール（ａ２）、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、および、鎖伸長剤（ａ３）の仕込み量から算出される値を示す。 The content of the urea bond in the urethane resin (A) is preferably in the range of 315 to 850 mmol / kg from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance, The range is more preferably from 350 to 830 mmol / kg, still more preferably from 400 to 800 mmol / kg, even more preferably from 410 to 770 mmol / kg. In addition, the content of the urea bond of the urethane resin (A) is based on the polyisocyanate (a1), the polyol (a2), the raw material used for producing the urethane resin having a hydrophilic group, and the chain extender. A value calculated from the charged amount of (a3) is shown.
　前記ウレタン樹脂（Ａ）の脂環構造の含有量としては、より一層優れた耐薬品性、耐摩耗性、及び、耐候性が得られる点から、５００～３，０００ｍｍｏｌ／ｋｇの範囲であることが好ましく、６００～２，９００ｍｍｏｌ／ｋｇの範囲がより好ましく、７００～２，７００ｍｍｏｌ／ｋｇの範囲が更に好ましい。なお、なお、前記ウレタン樹脂（Ａ）の脂環構造の含有量は、前記ポリイソシアネート（ａ１）、ポリオール（ａ２）、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、および、鎖伸長剤（ａ３）の仕込み量から算出される値を示す。 The content of the alicyclic structure of the urethane resin (A) is in the range of 500 to 3,000 mmol / kg from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. Is preferably in the range of 600 to 2,900 mmol / kg, and more preferably in the range of 700 to 2,700 mmol / kg. In addition, the content of the alicyclic structure of the urethane resin (A) is based on the polyisocyanate (a1), the polyol (a2), the raw material used for producing the urethane resin having a hydrophilic group, and the chain extension. This shows a value calculated from the charged amount of the agent (a3).
　前記ウレタン樹脂（Ａ）の含有量としては、塗工性、作業性および保存安定性の点から、ウレタン樹脂組成物中３～５０質量％の範囲であることが好ましく、５～３０質量％の範囲がより好ましい。 The content of the urethane resin (A) is preferably in the range of 3 to 50% by mass, and more preferably 5 to 30% by mass in the urethane resin composition from the viewpoint of coating properties, workability and storage stability. The range is more preferable.
　前記水（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。前記水（Ｂ）の含有量としては、ウレタン樹脂組成物の塗工性、作業性および保存安定性の点から、ウレタン樹脂組成物中３０～９５質量％の範囲であることが好ましく、５０～９０質量％の範囲がより好ましい。 イ オ ン As the water (B), ion-exchanged water, distilled water or the like can be used. The content of the water (B) is preferably in the range of 30 to 95% by mass in the urethane resin composition, from the viewpoint of coatability, workability and storage stability of the urethane resin composition, A range of 90% by mass is more preferable.
　前記シリコーン化合物（Ｃ）としては、優れた耐摩耗性を得るうえで、数平均分子量が１５万以上３３万未満であるものを用いることが必須である。このように比較的高分子量のシリコーン化合物を用いることで、表面強度が高く、摩擦係数の小さな塗膜が形成され、優れた耐摩耗性を得ることができる。前記シリコーン化合物（Ｃ）の数平均分子量としては、より一層優れた耐摩耗性が得られる点から、２０万～３０万の範囲であることが好ましく、２２万～２７万の範囲がより好ましい。なお、前記シリコーン化合物（Ｃ）の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定した値を示し、具体的には実施例にてその測定方法を示す。 As the silicone compound (C), it is essential to use a compound having a number average molecular weight of 150,000 or more and less than 330,000 in order to obtain excellent wear resistance. By using a silicone compound having a relatively high molecular weight, a coating film having a high surface strength and a small coefficient of friction is formed, and excellent wear resistance can be obtained. The number average molecular weight of the silicone compound (C) is preferably in the range of 200,000 to 300,000, more preferably 220,000 to 270,000, from the viewpoint of obtaining more excellent abrasion resistance. The number average molecular weight of the silicone compound (C) indicates a value measured by a gel permeation chromatography (GPC) method, and specifically, the measuring method is described in Examples.
　前記シリコーン化合物（Ｃ）としては、具体的には、例えば、ポリジメチルシロキサン、ポリメチルフェニルシロキサン、ポリメチルハイドロジェンシロキサン、ポリメチルフェニルハイドロジェンシロキサン；これらの変性物；これらのシリコーン化合物とアクリルとの共重合体などを用いることができる。これらのシリコーン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、より一層優れた耐摩耗性が得られる点から、ポリジメチルシロキサンを用いることが好ましい。 Specific examples of the silicone compound (C) include polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, and polymethylphenylhydrogensiloxane; modified products thereof; these silicone compounds and acryl. And the like can be used. These silicone compounds may be used alone or in combination of two or more. Among these, it is preferable to use polydimethylsiloxane from the viewpoint that more excellent wear resistance can be obtained.
　前記シリコーン化合物（Ｃ）は、水（Ｂ）との親和性の点から、水（Ｂ）に分散したエマルジョンの形態をとっていることが好ましい。またかかる際には、公知の界面活性剤が含有されていてもよい。 シ リ コ ー ン The silicone compound (C) is preferably in the form of an emulsion dispersed in water (B) from the viewpoint of affinity with water (B). In such a case, a known surfactant may be contained.
　前記シリコーン化合物（Ｃ）の含有量（＝シリコーン化合物（Ｃ）固形分）としては、より一層優れた耐摩耗性が得られる点から０．０１～１０質量％の範囲であることが好ましく、０．１～７質量％の範囲がより好ましく、０．５～５質量％の範囲が更に好ましい。 The content of the silicone compound (C) (= solid content of the silicone compound (C)) is preferably in the range of 0.01 to 10% by mass from the viewpoint of obtaining more excellent wear resistance. The range is more preferably from 1 to 7% by mass, and even more preferably from 0.5 to 5% by mass.
　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、シリコーン化合物（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用いてもよい。 ウ The urethane resin composition of the present invention contains the urethane resin (A), water (B), and silicone compound (C) as essential components, but may use other additives as necessary.
　前記その他の添加剤としては、例えば、フィラー（Ｄ）、架橋剤（Ｅ）、乳化剤、消泡剤、レベリング剤、増粘剤、粘弾性調整剤、消泡剤、湿潤剤、分散剤、防腐剤、可塑剤、浸透剤、香料、殺菌剤、殺ダニ剤、防かび剤、紫外線吸収剤、酸化防止剤、帯電防止剤、難燃剤、染料、顔料（例えば、チタン白、ベンガラ、フタロシアニン、カーボンブラック、パーマネントイエロー等）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良い。 Examples of the other additives include a filler (D), a crosslinking agent (E), an emulsifier, an antifoaming agent, a leveling agent, a thickener, a viscoelasticity adjusting agent, an antifoaming agent, a wetting agent, a dispersant, and a preservative. Agents, plasticizers, penetrants, fragrances, bactericides, acaricides, fungicides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (e.g., titanium white, redwood, phthalocyanine, carbon Black, permanent yellow, etc.) can be used. These additives may be used alone or in combination of two or more.
　前記その他の添加剤としては、本発明のウレタン樹脂組成物が表面処理剤として使用される場合には、その塗膜にマット感を付与するためにフィラー（Ｄ）、及び、塗膜の機械的強度を向上するために架橋剤（Ｅ）を含有することが好ましい。 As the other additives, when the urethane resin composition of the present invention is used as a surface treatment agent, a filler (D) for imparting a matte feeling to the coating film, and mechanical properties of the coating film It is preferable to include a crosslinking agent (E) in order to improve the strength.
　前記フィラー（Ｄ）としては、例えば、シリカ粒子、有機ビーズ、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、タルク、水酸化アルミニウム、硫酸カルシウム、カオリン、雲母、アスベスト、マイカ、ケイ酸カルシウム、アルミナシリケイト等を用いることができる。これらのフィラーは、単独で用いても２種以上を併用してもよい。 Examples of the filler (D) include silica particles, organic beads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, and alumina silicate. Can be used. These fillers may be used alone or in combination of two or more.
　前記シリカ粒子としては、例えば、乾式シリカ、湿式シリカ等を用いることができる。これらの中でも、散乱効果が高く光沢値の調整範囲が広くなることから、乾式シリカが好ましい。これらシリカ粒子の平均粒子径としては、２～１４μｍの範囲であることが好ましく、３～１２μｍの範囲がより好ましい。なお、前記シリカ粒子の平均粒子径は、粒度分布測定結果の積算粒子量曲線において、その積算量が５０％を占めるときの粒子径（粒度分布におけるＤ５０での粒子径）を示す。 、 As the silica particles, for example, dry silica, wet silica and the like can be used. Of these, dry silica is preferred because of its high scattering effect and wide adjustment range of gloss value. The average particle size of these silica particles is preferably in the range of 2 to 14 μm, and more preferably in the range of 3 to 12 μm. The average particle size of the silica particles indicates the particle size (the particle size at D50 in the particle size distribution) when the integrated amount occupies 50% in the integrated particle amount curve of the particle size distribution measurement result.
　前記有機ビーズとしては、例えば、アクリルビーズ、ウレタンビーズ、シリコンビーズ、オレフィンビーズ等を用いることができる。 ア ク リ ル As the organic beads, for example, acrylic beads, urethane beads, silicon beads, olefin beads and the like can be used.
　前記フィラー（Ｄ）の使用量は、付与するマット感に応じて適宜決定することができるが、例えば、ウレタン樹脂（Ａ）１００質量部に対して、１～３０質量部の範囲であることが好ましく、３～１０質量部の範囲がより好ましい。 The amount of the filler (D) to be used can be appropriately determined according to the matt feeling to be imparted. For example, the amount is 1 to 30 parts by mass with respect to 100 parts by mass of the urethane resin (A). Preferably, the range is 3 to 10 parts by mass.
　前記架橋剤（Ｅ）としては、例えば、イソシアネート架橋剤、エポキシ架橋剤、カルボジイミド架橋剤、オキサゾリジン架橋剤、オキサゾリン架橋剤、メラミ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。 架橋 As the crosslinking agent (E), for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a carbodiimide crosslinking agent, an oxazolidine crosslinking agent, an oxazoline crosslinking agent, a melamine crosslinking agent and the like can be used. These crosslinking agents may be used alone or in combination of two or more.
　前記架橋剤（Ｅ）の使用量としては、例えば、前記ウレタン樹脂（Ａ）１００質量部に対して、５～４０質量部の範囲であることが好ましく、１０～３０質量部の範囲がより好ましい。 The amount of the crosslinking agent (E) to be used is, for example, preferably in the range of 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, based on 100 parts by mass of the urethane resin (A). .
　以上、本発明のウレタン樹脂組成物は、耐薬品性に優れる皮膜を得ることができる。よって、本発明のウレタン樹脂組成物は、合成皮革、ポリ塩化ビニル（ＰＶＣ）レザー、熱可塑性オレフィン樹脂（ＴＰＯ）レザー、ダッシュボード、インスツルメントパネル等の各種物品の表面処理剤として好適に用いることができる。 As described above, the urethane resin composition of the present invention can provide a film having excellent chemical resistance. Therefore, the urethane resin composition of the present invention is suitably used as a surface treatment agent for various articles such as synthetic leather, polyvinyl chloride (PVC) leather, thermoplastic olefin resin (TPO) leather, dashboard, and instrument panel. be able to.
　本発明の物品は、前記表面処理剤により形成された層を有する。 物品 The article of the present invention has a layer formed by the surface treatment agent.
　前記物品の具体的としては、例えば、合成皮革、人工皮革、天然皮革、ポリ塩化ビニル（ＰＶＣ）レザーを用いた自動車内装シート、スポーツ靴、衣料、家具、熱可塑性オレフィン（ＴＰＯ）レザー、ダッシュボード、インスツルメントパネル等が挙げられる。 Specific examples of the article include, for example, synthetic leather, artificial leather, natural leather, automobile interior seats using polyvinyl chloride (PVC) leather, sports shoes, clothing, furniture, thermoplastic olefin (TPO) leather, and dashboard. , Instrument panels and the like.
　前記表面処理剤による層の厚さとしては、例えば、０．１～１００μｍの範囲である。 層 The thickness of the layer made of the surface treatment agent is, for example, in the range of 0.1 to 100 μm.
　以下、実施例を用いて、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
［合成例１］ウレタン樹脂（Ａ－１）水分散体の調製
　攪拌機、温度計、および窒素還流管を備えた四つ口フラスコに、メチルエチルケトン２５０質量部、及びオクチル酸第一錫０．００１質量部を入れ、次いで、ポリカーボネートポリオール－１（１，４－ブタンジオール及び１，６－ヘキサンジオールを原料とするもの、数平均分子量：１，０００）２００質量部、２，２－ジメチロールプロピオン酸１５質量部、イソホロンジイソシアネート４９質量部、ヘキサメチレンジイソシアネート３４質量部を入れ、７０℃で１時間反応させ、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。
　次いで、このウレタンプレポリマーのメチルエチルケトン溶液に、ヒドラジン６．８質量部、トリエチルアミン１５質量部を混合させた後に、イオン交換水８２０質量部を加えてウレタン樹脂（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し、更にイオン交換水を加えることで、不揮発分３０質量％のウレタン樹脂（Ａ－１）水分散体を得た。
　得られたウレタン樹脂（Ａ－１）のウレタン結合の含有量は２，０５２ｍｍｏｌ／ｋｇ、ウレア結合の含有量は６９８ｍｍｏｌ／ｋｇ、脂環構造の含有量は７１５ｍｍｏｌ／ｋｇであった。 [Synthesis Example 1] Preparation of aqueous dispersion of urethane resin (A-1) In a four-necked flask equipped with a stirrer, a thermometer, and a nitrogen reflux tube, 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octylate Parts, then 200 parts by mass of polycarbonate polyol-1 (based on 1,4-butanediol and 1,6-hexanediol, number average molecular weight: 1,000), 2,2-dimethylolpropionic acid 15 parts by mass, 49 parts by mass of isophorone diisocyanate, and 34 parts by mass of hexamethylene diisocyanate were added and reacted at 70 ° C. for 1 hour to obtain a urethane prepolymer solution in methyl ethyl ketone.
Next, 6.8 parts by mass of hydrazine and 15 parts by mass of triethylamine were mixed with the methyl ethyl ketone solution of the urethane prepolymer, and then 820 parts by mass of ion-exchanged water was added to disperse the urethane resin (A-1) in water. A liquid was obtained.
Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain an aqueous dispersion of a urethane resin (A-1) having a nonvolatile content of 30% by mass.
The resulting urethane resin (A-1) had a urethane bond content of 2,052 mmol / kg, a urea bond content of 698 mmol / kg, and an alicyclic structure content of 715 mmol / kg.
［合成例２］ウレタン樹脂（Ａ－２）水分散体の調製
　攪拌機、温度計、および窒素還流管を備えた四つ口フラスコに、メチルエチルケトン２５０質量部、及びオクチル酸第一錫０．００１質量部を入れ、次いで、ポリカーボネートポリオール－３（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２２０質量部、２，２－ジメチロールプロピオン酸１２質量部、ジシクロヘキシルメタンジイソシアネート７０質量部を入れ、７０℃で１時間反応させ、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。
　次いで、このウレタンプレポリマーのメチルエチルケトン溶液に、ピペラジン４．５質量部、トリエチルアミン９質量部を混合させた後に、イオン交換水８８０質量部を加えてウレタン樹脂（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し、更にイオン交換水を加えることで、不揮発分３２質量％のウレタン樹脂（Ａ－２）水分散体を得た。
　得られたウレタン樹脂（Ａ－２）のウレタン結合の含有量は１，２７８ｍｍｏｌ／ｋｇ、ウレア結合の含有量は４３５ｍｍｏｌ／ｋｇ、脂環構造の含有量は１，７１３ｍｍｏｌ／ｋｇであった。 [Synthesis Example 2] Preparation of aqueous dispersion of urethane resin (A-2) In a four-necked flask equipped with a stirrer, a thermometer, and a nitrogen reflux tube, 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octylate Parts, then 220 parts by mass of polycarbonate polyol-3 (based on 1,6-hexanediol, number average molecular weight: 2,000), 12 parts by mass of 2,2-dimethylolpropionic acid, dicyclohexylmethane 70 parts by mass of diisocyanate was added and reacted at 70 ° C. for 1 hour to obtain a urethane prepolymer solution in methyl ethyl ketone.
Next, 4.5 parts by mass of piperazine and 9 parts by mass of triethylamine were mixed with the methyl ethyl ketone solution of the urethane prepolymer, and 880 parts by mass of ion-exchanged water was added thereto to emulsify the urethane resin (A-2) dispersed in water. A liquid was obtained.
Then, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain an aqueous dispersion of a urethane resin (A-2) having a nonvolatile content of 32% by mass.
The urethane resin (A-2) obtained had a urethane bond content of 1,278 mmol / kg, a urea bond content of 435 mmol / kg, and an alicyclic structure content of 1,713 mmol / kg.
［合成例３］ウレタン樹脂（Ａ－３）水分散体の調製
　攪拌機、温度計、および窒素還流管を備えた四つ口フラスコに、メチルエチルケトン２５０質量部、及びオクチル酸第一錫０．００１質量部を入れ、次いで、ポリカーボネートポリオール－４（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１３８質量部、ポリカーボネートポリオール－５（１，６－ヘキサンジオールを原料とするもの、数平均分子量：５００）を５５質量部、２，２－ジメチロールプロピオン酸１３質量部、ジシクロヘキシルメタンジイソシアネート１００質量部を入れ、７０℃で１時間反応させ、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。
　次いで、このウレタンプレポリマーのメチルエチルケトン溶液に、ピペラジン５．６質量部、トリエチルアミン１０質量部を混合させた後に、イオン交換水８８０質量部を加えてウレタン樹脂（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し、更にイオン交換水を加えることで、不揮発分３０質量％のウレタン樹脂（Ａ－３）水分散体を得た。
　得られたウレタン樹脂（Ａ－３）のウレタン結合の含有量は１，７４７ｍｍｏｌ／ｋｇ、ウレア結合の含有量は５７６ｍｍｏｌ／ｋｇ、脂環構造の含有量は２，３４１ｍｍｏｌ／ｋｇであった。 [Synthesis Example 3] Preparation of aqueous dispersion of urethane resin (A-3) In a four-necked flask equipped with a stirrer, a thermometer, and a nitrogen reflux tube, 250 parts by mass of methyl ethyl ketone and 0.001 parts by mass of stannous octylate Parts, and then 138 parts by mass of polycarbonate polyol-4 (based on 1,6-hexanediol as a raw material, number average molecular weight: 2,000), and polycarbonate polyol-5 (based on 1,6-hexanediol as a raw material). 55 parts by mass, 13 parts by mass of 2,2-dimethylolpropionic acid, and 100 parts by mass of dicyclohexylmethane diisocyanate, and reacted at 70 ° C. for 1 hour to prepare a urethane prepolymer solution in methyl ethyl ketone. Obtained.
Next, 5.6 parts by mass of piperazine and 10 parts by mass of triethylamine were mixed with the methyl ethyl ketone solution of the urethane prepolymer, and then 880 parts by mass of ion-exchanged water was added to disperse the urethane resin (A-3) in water. A liquid was obtained.
Then, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added to obtain an aqueous dispersion of a urethane resin (A-3) having a nonvolatile content of 30% by mass.
The urethane resin (A-3) obtained had a urethane bond content of 1,747 mmol / kg, a urea bond content of 576 mmol / kg, and an alicyclic structure content of 2,341 mmol / kg.
［実施例１］
　合成例１で得られたウレタン樹脂（Ａ－１）水分散体３５質量部、カルボジイミド架橋剤（日清紡ケミカル株式会社製「カルボジライトＶ－０２－Ｌ２」）３質量部、フィラー（エボニックデグサ社製「ＡＣＥＭＡＴＴ　ＴＳ　１００」、乾式法で製造されたシリカ粒子、平均粒子径：１０μｍ）２質量部、ポリジメチルシロキサンの水分散体（ポリジメチルシロキサンの含有率；６５質量％、数平均分子量；２５．５万）３質量部、水５７質量部を混合することで、ウレタン樹脂組成物を得た。 [Example 1]
35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc.), and a filler (manufactured by Evonik Degussa) ACEMATT TS 100, 2 parts by mass of silica particles produced by a dry method, average particle size: 10 μm, water dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 25.5) By mixing 3 parts by mass of water and 57 parts by mass of water, a urethane resin composition was obtained.
［実施例２］
　合成例１で得られたウレタン樹脂（Ａ－１）水分散体３５質量部、カルボジイミド架橋剤（日清紡ケミカル株式会社製「カルボジライトＶ－０２－Ｌ２」）３質量部、フィラー（エボニックデグサ社製「ＡＣＥＭＡＴＴ　ＴＳ　１００」、乾式法で製造されたシリカ粒子、平均粒子径：１０μｍ）２質量部、ポリジメチルシロキサンの水分散体（ポリジメチルシロキサンの含有率；６５質量％、数平均分子量；２５．５万）６質量部、水５４質量部を混合することで、ウレタン樹脂組成物を得た。 [Example 2]
35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc.), and a filler (manufactured by Evonik Degussa) ACEMATT TS 100, 2 parts by mass of silica particles produced by a dry method, average particle size: 10 μm, water dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 25.5) A urethane resin composition was obtained by mixing 6 parts by mass of water and 54 parts by mass of water.
［実施例３］
　合成例１で得られたウレタン樹脂（Ａ－１）水分散体３５質量部、カルボジイミド架橋剤（日清紡ケミカル株式会社製「カルボジライトＶ－０２－Ｌ２」）３質量部、フィラー（エボニックデグサ社製「ＡＣＥＭＡＴＴ　ＴＳ　１００」、乾式法で製造されたシリカ粒子、平均粒子径：１０μｍ）２質量部、ポリジメチルシロキサンの水分散体（ポリジメチルシロキサンの含有率；６５質量％、数平均分子量；２５．５万）０．５質量部、水５９．５質量部を混合することで、ウレタン樹脂組成物を得た。 [Example 3]
35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc.), and a filler (manufactured by Evonik Degussa) ACEMATT TS 100, 2 parts by mass of silica particles produced by a dry method, average particle size: 10 μm, water dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 25.5) Urethane resin composition was obtained by mixing 0.5 parts by mass of 50000 parts by mass and 59.5 parts by mass of water.
［実施例４］
　合成例１で得られたウレタン樹脂（Ａ－２）水分散体３５質量部、カルボジイミド架橋剤日清紡ケミカル株式会社製「カルボジライトＶ－０２－Ｌ２」）３質量部、フィラー（エボニックデグサ社製「ＡＣＥＭＡＴＴ　ＴＳ　１００」、乾式法で製造されたシリカ粒子、平均粒子径：１０μｍ）２質量部、ポリジメチルシロキサンの水分散体（ポリジメチルシロキサンの含有率；６５質量％、数平均分子量；２０万）３質量部、水５７質量部を混合することで、ウレタン樹脂組成物を得た。 [Example 4]
35 parts by weight of the aqueous dispersion of the urethane resin (A-2) obtained in Synthesis Example 1, 3 parts by weight of a carbodiimide crosslinking agent “Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd., and a filler (“ACEMATT” manufactured by Evonik Degussa) TS 100, 2 parts by mass of silica particles produced by a dry method, average particle size: 10 μm), aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 200,000) 3 A urethane resin composition was obtained by mixing parts by mass and 57 parts by mass of water.
［実施例５］
　合成例１で得られたウレタン樹脂（Ａ－３）水分散体３５質量部、カルボジイミド架橋剤日清紡ケミカル株式会社製「カルボジライトＶ－０２－Ｌ２」）３質量部、フィラー（エボニックデグサ社製「ＡＣＥＭＡＴＴ　ＴＳ　１００」、乾式法で製造されたシリカ粒子、平均粒子径：１０μｍ）２質量部、ポリジメチルシロキサンの水分散体（ポリジメチルシロキサンの含有率；６５質量％、数平均分子量；３０万）３質量部、水５７質量部を混合することで、ウレタン樹脂組成物を得た。 [Example 5]
35 parts by mass of the aqueous dispersion of the urethane resin (A-3) obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide crosslinking agent “Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd., and a filler (“ACEMATT” manufactured by Evonik Degussa) TS 100 ", 2 parts by mass of silica particles produced by a dry method, average particle size: 10 μm), aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 300,000) 3 A urethane resin composition was obtained by mixing parts by mass and 57 parts by mass of water.
［比較例１］
　実施例１において、ポリジメチルシロキサンの水分散体を除いた以外は、実施例１と同様にしてウレタン樹脂組成物を得た。 [Comparative Example 1]
A urethane resin composition was obtained in the same manner as in Example 1 except that the aqueous dispersion of polydimethylsiloxane was omitted.
［比較例２］
　合成例１で得られたウレタン樹脂（Ａ－１）水分散体３５質量部、カルボジイミド架橋剤日清紡ケミカル株式会社製「カルボジライトＶ－０２－Ｌ２」）３質量部、フィラー（エボニックデグサ社製「ＡＣＥＭＡＴＴ　ＴＳ　１００」、乾式法で製造されたシリカ粒子、平均粒子径：１０μｍ）２質量部、ポリジメチルシロキサンの水分散体（ポリジメチルシロキサンの含有率；６５質量％、数平均分子量；１０万）３質量部、水５７質量部を混合することで、ウレタン樹脂組成物を得た。 [Comparative Example 2]
35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide cross-linking agent “Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Inc., and a filler (“ACEMATT” manufactured by Evonik Degussa) TS 100 ", 2 parts by mass of silica particles produced by a dry method, average particle diameter: 10 μm, aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass, number average molecular weight: 100,000) 3 A urethane resin composition was obtained by mixing parts by mass and 57 parts by mass of water.
［比較例３］
　合成例１で得られたウレタン樹脂（Ａ－１）水分散体３５質量部、カルボジイミド架橋剤日清紡ケミカル株式会社製「カルボジライトＶ－０２－Ｌ２」）３質量部、フィラー（エボニックデグサ社製「ＡＣＥＭＡＴＴ　ＴＳ　１００」、乾式法で製造されたシリカ粒子、平均粒子径：１０μｍ）２質量部、水５７質量部を混合した後、ポリジメチルシロキサンの水分散体（ポリジメチルシロキサンの含有率；６５質量％、数平均分子量；５０万）３質量部を添加したが、混合せず、耐摩耗性の試験を行うことができなかった。 [Comparative Example 3]
35 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 3 parts by mass of a carbodiimide crosslinking agent "Carbodilite V-02-L2" manufactured by Nisshinbo Chemical Co., Ltd., and a filler ("ACEMATT" manufactured by Evonik Degussa) TS 100 ", 2 parts by mass of silica particles produced by a dry method, average particle size: 10 μm) and 57 parts by mass of water were mixed, and then an aqueous dispersion of polydimethylsiloxane (polydimethylsiloxane content: 65% by mass) , Number average molecular weight: 500,000), but 3 parts by mass were added, but they were not mixed and the abrasion resistance test could not be performed.
［数平均分子量の測定方法（１）］
　合成例で用いたポリオールの数平均分子量は、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。 [Method for measuring number average molecular weight (1)]
The number average molecular weight of the polyol used in the synthesis example is a value measured by gel permeation column chromatography (GPC) under the following conditions.
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。 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" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 Book “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 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（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」 (Standard polystyrene)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation
［数平均分子量の測定方法（２）］
　シリコーン化合物（Ｃ）の数平均分子量は、ＧＰＣ(ゲル・パーミエーション・クロマトグラフィー）法により、下記の条件で測定し得られた値を示す。 [Method for measuring number average molecular weight (2)]
The number average molecular weight of the silicone compound (C) is a value measured by GPC (gel permeation chromatography) under the following conditions.
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　ＧＭＨＸＬ」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×４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
濃度：分析試料：４ｍｇ／ｍＬのテトラヒドロフラン溶液
標準物質：１ｍｇ／ｍＬのテトラヒドロフラン溶液
標準物質：下記のポリエチレンオキシド／ポリエチレングリコールを用いて検量線を作成した。 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 GMHXL" (7.8 mm ID x 30 cm) x 4 detectors: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL
Concentration: Analytical sample: 4 mg / mL tetrahydrofuran solution standard: 1 mg / mL tetrahydrofuran solution standard: A calibration curve was prepared using the following polyethylene oxide / polyethylene glycol.
標準物質
〈ポリエチレンオキシド〉
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリエチレンオキシド　ＳＥ－７０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリエチレンオキシド　ＳＥ－３０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリエチレンオキシド　ＳＥ－１５」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリエチレンオキシド　ＳＥ－８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリエチレンオキシド　ＳＥ－５」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリエチレンオキシド　ＳＥ－２」
〈ポリエチレングリコール〉
　ポリエチレングリコール６，０００
　ポリエチレングリコール３，０００
　ポリエチレングリコール１，０００
　ポリエチレングリコール６００ Standard substance <polyethylene oxide>
"TSKgel Standard Polyethylene Oxide SE-70" manufactured by Tosoh Corporation
"TSKgel Standard Polyethylene Oxide SE-30" manufactured by Tosoh Corporation
"TSKgel Standard Polyethylene Oxide SE-15" manufactured by Tosoh Corporation
"TSKgel Standard Polyethylene Oxide SE-8" manufactured by Tosoh Corporation
"TSKgel Standard Polyethylene Oxide SE-5" manufactured by Tosoh Corporation
"TSKgel Standard Polyethylene Oxide SE-2" manufactured by Tosoh Corporation
<Polyethylene glycol>
Polyethylene glycol 6,000
Polyethylene glycol 3,000
Polyethylene glycol 1,000
Polyethylene glycol 600
［耐摩耗性の評価方法］
　離型紙上に５０μｍバーコーターを用いて実施例および比較例で得られたウレタン樹脂組成物を塗工し、１２０℃で２分間ギアオーブンにて乾燥させ、評価用サンプルを得た。この評価サンプルについて、平面摩耗試験機（インテック株式会社製「ＡＲ－４Ｓ」）を使用して、２ｋｇ荷重、６号帆布を使用して評価した。具体的には、平面摩耗試験機の上に、４．５ｍｍφのステンレスワイヤー、クッション材（厚さ；１０ｍｍ、圧縮応力；１Ｎ／ｃｍ２）、試験片の順に置き、５％引っ張って固定した。このサンプルの摩耗状態を１千回毎に観察し、塗膜が破れて生地が露出するまでの回数を測定した。なお、耐摩耗性の評価ができなかったものは「－」とした。 [Method for evaluating wear resistance]
The urethane resin compositions obtained in Examples and Comparative Examples were coated on release paper using a 50 μm bar coater, and dried in a gear oven at 120 ° C. for 2 minutes to obtain a sample for evaluation. This evaluation sample was evaluated using a flat wear tester (“AR-4S” manufactured by INTEC Corporation) using a 2 kg load and No. 6 canvas. Specifically, a 4.5 mmφ stainless steel wire, a cushion material (thickness: 10 mm, compressive stress; 1 N / cm 2 ), and a test piece were placed in this order on a flat abrasion tester, and fixed by pulling 5%. The abrasion state of this sample was observed every 1,000 times, and the number of times until the coating film was broken and the fabric was exposed was measured. In addition, when the abrasion resistance could not be evaluated, "-" was used.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び２中の「ＰＤＭＳｉ」は、ポリジメチルシロキサンを示す。 「" PDMSi "in Tables 1 and 2 indicates polydimethylsiloxane.
　本発明のウレタン樹脂組成物は、優れた耐摩耗性を有することがわかった。 わ か っ It was found that the urethane resin composition of the present invention has excellent abrasion resistance.
　一方、比較例１はシリコーン化合物（Ｃ）を一切使用しない態様であるが、耐摩耗性が不十分であった。 On the other hand, Comparative Example 1 was an embodiment in which no silicone compound (C) was used, but the abrasion resistance was insufficient.
　比較例２は、シリコーン化合物（Ｃ）の代わりに、本発明で規定する範囲を下回る数平均分子量を有するシリコーン化合物を用いた態様であるが、耐摩耗性が不十分であった。 Comparative Example 2 is an embodiment in which a silicone compound having a number average molecular weight below the range specified in the present invention was used instead of the silicone compound (C), but the abrasion resistance was insufficient.
　比較例３は、シリコーン化合物（Ｃ）の代わりに、本発明で規定する範囲を上回る数平均分子量を有するシリコーン化合物を用いた態様であるが、ウレタン樹脂組成物としてうまく混合できず、表面処理剤として使用することが困難であった。 Comparative Example 3 is an embodiment in which a silicone compound having a number average molecular weight exceeding the range specified in the present invention is used instead of the silicone compound (C). It was difficult to use as.

Claims (6)

  1. ウレタン樹脂（Ａ）、水（Ｂ）、及び、数平均分子量が１５万以上３３万未満であるシリコーン化合物（Ｃ）を含有することを特徴とするウレタン樹脂組成物。 A urethane resin composition comprising a urethane resin (A), water (B), and a silicone compound (C) having a number average molecular weight of 150,000 or more and less than 330,000.
  2. 前記シリコーン化合物（Ｃ）の含有量が、０．０１～１０質量％の範囲である請求項１記載のウレタン樹脂組成物。 The urethane resin composition according to claim 1, wherein the content of the silicone compound (C) is in a range of 0.01 to 10% by mass.
  3. 前記シリコーン化合物（Ｃ）が、ポリジメチルシロキサンである請求項１又は２記載のウレタン樹脂組成物。 The urethane resin composition according to claim 1 or 2, wherein the silicone compound (C) is polydimethylsiloxane.
  4. 請求項１～３のいずれか１項記載のウレタン樹脂組成物を含有することを特徴とする表面処理剤。 A surface treatment agent comprising the urethane resin composition according to any one of claims 1 to 3.
  5. 更にフィラー（Ｄ）を含有する請求項４記載の表面処理剤。 The surface treating agent according to claim 4, further comprising a filler (D).
  6. 請求項４又は５記載の表面処理剤により形成された層を有することを特徴とする物品。 An article comprising a layer formed by the surface treatment agent according to claim 4.
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