WO2020003779A1 - Composition de résine d'uréthane, agent de traitement de surface et article - Google Patents

Composition de résine d'uréthane, agent de traitement de surface et 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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English (en)
Japanese (ja)
Inventor
竹村　潔
宏之 千々和
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2020527264A priority Critical patent/JP7298608B2/ja
Priority to CN201980041730.7A priority patent/CN112313285B/zh
Publication of WO2020003779A1 publication Critical patent/WO2020003779A1/fr
Anticipated expiration legal-status Critical
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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une composition de résine d'uréthane caractérisée en ce qu'elle contient une résine d'uréthane (A), de l'eau (B) et un composé de silicone (C) présentant un poids moléculaire moyen en nombre de pas moins de 150 000 mais inférieur à 330 000. La présente invention concerne également : un agent de traitement de surface caractérisé en ce qu'il contient la composition de résine d'uréthane; et un article présentant une couche formée de l'agent de revêtement de surface. La quantité contenue du composé de silicone (C) est de préférence située dans la plage de 0,01 à 10 % en masse. Le composé de silicone (C) est de préférence le polydiméthylsiloxane. Le composé de silicone (C) est de préférence le polydiméthylsiloxane. De préférence, l'agent de traitement de surface contient en outre une charge (D).
PCT/JP2019/019055 2018-06-27 2019-05-14 Composition de résine d'uréthane, agent de traitement de surface et article Ceased WO2020003779A1 (fr)

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CN118159424A (zh) * 2021-10-12 2024-06-07 Dic株式会社 层叠体及合成皮革

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CN118159424A (zh) * 2021-10-12 2024-06-07 Dic株式会社 层叠体及合成皮革
CN115975492A (zh) * 2023-01-16 2023-04-18 帕珂表面处理技术(上海)有限公司 一种金属材料表面处理剂及其制备方法和用途

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