WO2020003780A1 - Composition de résine d'uréthanne, agent de traitement de surface et article - Google Patents

Composition de résine d'uréthanne, agent de traitement de surface et article Download PDF

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Publication number
WO2020003780A1
WO2020003780A1 PCT/JP2019/019056 JP2019019056W WO2020003780A1 WO 2020003780 A1 WO2020003780 A1 WO 2020003780A1 JP 2019019056 W JP2019019056 W JP 2019019056W WO 2020003780 A1 WO2020003780 A1 WO 2020003780A1
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Prior art keywords
urethane resin
mass
resin composition
parts
range
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PCT/JP2019/019056
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English (en)
Japanese (ja)
Inventor
竹村　潔
隆典 中庄谷
宏之 千々和
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DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2020527265A priority Critical patent/JP7294338B2/ja
Priority to CN201980041738.3A priority patent/CN112313286B/zh
Publication of WO2020003780A1 publication Critical patent/WO2020003780A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • 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
    • 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
    • C09D7/65—Additives macromolecular

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).
  • PVC vinyl chloride
  • the problem to be solved by the present invention is to provide a urethane resin composition which can provide a film having excellent adhesion to vinyl chloride (PVC) in a water-containing urethane resin composition.
  • PVC vinyl chloride
  • the present invention is characterized by containing a urethane resin (A) using dicyclohexylmethane diisocyanate (a1-1) as a raw material, water (B), and an adhesion promoter (C) having a number average molecular weight of 300 or more.
  • A dicyclohexylmethane diisocyanate
  • B water
  • C adhesion promoter
  • 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 adhesion to vinyl chloride (PVC) (hereinafter, abbreviated as “PVC adhesion”). Therefore, the urethane resin composition of the present invention can be suitably used as a surface treatment agent for various articles, and particularly suitably as a surface treatment agent for PVC leather.
  • PVC adhesion a film having excellent adhesion to vinyl chloride
  • the urethane resin composition of the present invention contains a urethane resin (A) starting from dicyclohexylmethane diisocyanate (a1-1), water (B), and an adhesion promoter (C) having a number average molecular weight of 300 or more. Is what you do.
  • 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 preferably in the range of 0.1 to 15% by mass, more preferably in the range of 1 to 10% by mass, and still more preferably in the range of 1.5 to 7% by mass in the raw material of the urethane 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,
  • the urethane resin (A) include a raw material used for producing the urethane resin having a hydrophilic group, a polyisocyanate (a1) containing dicyclohexylmethane diisocyanate (a1-1), and a polyol.
  • a reaction product of (a2) and a chain extender (a3) can be used. For these reactions, known urethanation reactions can be used.
  • the polyisocyanate as a raw material of the urethane resin (A) it is essential to use dicyclohexylmethane diisocyanate (a1-1). Thereby, a urethane resin film having excellent PVC adhesion can be obtained.
  • the amount of the dicyclohexylmethane diisocyanate (a1-1) to be used is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and more preferably 80% by mass in the polyisocyanate (a1). The above is more preferable, and 90% by mass or more is particularly preferable.
  • polyisocyanate (a1) that can be used other than the dicyclohexylmethane diisocyanate (a1-1) include, for example, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimide Aromatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate and the like. Or the like can be used over door. These polyisocyanates may be used alone or in combination of two 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 PVC adhesion, chemical resistance, and abrasion resistance can be obtained. Is preferably in the range of 15 to 40% by mass, and 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, when the urethane resin composition of the present invention is used as a surface treatment agent, it is preferable to use a polycarbonate polyol from the viewpoint of obtaining more excellent chemical resistance and abrasion 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.
  • 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.
  • 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, and 1,6-hexanediol are more preferred in that they provide even more excellent chemical resistance and abrasion resistance. It is preferable to use at least one compound selected from the group consisting of 1,4-cyclohexanedimethanol, 3-methylpentanediol, and 1,10-decanediol, and 1,6-hexanediol is more preferable.
  • the amount of the polycarbonate polyol to be used is preferably 85% by mass or more, more preferably 90% by mass or more in the polyol (a2) from the viewpoint of obtaining more excellent chemical resistance and abrasion resistance. , 95% by mass or more is 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, and abrasion resistance. 000, more preferably 200 to 2,500.
  • 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 in the range of 500 to 100,000 from the viewpoint of obtaining more excellent chemical resistance, mechanical strength, and abrasion resistance. Is preferable, more preferably in the range of 700 to 50,000, and still more preferably in the range of 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
  • the chain extender (a3) among the above, it is preferable to use a chain extender having an amino group from the viewpoint of obtaining more excellent chemical resistance, mechanical strength, and abrasion resistance, Piperazine and / or hydrazine are more preferable, and 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 still more preferably 60% by mass or more. preferable.
  • the chain extender (a3) preferably has an average number of functional groups of less than 3, more preferably less than 2.5. Also,
  • the amount of the chain extender (a3) to be used is 0.5 to 10% by mass in the raw material of the urethane resin (A), since more excellent chemical resistance, mechanical strength and abrasion resistance can be obtained. %, More preferably from 0.7 to 5% by mass, even more preferably from 0.9 to 2.3%.
  • 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 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.
  • 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 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.
  • 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).
  • 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 adhesion-imparting agent (C) it is essential to use one having a number average molecular weight of 300 or more from the viewpoint of obtaining excellent PVC adhesion.
  • the number-average molecular weight of the adhesion-imparting agent is preferably in the range of 400 to 10,000, more preferably in the range of 500 to 5,000, since more excellent PVC adhesion can be obtained.
  • the range is more preferably from 2,000 to 4,000.
  • the number average molecular weight of the adhesiveness-imparting agent (C) indicates the value when it can be calculated from the chemical structural formula, and the other values indicate the values measured by gel permeation column chromatography (GPC).
  • the adhesiveness imparting agent (C) for example, a polymer having an acid group, a polymer having an acidic group, a polymer having a functional group, and the like can be used. These adhesion promoters may be used alone or in combination of two or more. Among these, it is preferable to use a polymer having an acid group from the viewpoint that even better PVC adhesion can be obtained.
  • polymer having an acid group examples include a polyester having an acid group, an acrylic polymer having an acid group, a styrene polymer having an acid group, a styrene-isoprene polymer having an acid group, and a styrene-butadiene polymer having an acid group.
  • a polyester having an acid group an acrylic polymer having an acid group
  • a styrene polymer having an acid group a styrene-isoprene polymer having an acid group
  • styrene-butadiene polymer having an acid group examples include a polyester having an acid group, an acrylic polymer having an acid group, a styrene polymer having an acid group, a styrene-isoprene polymer having an acid group, and a styrene-butadiene polymer having an acid group.
  • These polymers may be used alone or in combination of two or more.
  • polyester having an acid group for example, a reaction product of a compound having two or more hydroxyl groups and a polybasic acid can be used.
  • Examples of the compound having two or more hydroxyl groups include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1, 3-butanediol, 2,2-diethyl-1,3-propanediol, 2,2-diethylpropanediol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propane Diol, 2-methyl-1,8-octanediol, 2,4-
  • These compounds may be used alone or in combination of two or more.
  • a compound having two to three hydroxyl groups is preferably used, and more preferably a compound having three hydroxyl groups is used, from the viewpoint that more excellent PVC adhesion can be obtained.
  • polybasic acid examples include oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecandioic acid, dodecandioic acid, and aliphatic polybasic acids such as azelaic acid A polybasic acid having an unsaturated group such as citraconic acid, itaconic acid, citraconic anhydride, itaconic anhydride; and an aromatic polybasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride. . These polybasic acids may be used alone or in combination of two or more. Among these, it is preferable to use an aliphatic polybasic acid from the viewpoint that more excellent PVC adhesion can be obtained.
  • the acid value of the polymer having an acid group is preferably in the range of 10 to 70 mgKOH / g, more preferably 15 to 40 mgKOH / g, from the viewpoint that more excellent PVC adhesion can be obtained.
  • the acid value of the polymer having an acid group is a value measured by a potentiometric titration method based on JIS K0070-1992.
  • the adhesiveness-imparting agent (C) may contain other components such as a solvent and a neutralizing agent, if necessary. Among these, it is preferable to contain a neutralizer from the viewpoint of further improving the affinity for water (B) and the storage stability.
  • the solvent examples include 1-methoxy-2-hydroxypropane, 1-methoxy-2-propyl acetate, dipyrropyrene glycol monomethyl ether, 2,2,4-trimethyl-3-hydroxyoentyl isobutyrate , Methanol, ethanol, propanol, butanol, diacetone alcohol, diacetone alcohol, dimethyl carbitol, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetylacetone, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, Dimethyl carbonate and the like can be used. These solvents may be used alone or in combination of two or more. When the solvent is used, the content thereof is, for example, in the range of 1 to 30% by mass in the adhesion promoter (C).
  • the neutralizing agent examples include nonvolatile bases such as sodium hydroxide and potassium hydroxide; tertiary amine compounds such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine and triethanol; dimethylamine, diethylamine, dibutylamine and the like. Secondary amine compounds, primary amine compounds such as ethylenediamine, methylamine, ethylamine, and butylamine, and ammonia can be used. These neutralizers may be used alone or in combination of two or more. When the neutralizing agent is used, the content thereof is, for example, in the range of 0.001 to 3% by mass in the adhesion-imparting agent (C).
  • nonvolatile bases such as sodium hydroxide and potassium hydroxide
  • tertiary amine compounds such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine and triethanol
  • dimethylamine, diethylamine, dibutylamine and the like Secondary
  • the urethane resin composition of the present invention contains the urethane resin (A), water (B), and the adhesion-imparting agent (C) as essential components, but may use other additives as necessary. Good.
  • 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 use 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 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). .
  • the urethane resin composition of the present invention can provide a film having excellent PVC adhesion. 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. In particular, it can be suitably used as a surface treatment agent for PVC leather.
  • 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 resin (A-1) having a nonvolatile content of 32% by mass.
  • the urethane resin (A-1) 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.
  • urethane resin (A-2) having a nonvolatile content of 30% by mass.
  • the urethane resin (A-2) 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.
  • the urethane resin (AR-1) obtained 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.
  • Example 1 25 parts by mass of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 5 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, an adhesion-imparting agent (polyester having an acid group obtained by reacting adipic acid and trimethylolpropane, number average molecular weight; 2) 788, acid value; 29 mg KOH / g, solid content; 80% by mass (including a neutralizing agent; 0.5% by mass of dimethylethanolamine and a solvent: 1-methoxy-2-hydroxypropane), the following: By mixing 3 parts by mass and 65 parts by mass of water, a urethane resin composition was
  • Example 2 25 parts by weight of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 5 parts by weight of a carbodiimide crosslinking agent ("Carbodilite V-02-L2” manufactured by Co., Ltd.), and a filler ("ACEMATTS” manufactured by Evonik Degussa Co., Ltd.) 100 ", 2 parts by mass of silica particles produced by a dry method, average particle size: 10 ⁇ m), 10 parts by mass of C-1 and 58 parts by mass of water were mixed to obtain a urethane resin composition.
  • a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Co., Ltd.)
  • ACEMATTS manufactured by Evonik Degussa Co., Ltd.
  • Example 3 25 parts by weight of the aqueous dispersion of the urethane resin (A-1) obtained in Synthesis Example 1, 5 parts by weight of a carbodiimide crosslinking agent ("Carbodilite V-02-L2” manufactured by Co., Ltd.), and a filler ("ACEMATTS” manufactured by Evonik Degussa Co., Ltd.) 100 ", silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, 1 part by mass of C-1 and 67 parts by mass of water were mixed to obtain a urethane resin composition.
  • a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Co., Ltd.)
  • ACEMATTS ACEMATTS manufactured by Evonik Degussa Co., Ltd.
  • Example 4 25 parts by mass of the aqueous dispersion of the urethane resin (A-2) obtained in Synthesis Example 2, 5 parts by mass of a carbodiimide crosslinking agent ("Carbodilite V-02-L2” manufactured by Co., Ltd.), and a filler ("ACEMATTS” manufactured by Evonik Degussa) 100 ", 2 parts by mass of silica particles produced by a dry method, average particle size: 10 ⁇ m), 3 parts by mass of C-1 and 65 parts by mass of water were mixed to obtain a urethane resin composition.
  • a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Co., Ltd.)
  • ACEMATTS manufactured by Evonik Degussa
  • Example 5 25 parts by mass of the aqueous dispersion of the urethane resin (A-2) obtained in Synthesis Example 2, 5 parts by mass of a carbodiimide crosslinking agent ("Carbodilite V-02-L2” manufactured by Co., Ltd.), and a filler ("ACEMATTS” manufactured by Evonik Degussa) 100 ", 2 parts by mass of silica particles produced by a dry method, average particle size: 10 ⁇ m), 10 parts by mass of C-1 and 58 parts by mass of water were mixed to obtain a urethane resin composition.
  • a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Co., Ltd.)
  • ACEMATTS manufactured by Evonik Degussa
  • Example 6 25 parts by mass of the aqueous dispersion of the urethane resin (A-2) obtained in Synthesis Example 1, 5 parts by mass of a carbodiimide crosslinking agent ("Carbodilite V-02-L2” manufactured by Co., Ltd.), and a filler ("ACEMATTS” manufactured by Evonik Degussa) 100 ", silica particles produced by a dry method, average particle diameter: 10 ⁇ m) 2 parts by mass, 1 part by mass of C-1 and 67 parts by mass of water were mixed to obtain a urethane resin composition.
  • a carbodiimide crosslinking agent (“Carbodilite V-02-L2” manufactured by Co., Ltd.)
  • ACEMATTS manufactured by Evonik Degussa
  • Example 2 In Example 1, urethane was used in the same manner as in Example 1 except that a silane coupling agent (KBM-403, manufactured by Shin-Etsu Silicone Co., number average molecular weight: 236.3) was used instead of C-1. A resin composition was obtained.
  • a silane coupling agent KBM-403, manufactured by Shin-Etsu Silicone Co., number average molecular weight: 236.3
  • Example 3 In Example 1, urethane was used in the same manner as in Example 1 except that a silane coupling agent ([KBE-503], number average molecular weight: 290.4, manufactured by Shin-Etsu Silicone Co., Ltd.) was used instead of C-1. A resin composition was obtained.
  • a silane coupling agent [KBE-503], number average molecular weight: 290.4, manufactured by Shin-Etsu Silicone Co., Ltd.
  • Example 4 A urethane resin composition was obtained in the same manner as in Example 1, except that the urethane resin (AR-1) was used instead of the urethane resin (A-1).
  • the number average molecular weights of the polyol and the adhesion-imparting agent used in the synthesis examples are values 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 aqueous surface treating agent was coated on PVC leather using a 50 ⁇ m bar coater, and dried in a gear oven at 120 ° C. for 2 minutes to obtain a sample for evaluation.
  • the evaluation sample was evaluated under a condition of 1 kg load and 2,000 times using a Scott type anti-rubbing abrasion tester (“IT-SCA-W” manufactured by INTEC Corporation).
  • IT-SCA-W Scott type anti-rubbing abrasion tester
  • a test piece having a width of 30 mm and a length of 1,200 mm was taken one by one from the vertical and horizontal directions, and visually judged according to the following criteria.
  • T No change in appearance.
  • F The surface treatment layer floated from the PVC sheet and caused whitening.
  • the urethane resin composition of the present invention has excellent PVC adhesion.
  • Comparative Example 1 is an embodiment in which no specific adhesion-imparting agent (C) is used, and Comparative Examples 2 and 3 each have a number-average molecular weight defined by the present invention instead of the adhesion-imparting agent (C).
  • an adhesion-imparting agent was used which was less than the above range, but in all cases, the PVC adhesion was poor.
  • Comparative Example 4 is an embodiment using a urethane resin using isophorone diisocyanate and hexamethylene diisocyanate as raw materials instead of the urethane resin (A), but the PVC adhesion was poor.

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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)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de résine d'uréthanne caractérisée en ce qu'elle contient une résine d'uréthanne (A) obtenue à partir d'une matière première qui est le diisocyanate de dicyclohexylméthane (a1-1), d'eau (B) et d'un agent de pégosité (C) présentant une masse moléculaire moyenne en nombre de 300 ou plus. La présente invention concerne également : un agent de traitement de surface, caractérisé en ce qu'il contient la composition de résine d'uréthanne ; et un article caractérisé en ce qu'il présente une couche formée de l'agent de traitement de surface. L'agent de pégosité (C) comprend de préférence un groupe acide. L'indice d'acide de l'agent de pégosité (C) est de préférence compris dans la plage de 10 à 70 mg KOH/g. L'agent de pégosité (C) est de préférence un polyester. La quantité contenue de l'agent de pégosité (C) est de préférence comprise dans la plage de 0,45 à 15,5 % en masse.
PCT/JP2019/019056 2018-06-27 2019-05-14 Composition de résine d'uréthanne, agent de traitement de surface et article Ceased WO2020003780A1 (fr)

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