CN113573906B - Surface treating agent and article - Google Patents

Surface treating agent and article Download PDF

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Publication number
CN113573906B
CN113573906B CN201980094262.XA CN201980094262A CN113573906B CN 113573906 B CN113573906 B CN 113573906B CN 201980094262 A CN201980094262 A CN 201980094262A CN 113573906 B CN113573906 B CN 113573906B
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mass
surface treatment
parts
treatment agent
urethane resin
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CN113573906A (en
Inventor
中庄谷隆典
千千和宏之
竹村洁
佐藤盛绪
坂井美代
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DIC Corp
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DIC Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • 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

Abstract

The present invention provides a surface treatment agent characterized by comprising a urethane resin (A), water (B) and a crosslinking agent (C), wherein the crosslinking agent (C) comprises an oxazoline compound (C-1). The present invention also provides an article comprising a layer formed of the surface treatment agent. The aforementioned crosslinking agent (C) is preferably used alone or in combination of the oxazoline compound (C-1) and the carbodiimide compound (C-2). The article has 2 layers formed of the surface treatment agent, and preferably at least 1 layer thereof is a layer formed of the surface treatment agent.

Description

Surface treating agent and article
Technical Field
The present invention relates to a surface treatment agent and an article having a layer based on the surface treatment agent.
Background
In the process for producing a sheet for automobile interior leather, from the viewpoint of imparting durability and appearance to the surface thereof, finishing is performed with a surface treatment agent. Among materials used in conventional surface treatment agents, solvent-based resin compositions containing an organic solvent are mainly used, but aqueous surface treatment agents containing substantially no organic solvent have been developed under the influence of recent environmental restrictions.
As the aqueous surface treatment agent, for example, a surface treatment agent containing an aqueous polyurethane dispersion and an ultraviolet absorbing polymer is disclosed (for example, refer to patent document 1). However, the level of light resistance of the surface treatment agent is not yet sufficient.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2013-53206
Disclosure of Invention
Problems to be solved by the invention
The problem to be solved by the present invention is to provide a surface treatment agent excellent in light resistance among aqueous surface treatment agents.
Solution for solving the problem
The present invention provides a surface treatment agent characterized by comprising a urethane resin (A), water (B) and a crosslinking agent (C), wherein the crosslinking agent (C) comprises an oxazoline compound (C-1).
The present invention also provides an article comprising a layer formed of the surface treatment agent.
ADVANTAGEOUS EFFECTS OF INVENTION
The surface treatment agent of the present invention is excellent in light resistance. In addition, the surface treatment agent of the present invention contains water and is an environmentally friendly material.
Detailed Description
The surface treating agent of the present invention contains a urethane resin (A), water (B) and a crosslinking agent (C) containing an oxazoline compound (C-1).
The urethane resin (a) may be dispersed in water (B), and for example, a urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group; a urethane resin forcibly dispersed in water (B) with an emulsifier, and the like. These urethane resins (A) may be used alone or in combination of 2 or more.
As a method for obtaining the urethane resin having an anionic group, for example, a method in which 1 or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group are used as a raw material is exemplified.
Examples of the compound having a carboxyl group include 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, 2-dimethylolpropionic acid, and 2, 2-valeric acid. These compounds may be used singly or in combination of 2 or more.
As the compound having a sulfonyl group, for example, 3, 4-diaminobutane sulfonic acid, 3, 6-diamino-2-toluene sulfonic acid, 2, 6-diaminobenzene sulfonic acid, N- (2-aminoethyl) -2-aminoethyl sulfonic acid, and the like can be used. These compounds may be used singly or in combination of 2 or more.
In the resin composition, the carboxyl group and the sulfonyl group may be partially or completely neutralized with a basic compound. As the basic compound, for example, an organic amine such as ammonia, triethylamine, pyridine, morpholine, etc. can be used; alkanolamines such as monoethanolamine and dimethylethanolamine; metal base compounds containing sodium, potassium, lithium, calcium, etc.
As a method for obtaining the above-mentioned urethane resin having a cationic group, for example, a method in which 1 or 2 or more kinds of compounds having an amino group are used as a raw material can be mentioned.
As the compound having an amino group, for example, compounds having a primary amino group and a secondary amino group such as triethylenetetramine and diethylenetriamine; and compounds having a tertiary amino group such as N-alkyl dialkanolamine, e.g., N-methyl diethanolamine and N-ethyl diethanolamine, and N-alkyl diaminoalkylamine, e.g., N-methyl diaminoethylamine and N-ethyl diaminoethylamine. These compounds may be used singly or in combination of 2 or more.
As a method for obtaining the urethane resin having a nonionic group, for example, a method in which 1 or 2 or more kinds of compounds having an oxyethylene structure are used as a raw material is exemplified.
As the compound having an oxyethylene structure, for example, polyether polyols having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol and the like can be used. These compounds may be used singly or in combination of 2 or more.
The amount of the raw material used for producing the above urethane resin having a 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 even more preferably in the range of 1.5 to 7% by mass, in view of obtaining further excellent chemical resistance, abrasion resistance, weather resistance and hydrolysis resistance.
As the emulsifier that can be used to obtain the urethane resin forcibly dispersed in water (B), for example, nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene/polyoxypropylene copolymer, and the like can be used; anionic emulsifiers such as fatty acid salts such as sodium oleate, alkyl sulfate salts, alkylbenzene sulfonate salts, alkyl sulfosuccinate salts, naphthalene sulfonate salts, polyoxyethylene alkyl sulfate salts, sodium alkane sulfonate salts, sodium alkyl diphenyl ether sulfonate salts, and the like; cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, alkyldimethylbenzyl ammonium salts, and the like. These emulsifiers may be used alone or in combination of 2 or more.
Specifically, as the urethane resin (a), for example, a reaction product of a raw material for producing the urethane resin having a hydrophilic group, a polyisocyanate (a 1), a polyol (a 2), and a chain extender (a 3) can be used. As such a reaction, a known urethanization reaction can be used.
As the polyisocyanate (a 1), for example, an aromatic polyisocyanate such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimide diphenylmethane polyisocyanate, or the like; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate. These polyisocyanates may be used alone or in combination of 2 or more.
The polyisocyanate (a 1) is preferably an alicyclic polyisocyanate, more preferably a polyisocyanate having at least 1 structure in which the nitrogen atom of the isocyanate group is directly bonded to the cyclohexane ring, and even more preferably isophorone diisocyanate and/or dicyclohexylmethane diisocyanate, from the viewpoint of further improving the adhesion to a vinyl chloride (PVC) sheet (hereinafter referred to as "PVC adhesion"). The amount of the alicyclic polyisocyanate used is preferably 30 mass% or more, more preferably 40 mass% or more, and even more preferably 50 mass% or more in the polyisocyanate (a 1) from the viewpoint of obtaining further excellent light resistance, chemical resistance, abrasion resistance and weather resistance.
The amount of the polyisocyanate (a 1) is preferably in the range of 5 to 50% by mass, more preferably in the range of 15 to 40% by mass, and even more preferably in the range of 20 to 37% by mass, in the raw material of the urethane resin (a), from the viewpoint of obtaining further excellent light resistance, chemical resistance, abrasion resistance and weather resistance.
As the polyol (a 2), for example, polyether polyol, polyester polyol, polyacrylic polyol, polycarbonate polyol, polybutadiene polyol, and the like can be used. These polyols may be used alone or in combination of 2 or more. Among these, polycarbonate polyols are preferably used in view of obtaining further excellent chemical resistance, abrasion resistance and weather resistance.
As the polycarbonate polyol, for example, a reaction product of a carbonate and/or phosgene and a compound having 2 or more hydroxyl groups can be used.
As the above-mentioned carbonate, for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, and the like can be used. These compounds may be used singly or in combination of 2 or more.
As the above-mentioned compound having 2 or more hydroxyl groups, for example, 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, trimethylol propane, 3-methylpentanediol, neopentyl glycol, trimethylol ethane, glycerol and the like can be used. These compounds may be used singly or in combination of 2 or more. Among these, 1 or more compounds selected from the group consisting of 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 3-methylpentanediol and 1, 10-decanediol are preferably used, and 1, 6-hexanediol is more preferably used, from the viewpoint of obtaining further excellent chemical resistance, abrasion resistance and weather resistance.
The amount of the polycarbonate polyol is preferably 85 mass% or more, more preferably 90 mass% or more, and even more preferably 95 mass% or more in the polyol (a 2) in view of obtaining further excellent chemical resistance, abrasion resistance and weather resistance.
The number average molecular weight of the polycarbonate polyol is preferably in the range of 100 to 100000, more preferably in the range of 150 to 10000, and even more preferably in the range of 200 to 2500, from the viewpoint of obtaining further excellent chemical resistance, mechanical strength, abrasion resistance and weather resistance. The number average molecular weight of the polycarbonate polyol means a value measured by a Gel Permeation Chromatography (GPC) method.
The number average molecular weight of the polyol (a 2) other than the polycarbonate polyol is preferably 500 to 100000, more preferably 700 to 50000, and even more preferably 800 to 10000, from the viewpoint of obtaining further excellent weather resistance. The number average molecular weight of the polyol (a 2) represents a value measured by a Gel Permeation Chromatography (GPC) method.
The amount of the polyol (a 2) used is preferably in the range of 30 to 80% by mass, more preferably in the range of 40 to 75% by mass, and even more preferably in the range of 50 to 70% by mass, based on the raw material of the urethane resin (a).
The chain extender (a 3) is, for example, one having an amino group such as ethylenediamine, 1, 2-propylenediamine, 1, 6-hexamethylenediamine, piperazine, 2, 5-dimethylpiperazine, isophoronediamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 4' -dicyclohexylmethane diamine, 3' -dimethyl-4, 4' -dicyclohexylmethane diamine, 1, 4-cyclohexanediamine, hydrazine, and the like, and has a number average molecular weight in the range of 50 to 450 (excluding the polycarbonate polyol); chain extenders having hydroxyl groups such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, hexanediol, sucrose, methyl glycol, glycerol, sorbitol, bisphenol A, 4 '-dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, and trimethylolpropane. These chain extenders may be used alone or in combination of 2 or more.
Among the above, the chain extender having an amino group is preferably used, and piperazine and/or hydrazine are more preferably used, from the viewpoint of obtaining further excellent chemical resistance, mechanical strength, abrasion resistance and weather resistance, and the total amount of piperazine and hydrazine in the chain extender (a 3) is preferably 30 mass% or more, more preferably 50 mass% or more, further preferably 60 mass% or more, and particularly preferably 80 mass% or more. The chain extender (a 3) preferably has an average functional group number of less than 3, more preferably less than 2.5.
The amount of the chain extender (a 3) is preferably in the range of 0.5 to 10 mass%, more preferably in the range of 0.7 to 5 mass%, and even more preferably in the range of 0.9 to 2.3, in terms of obtaining further excellent chemical resistance, mechanical strength, abrasion resistance and weather resistance.
As a method for producing the urethane resin (a), for example, the following method can be mentioned: a method for producing a urethane resin (a) by reacting the polyisocyanate (a 1), the polyol (a 2), and a raw material for producing the urethane resin having a hydrophilic group, thereby producing a urethane prepolymer having an isocyanate group, and then reacting the urethane prepolymer with the chain extender (a 3); and a method in which the polyisocyanate (a 1), the polyol (a 2), a raw material for producing a urethane resin having a hydrophilic group, and the chain extender (a 3) are fed at one time and reacted. These reactions are carried out, for example, at 50 to 100℃for 3 to 10 hours.
The molar ratio [ (isocyanate group)/(hydroxyl group and amino group) ] of the total of the isocyanate group of the polyisocyanate (a 1) and the hydroxyl group of the raw material for producing the urethane resin having a hydrophilic group, the hydroxyl group of the polyol (a 2) and the hydroxyl group and amino group of the chain extender (a 3) is preferably in the range of 0.8 to 1.2, more preferably in the range of 0.9 to 1.1.
In the production of the urethane resin (a), it is preferable to deactivate the isocyanate groups remaining in the urethane resin (a). In the case of inactivating the isocyanate group, an alcohol having 1 hydroxyl group such as methanol is preferably used. The amount of the alcohol is preferably in the range of 0.001 to 10 parts by mass per 100 parts by mass of the urethane resin (a).
In addition, an organic solvent may be used in the production of the urethane resin (a). As the organic solvent, for example, ketone compounds such as acetone and methyl ethyl ketone can be used; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; amide compounds such as dimethylformamide and N-methylpyrrolidone. These organic solvents may be used alone or in combination of 2 or more. The organic solvent is preferably finally removed by distillation or the like.
The content of the urethane bond in the urethane resin (a) is preferably in the range of 980 to 4000mmol/kg, more preferably in the range of 1000 to 3500mmol/kg, even more preferably in the range of 1100 to 3000mmol/kg, and even more preferably in the range of 1150 to 2500mmol/kg, from the viewpoint of obtaining further excellent chemical resistance, abrasion resistance and weather resistance. The content of the urethane bond in the urethane resin (a) is a value calculated from the amounts of the polyisocyanate (a 1), the polyol (a 2), the raw material for producing the urethane resin having a hydrophilic group, and the chain extender (a 3).
The content of the urea bond in the urethane resin (a) is preferably in the range of 315 to 850mmol/kg, more preferably in the range of 350 to 830mmol/kg, even more preferably in the range of 400 to 800mmol/kg, and even more preferably in the range of 410 to 770mmol/kg, from the viewpoint of obtaining further excellent chemical resistance, abrasion resistance and weather resistance. The urea bond content of the urethane resin (a) is a value calculated from the amounts of the polyisocyanate (a 1), the polyol (a 2), the raw material for producing the urethane resin having a hydrophilic group, and the chain extender (a 3).
The content of the alicyclic structure of the urethane resin (a) is preferably 500 to 3000mmol/kg, more preferably 600 to 2900mmol/kg, and even more preferably 700 to 2700mmol/kg, from the viewpoint of obtaining further excellent chemical resistance, abrasion resistance and weather resistance. The alicyclic structure content of the urethane resin (a) is a value calculated from the amounts of the polyisocyanate (a 1), the polyol (a 2), the raw material for producing the urethane resin having a hydrophilic group, and the chain extender (a 3).
The content of the urethane resin (a) is preferably in the range of 3 to 50% by mass, more preferably in the range of 5 to 30% by mass, in view of coatability, handleability and storage stability.
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, more preferably in the range of 50 to 90% by mass, in view of the coatability, handleability and storage stability of the urethane resin composition.
In order to obtain excellent light resistance, the aforementioned crosslinking agent (C) must contain an oxazoline compound (C-1).
As the oxazoline compound (c-1), an oxazoline group-containing compound such as 2,2' -bis (2-oxazoline), 1, 2-bis (2-oxazoline-2-yl) ethane, 1, 4-bis (2-oxazoline-2-yl) butane, 1, 8-bis (2-oxazoline-2-yl) butane, 1, 4-bis (2-oxazoline-2-yl) cyclohexane, 1, 2-bis (2-oxazoline-2-yl) benzene, 1, 3-bis (2-oxazoline-2-yl) benzene, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropyl-4-methyl-2-oxazoline, 2-isopropyl-5-ethyl-2-oxazoline; polymers having oxazoline groups, and the like. These oxazoline crosslinking agents may be used alone or in combination of 2 or more. Among these, from the viewpoint of obtaining further excellent light resistance, a polymer having an oxazoline group is preferably used.
As the polymer having an oxazoline group, a polymer of a polymerizable oxazoline compound such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropyl-2-oxazoline, or the like can be used.
The oxazoline group-containing polymer is preferably available as a commercially available product as "eporos" series manufactured by japan catalyst, ltd, specifically, water-soluble "eporos WS-500", "eporos WS-700", and the like.
The content of the oxazoline compound (c-1) is preferably in the range of 0.01 to 20 mass%, more preferably in the range of 0.01 to 15 mass%, from the viewpoint of obtaining further excellent light resistance.
The amount of the oxazoline compound (c-1) (=solid content) is preferably in the range of 0.1 to 100 parts by mass, more preferably in the range of 0.5 to 50 parts by mass, per 100 parts by mass of the urethane resin (a) (=solid content).
In the crosslinking agent (C), other crosslinking agents may be used in combination as required in addition to the oxazoline compound (C-1).
As the other crosslinking agent, for example, a carbodiimide compound (c-2), a polyisocyanate crosslinking agent, a melamine crosslinking agent, an epoxy crosslinking agent, or the like can be used. These crosslinking agents may be used alone or in combination of 2 or more.
Examples of the carbodiimide compound (c-2) include carbodiimide compounds such as N, N ' -dicyclohexylcarbodiimide, N ' -diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, N- [3- (dimethylamino) propyl ] -N ' -ethylcarbodiimide methyl iodide, N-tert-butyl-N ' -ethylcarbodiimide, N-cyclohexyl-N ' - (2-morpholinoethyl) carbodiimide p-toluenesulfonate, N ' -di-tert-butylcarbodiimide, N ' -di-p-tolylcarbodiimide; a carbodiimide compound obtained by a well-known condensation reaction of a polyisocyanate in the presence of a carbodiimidization catalyst; and carbodiimide compounds using polyisocyanates and polyalkylene oxides as raw materials. These carbodiimide compounds may be used alone or in combination of 2 or more.
Among the above, the oxazoline compound (C-1) alone or the oxazoline compound (C-1) and the carbodiimide compound (C-2) are preferably used as the crosslinking agent (C), in view of obtaining further excellent light resistance.
The mass ratio (solid content) [ (c-1)/(c-2) ] of the oxazoline compound (c-1) and the carbodiimide compound (c-2) used in combination is preferably in the range of 10/90 to 90/10, more preferably in the range of 20/80 to 80/20, from the viewpoint of obtaining further excellent light resistance.
The urethane resin composition of the present invention contains the aforementioned urethane resin (a), water (B) and a crosslinking agent (C) as essential components, and other additives may be used as required.
As the other additives, for example, fillers (D), emulsifiers, defoamers, leveling agents, thickeners, viscoelastic modifiers, defoamers, wetting agents, dispersants, preservatives, plasticizers, penetrating agents, fragrances, bactericides, acaricides, mildewcides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (for example, titanium white, iron oxide red, phthalocyanine, carbon black, permanent yellow, etc.), and the like can be used. These additives may be used alone or in combination of 2 or more.
When the above-mentioned other additive is used in applications requiring a matting effect, the coating film of the surface treatment agent preferably contains the filler (D).
As the filler (D), for example, silica particles, organic microbeads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica (mother-of-cloud), asbestos, mica (Mica), calcium silicate, aluminum silicate, and the like can be used. These fillers may be used alone or in combination of 2 or more.
As the silica particles, for example, dry silica, wet silica, or the like can be used. Among these, dry silica is preferable in view of high scattering effect and wide adjustment range of gloss values. The average particle diameter of these silica particles is preferably in the range of 2 to 14. Mu.m, more preferably in the range of 3 to 12. Mu.m. The average particle diameter of the silica particles is the particle diameter at which the cumulative amount thereof is 50% (the particle diameter at D50 in the particle size distribution) in the cumulative particle amount curve of the particle size distribution measurement result.
As the organic beads, for example, acrylic beads, urethane beads, silicon beads, olefin beads, and the like can be used.
The amount of the filler (D) used may be appropriately determined depending on the matting effect to be imparted, and is, for example, preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 1 to 10 parts by mass, per 100 parts by mass of the urethane resin (a).
As described above, the surface treatment agent of the present invention is excellent in light resistance. In addition, the surface treatment agent of the present invention contains water and is an environmentally friendly material. Therefore, the surface treatment agent of the present invention can be suitably used as a surface treatment agent for various articles such as synthetic leather, polyvinyl chloride (PVC) leather, thermoplastic olefin resin (TPO) leather, instrument panels, and the like, and can be particularly suitably used for PVC leather.
The article of the present invention has a layer formed from the aforementioned surface treatment agent.
Specific examples of the articles include synthetic leather, artificial leather, natural leather, automobile interior sheets using polyvinyl chloride (PVC) leather, sports shoes, clothing, furniture, thermoplastic olefin (TPO) leather, instrument panels, and the like.
The thickness of the layer based on the surface treatment agent is, for example, in the range of 0.1 to 100. Mu.m.
The article has a layer formed of the surface treatment agent of the present invention, and preferably has 2 layers formed of the surface treatment agent in order to obtain further excellent light resistance, and examples thereof include: an article having 2 layers formed of the surface treatment agent of the present invention; an article having 2 layers of the surface treatment agent of the present invention and the other surface treatment agent.
Preferable modes of the article are as follows.
The surface treatment agents forming (primer)/(topcoat) can be exemplified by:
a surface treatment agent containing only the oxazoline compound (C-1) as the crosslinking agent (C), a surface treatment agent containing only the oxazoline compound (C-1) as the crosslinking agent (C),
A surface treatment agent containing only an oxazoline compound (C-1) as a crosslinking agent (C), a surface treatment agent containing an oxazoline compound (C-1) and a carbodiimide compound (C-2) as a crosslinking agent (C),
A surface treatment agent containing only an oxazoline compound (C-1) as a crosslinking agent (C)/a surface treatment agent containing only a carbodiimide compound (C-2) as a crosslinking agent (C),
A surface treatment agent containing an oxazoline compound (C-1) and a carbodiimide compound (C-2) as a crosslinking agent (C), a surface treatment agent containing only the oxazoline compound (C-1) as a crosslinking agent (C),
A surface treatment agent containing an oxazoline compound (C-1) and a carbodiimide compound (C-2) as a crosslinking agent (C), a surface treatment agent containing only a carbodiimide compound (C-2) as a crosslinking agent (C),
Surface treating agent containing oxazoline compound (C-1) and carbodiimide compound (C-2) as crosslinking agent (C),
Etc.
When forming 2 layers based on the surface treatment agent, the filler (D) preferably contains an over coat layer.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples.
Synthesis example 1 preparation of aqueous Dispersion of urethane resin (A-1)
To 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 part by mass of stannous octoate were added, and then 220 parts by mass of polycarbonate polyol-3 (using 1, 6-hexanediol as a raw material, number average molecular weight: 2000), 12 parts by mass of 2, 2-dimethylolpropionic acid and 70 parts by mass of dicyclohexylmethane diisocyanate were added and reacted at 70℃for 1 hour to obtain a methyl ethyl ketone solution of a urethane prepolymer.
Then, 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 obtain an emulsion in which the urethane resin (a-1) was dispersed in water.
Then, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added, whereby an aqueous urethane resin (a-1) dispersion having a nonvolatile content of 32 mass% was obtained.
The urethane resin (A-1) obtained had a urethane bond content of 1278mmol/kg, a urea bond content of 435mmol/kg and an alicyclic structure content of 1713mmol/kg.
Synthesis example 2 preparation of aqueous Dispersion of urethane resin (A-2)
To 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 part by mass of stannous octoate were added, and then 138 parts by mass of polycarbonate polyol-4 (1, 6-hexanediol as a raw material, number average molecular weight: 2000), 55 parts by mass of polycarbonate polyol-5 (1, 6-hexanediol as a raw material, number average molecular weight: 500), 13 parts by mass of 2, 2-dimethylolpropionic acid and 100 parts by mass of dicyclohexylmethane diisocyanate were added and reacted at 70℃for 1 hour to obtain a methyl ethyl ketone solution of a urethane prepolymer.
Then, 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 880 parts by mass of ion-exchanged water was added thereto to obtain an emulsion in which the urethane resin (a-2) was dispersed in water.
Then, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was further added, whereby an aqueous urethane resin (a-2) dispersion having a nonvolatile content of 30 mass% was obtained.
The urethane bond content of the obtained urethane resin (A-2) was 1747mmol/kg, the urea bond content was 576mmol/kg, and the alicyclic structure content was 2341mmol/kg.
Example 1
(surface treatment agent for undercoat layer)
50 parts by mass of the aqueous urethane resin (a-1) dispersion obtained in synthesis example 1, 45 parts by mass of water, 15 parts by mass of an oxazoline compound (hereinafter abbreviated as "OXZ" by japan catalyst system "WS-500", made by the corporation) and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (AC-1) for an undercoat layer.
(surface treatment agent for topcoat)
30 parts by mass of the aqueous urethane resin (A-1) dispersion obtained in Synthesis example 1,2 parts by mass of silica particles (average particle diameter: 10 μm, hereinafter referred to as "silica") produced by a dry method, 63 parts by mass of water, OXZ parts by mass, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (TC-1) for a topcoat layer.
Example 2
(surface treatment agent for undercoat layer)
50 parts by mass of the aqueous urethane resin (A-1) dispersion obtained in Synthesis example 1, 45 parts by mass of water, OXZ parts by mass, 4 parts by mass of a carbodiimide compound (nonvolatile component "CARBODILITE V-02-L2", manufactured by Nisshini chemical Co., ltd.; 40 parts by mass, hereinafter abbreviated as "NCN") and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (AC-2) for an undercoat layer.
(surface treatment agent for topcoat)
30 parts by mass of the aqueous urethane resin (a-1) dispersion obtained in synthesis example 1,2 parts by mass of silica, 63 parts by mass of water, OXZ parts by mass, 3 parts by mass of NCN, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (TC-2) for a topcoat layer.
Example 3
(surface treatment agent for undercoat layer)
50 parts by mass of the aqueous urethane resin (a-1) dispersion obtained in synthesis example 1, 45 parts by mass of water, OXZ parts by mass, 7 parts by mass of NCN, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (AC-3) for an undercoat layer.
(surface treatment agent for topcoat)
30 parts by mass of the aqueous urethane resin (a-1) dispersion obtained in synthesis example 1,2 parts by mass of silica, 63 parts by mass of water, OXZ parts by mass, 2 parts by mass of NCN, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (TC-3) for a topcoat layer.
Example 4
(surface treatment agent for undercoat layer)
50 parts by mass of the aqueous urethane resin (A-1) dispersion obtained in Synthesis example 1, 45 parts by mass of water, 9 parts by mass of NCN, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (AC-4) for an undercoat layer.
(surface treatment agent for topcoat)
30 parts by mass of the aqueous urethane resin (a-1) dispersion obtained in synthesis example 1,2 parts by mass of silica, 63 parts by mass of water, OXZ parts by mass, 3 parts by mass of NCN, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (TC-4) for a topcoat layer.
Example 5
(surface treatment agent for undercoat layer)
50 parts by mass of the aqueous urethane resin (a-2) dispersion obtained in synthesis example 2, 45 parts by mass of water, OXZ parts by mass, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (AC-5) for an undercoat layer.
(surface treatment agent for topcoat)
30 parts by mass of the aqueous urethane resin (a-2) dispersion obtained in synthesis example 2,2 parts by mass of silica, 63 parts by mass of water, OXZ parts by mass, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (TC-5) for a topcoat layer.
Comparative example 1
(surface treatment agent for undercoat layer)
50 parts by mass of the aqueous urethane resin (A-1) dispersion obtained in Synthesis example 1, 45 parts by mass of water, 9 parts by mass of NCN, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (ACR-1) for an undercoat layer.
(surface treatment agent for topcoat)
30 parts by mass of the aqueous urethane resin (a-1) dispersion obtained in synthesis example 1,2 parts by mass of silica, 63 parts by mass of water, 6 parts by mass of NCN, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (TCR-1) for a topcoat layer.
Comparative example 2
(surface treatment agent for undercoat layer)
50 parts by mass of the aqueous urethane resin (A-1) dispersion obtained in Synthesis example 1, 45 parts by mass of water, 9 parts by mass of NCN, and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (ACR-2) for an undercoat layer.
(surface treatment agent for topcoat)
30 parts by mass of the aqueous urethane resin (A-1) dispersion obtained in Synthesis example 1,2 parts by mass of silica, 63 parts by mass of water, 6 parts by mass of NCN, 0.3 part by mass of a hindered amine-based light stabilizer (Adekstab LA-52, manufactured by ADEKA, inc.), and 5 parts by mass of other additives (thickener, defoamer, leveling agent) were mixed to obtain a surface treatment agent (TCR-2) for a topcoat.
[ method for measuring number average molecular weight ]
The number average molecular weight of the polyol used in the synthesis example and the like represents a value measured by Gel Permeation Chromatography (GPC) under the following conditions.
Measurement device: high performance GPC apparatus (HLC-8220 GPC manufactured by Tosoh Co., ltd.)
Column: the following columns manufactured by Tosoh corporation were used in series.
"TSKgel G5000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G4000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G3000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G2000" (7.8 mmI.D..times.30 cm). Times.1 root
A detector: RI (differential refractometer)
Column temperature: 40 DEG C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100. Mu.L (tetrahydrofuran solution with sample concentration of 0.4% by mass)
Standard sample: standard curves were made using standard polystyrene as described below.
(Standard polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-5000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-1 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-2 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-4 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-10 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-20 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-40 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-80 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-128 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-288 manufactured by Tosoh Co., ltd "
TSKge Standard polystyrene F-550 manufactured by Tosoh Co., ltd "
[ evaluation method of light fastness ]
The surface treatment agent for primer and the surface treatment agent for primer obtained in examples and comparative examples were applied to PVC leather in this order 1 time using a bar coater, and dried at 120 ℃ for 2 minutes to obtain samples for evaluation.
A xenon lamp weathering tester (Xenon weather meter) (ATLAS Co., ltd. "Ci 4000") was used in accordance with ISO105-B06:1998, the light resistance test was performed on the sample for evaluation under the following conditions, and (i) visual evaluation of appearance, (ii) gradation-based gradation determination, and (iii) bending test were performed.
For this result, the whitener was evaluated as "o" when (i) no change in appearance, (ii) no less than 4 grades, and (iii) no whitening was confirmed at the time of bending, and the other was evaluated as "x".
TABLE 1
TABLE 2
The surface treatment agent of the present invention was found to have excellent light resistance.
On the other hand, comparative examples 1 and 2 were poor in light resistance in the case where the oxazoline compound (c-1) was not used in the surface treatment agent.

Claims (4)

1. A surface treatment agent comprising a urethane resin (A), water (B) and a crosslinking agent (C),
the urethane resin (A) has a urethane bond content in the range of 1000 to 4000mmol/kg,
the urethane resin (A) has a urea bond content in the range of 350 to 850mol/kg, and
the alicyclic structure content of the urethane resin (A) is in the range of 600 to 3000mmol/kg,
the crosslinking agent (C) contains an oxazoline compound (C-1) and a carbodiimide compound (C-2), and the content of the oxazoline compound (C-1) is in the range of 0.01 to 20 mass%.
2. The surface treatment agent according to claim 1, wherein the oxazoline compound (c-1) is contained in an amount of 0.01 to 15 mass%.
3. An article comprising a layer formed from the surface treatment agent according to any one of claims 1 to 2.
4. An article comprising 2 layers of the surface treatment agent, wherein at least 1 layer is a layer of the surface treatment agent according to any one of claims 1 to 2.
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