JP2003128983A - Water-based resin composition for coating artificial leather - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based resin composition for artificial leather, having high light resistance and durability and the like. SOLUTION: This water-based resin composition essentially comprises a water-based polyurethane resin and an ultraviolet-absorbing resin obtained by reaction of a specific ultraviolet-absorbing group-bearing polyester polyol; wherein the ultraviolet-absorbing resin is an ultraviolet-absorbing urethane resin which is obtained by reaction between the polyester polyol, a compound containing ionic and/or nonionic surface-active group(s), an organic polyisocyanate and, as necessary, an additional polyol.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ultraviolet absorbing resin obtained by using a polyester polyol having an ultraviolet absorbing group, and an aqueous resin composition for artificial leather coating, which comprises an aqueous urethane resin.

[0002]

2. Description of the Related Art In recent years, due to environmental problems, the coating agent for artificial leather is changing from solvent-based urethane resin to water-based urethane resin. Originally, the urethane resin itself did not have good light resistance, and an ultraviolet absorber or the like was added to improve the light resistance. However, it is known that when an ultraviolet absorber that can be used in a water-based urethane resin is added, since the ratio of hydrophilic groups contained in the ultraviolet absorber is large, the light resistance of the artificial leather rapidly decreases after the water resistance test. There is.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a water-based resin composition for artificial leather coating, which contains an ultraviolet absorbent having good ultraviolet absorption, water resistance and compatibility with resins. is there.

[0004]

Means for Solving the Problems As a result of intensive investigations, the present inventors have found that an artificial resin consisting of an ultraviolet absorbing resin and an aqueous urethane resin obtained by using a polyester polyol having an ultraviolet absorbing group as an ultraviolet absorbing agent. It has been found that the above problems can be solved by using a water-based resin composition for leather coating, and the present invention has been completed.

That is, the first aspect of the present invention is that water for artificial leather coating comprising an ultraviolet absorbing resin (I) obtained by using a polyester polyol (A) having an ultraviolet absorbing group and an aqueous urethane resin (IIu). A resin composition is provided. The second aspect of the present invention is the first aspect of the present invention, in which the polyester polyol (A) is represented by the following general formula (1).
The water-based resin composition for artificial leather coating described in 1.

[0006]

[Chemical 2]

(R ^{1 to} R ² are H, an alkyl group having 1 to 10 carbon atoms, n and n ′ are integers of 4 to 8, m and m ′ are 1 to 20, and n R ¹ and R ^{2 are} , N ′ R ¹ and R ² may be the same or different from each other, and m and m ′ constitutional units may be the same or different.) The third aspect of the present invention is an ultraviolet-absorbing resin. (I) reacts a polyester polyol (A), a compound (C) containing an ionic and / or nonionic surface-active group, an organic polyisocyanate (D), and a polyol (B) optionally added. The water-based resin composition for artificial leather coating according to the first or second aspect of the present invention, which is an ultraviolet absorbing urethane resin obtained by the above, is provided. A fourth aspect of the present invention provides the water-based resin composition for artificial leather coating according to the third aspect of the present invention, wherein the compound (C) is a compound (C1) containing a carboxyl group and an active hydrogen group. Fifth of the present invention
Provides the water-based resin composition for artificial leather coating according to the third aspect of the present invention, wherein the compound (C) is an alkyl (C 1-10) dialkanol (C 1-5) amine (C2). A sixth aspect of the present invention is the third aspect of the present invention, wherein the compound (C) is a macromonomer (C3) having a tertiary and / or quaternary nitrogen atom in the side chain and two or more hydroxyl groups at the terminals. The water-based resin composition for artificial leather coating described is provided. The seventh aspect of the present invention is an ultraviolet absorbing resin (I).
Is a water emulsion resin obtained by neutralizing a UV absorbing urethane resin solution obtained by reacting in an organic solvent with a neutralizing agent (h), and then dispersing it in water to form an emulsion. An aqueous resin composition for artificial leather coating is provided. The eighth aspect of the present invention is an ultraviolet absorbing resin (I).
Provides a water-based resin composition for artificial leather coating according to the seventh aspect of the present invention, which is a water emulsion resin obtained by dispersing in water and emulsifying and then removing an organic solvent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. (I) Ultraviolet Absorbing Resin The ultraviolet absorbing resin (I) is a resin obtained by using, for example, the polyester polyol (A) represented by the above formula (1), and preferably the polyester polyol (A) Is an ultraviolet absorbing urethane resin (Iu) obtained by reacting a polyol (B), a compound (C) and an organic polyisocyanate (D), and more preferably the urethane resin (Iu) is an aqueous urethane resin. is there.

Polyester Polyol (A) The polyester polyol (A) is a polyester polyol having an ultraviolet absorbing group, and is represented by the above formula (1) as described in, for example, JP-A-10-265557. In the present invention, it is used as a polyester-based UV absorber having good UV absorbency, water resistance, and compatibility with resins. The polyester polyol (A) is obtained by ring-opening addition polymerization of a lactone with an alcoholic hydroxyl group of bis [3- (2H-benzotriazol-2-yl) -4-hydroxy-benzeneethanol] methane. Ε for lactones
-Caprolactone, trimethyl-ε-caprolactone,
Examples thereof include monomethyl-ε-caprolactone, γ-butyrolactone, δ-valerolactone, and the like, preferably ε-
It is caprolactone, and m and m ′ in the general formula (1) are preferably 1 to 20.

Polyol (B) Examples of the polyol (B) added as necessary include polyester polyol, polyether polyol, polycarbonate polyol, poly (meth) acrylic polyol, polyalkyl polyol, polyalkylene polyol and the like. The compounds containing these polyol components are used alone or in combination of two or more. The polyol (B) may be a diol or a triol or higher, but is preferably a diol. The number average molecular weight of the polyol (B) is 500 to 10
000, preferably 500 to 5000. The component (B) is preferably used, and the component (B) is 0 to 200 parts by weight, and further 0 to 10 parts by weight with respect to 100 parts by weight of the component (A).
It is preferable to add 0 part by weight.

Compound (C) Containing Ionic and / or Nonionic Surface Active Group The compound (C) containing ionic and / or nonionic surface active group contains a carboxyl group and an active hydrogen group. Compound (C1), aryl or alkyl dialkanolamine compound (C2), macromonomer (C3) having a tertiary and / or quaternary nitrogen atom in the side chain and two or more hydroxyl groups at the end, and two or more A macromonomer (C4) obtained by radically polymerizing a radically polymerizable unsaturated monomer containing a nonionic surface-active group in the presence of a mercaptan-based chain transfer agent having a hydroxyl group and one mercapto group can be mentioned. Among the macromonomers, the macromonomer (C3) is preferable.

Examples of the compound (C1) containing a carboxyl group and an active hydrogen group include dialkylol (having 1 to 1 carbon atoms) such as dimethylolpropionic acid and dimethylolbutanoic acid.
5) Monoalkyl (C1-5) carboxylic acids; lactone adducts with dimethylolpropionic acid or dimethylolbutanoic acid as the initiator. As the aryl or alkyl dialkanol amine compound (C2), an alkyl (C 1-10) dialkanol (C 1-5) amine compound, for example, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine; Examples thereof include lactone adducts using these alkyl dialkanol amine compounds as an initiator. A macromonomer (C having a tertiary and / or quaternary nitrogen atom in its side chain and two or more hydroxyl groups at its terminal)
As 3), a di- or monoalkyl (carbon number 1 to 4) aminoalkyl (carbon number 1 to 6) (meth) acrylate such as dimethylaminoethyl methacrylate and a radically polymerizable unsaturated monomer added as necessary. Body (see macromonomer (C4) section) with 3-mercapto-
In the presence of a mercaptan-based chain transfer agent such as 1,2-propanediol (see the section on macromonomer (C4)), a radical polymerization agent (see the section on macromonomer (C4)) in an organic solvent such as methyl ethyl ketone. Examples thereof include macromonomers obtained by radical polymerization when used. The macromonomer (C3) is added in an amount of 10 to 45 parts by weight, preferably 10 to 25 parts by weight, based on 100 parts by weight of the component (A).

The macromonomer (C4) is a radical-polymerizable unsaturated monomer containing a nonionic surface-active group in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. Can be obtained. Examples of the mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group include 1-
Mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-
Propanediol, 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-
Propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3
-Propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like can be mentioned. Examples of the radical-polymerizable unsaturated monomer containing a nonionic surface-active group include terminal-alkoxylated polyethylene glycol mono (meth) acrylate and terminal-alkoxylated polytetramethylene glycol mono (meth) acrylate. The radical-polymerizable unsaturated monomer containing such a nonionic surface-active group can be used alone or in combination of two or more kinds. Further, depending on the case, it is possible to copolymerize with the following monomers.
Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, alkyl (meth) acrylate such as octyl (meth) acrylate, (meth) acrylonitrile, styrene, vinyl acetate, glycidyl ( Glycidyl group-containing monomer such as (meth) acrylate, aryl glycidyl ether, perfluoroalkyl group-containing monomer such as perfluorooctylethyl (meth) acrylate, N-methyl (propyl) perfluorooctylsulfonamidoethyl (meth) acrylate And a polydimethylsiloxane group-containing monomer such as polydimethylsiloxylpropyl (meth) acrylate. A conventionally known method can be applied as a method for producing the macromonomer (C4). For example, in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group, the nonionic surface-active group-containing radically polymerizable unsaturated monomer is used as an essential component, and if necessary, other radically polymerizable group Radical polymerization is performed on the saturated monomer, if necessary, using a polymerization initiator to obtain a nonionic surfactant-containing macromonomer (C4). Examples of the polymerization initiator include peroxide compounds such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile.

Examples of the organic polyisocyanate (D) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate. Aromatic diisocyanates such as diphenyldimethylmethane diisocyanate, dibenzyl diisocyanate, naphthylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, and tetramethyl xylylene diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5 -Diisocyanate, 3-methylpentane-1,
5-diisocyanate, 2,2,4-trimethylhexamethylene
-1,6-diisocyanate and other aliphatic diisocyanates;
There are alicyclic diisocyanates such as isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethylxylylene diisocyanate. These organic polyisocyanates are used alone or in combination of two or more. Further, modified products such as adduct modified products, carbodiimide modified products, allophanate modified products, biuret modified products, uretdione modified products, uretoimine modified products and isocyanurate modified products can also be used. Considering light resistance, these polyisocyanates are preferably hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like. Component (D) is 15 parts by weight per 100 parts by weight of component (A).
It is preferably 50 to 50 parts by weight, more preferably 25 to 40 parts by weight. In the case of the macromonomer (C4), the proportion of the polyisocyanate (D) used is usually 10 to 9000 parts by weight, and further 25 parts by weight based on 100 parts by weight of the macromonomer (C4).
It is preferably ˜8000 parts by weight. If the amount is less than 10 parts by weight, the molecular weight may be low and the dispersion stability of the emulsion may be reduced. If the amount is more than 9000 parts by weight, a large amount of unreacted isocyanate may remain and the dispersion stability of the emulsion may be reduced. .

The ultraviolet absorbing urethane resin (Iu) is emulsified. The compound (C) is introduced into the molecule as a hydrophilic group in order to give the ultraviolet absorbing urethane resin a water-dispersing ability, but if necessary, a carboxylate, a sulfonate, a phosphate, Anionic polar groups such as phosphonates, cationic polar groups other than quaternary ammonium salts, and nonionic polar groups such as ether groups may be introduced.

The reaction of the polyester polyol (A), the polyol (B), the compound (C) and the organic polyisocyanate (D) when obtaining the above-mentioned ultraviolet absorbing urethane resin is preferably carried out in the presence of an organic solvent. Done below. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane and heptane; alicyclic hydrocarbons such as cyclohexane; esters such as ethyl acetate and n-butyl acetate. Ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, dioxane, and tetrahydrofuran, and the like can be used. You may use these organic solvents individually or in combination of 2 or more types.

In the present invention, the ultraviolet absorbing resin (I) is
A solution of an ultraviolet absorbing urethane resin (Iu) obtained by reacting in an organic solvent is neutralized with a neutralizing agent (h) and then dispersed in water to be emulsified to be used as a water emulsion resin. As an emulsification method, a conventionally known method can be used. Further, the organic solvent may be removed after emulsification.

Examples of the neutralizing agent (h) include ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethyl. Organic amines such as ethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, alkali metals such as lithium, potassium and sodium, inorganic alkalis such as sodium hydroxide and potassium hydroxide However, in order to improve weather resistance and water resistance after drying, a highly volatile substance that is easily dissociated by heating is preferable, and ammonia,
Trimethylamine and triethylamine are preferred. Also, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, methyl chloride, methyl bromide, dimethyl sulfate, diethyl sulfate, benzyl chloride, p-nitrobenzyl chloride, benzyl bromide. , Ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, bromobutane and the like. These neutralizing agents are used alone or in combination of two or more.

Water-based urethane resin (IIu) As the water-based urethane resin (IIu) used in the present invention,
Water-based polyester polyurethane, water-based polyether polyurethane, water-based polycarbonate polyurethane,
Examples include water-based polyester / polycarbonate-based polyurethane. These can be used alone or in combination. As the water-based urethane resin (IIu), commercially available products can be used, and examples thereof include NeoRez R-960 and NeoRez R-970 (both manufactured by Avicia).

An ultraviolet absorbing resin (I), a water-based urethane resin (IIu) and, if necessary, a resin additive described below are mixed to prepare a water-based resin composition for artificial leather coating. As a mixing method, a conventionally known method can be used. The mixing ratio is not particularly limited and can be selected from a wide range, but the ultraviolet absorbing resin (I) and the urethane resin (II
u) is 100% by weight, the proportion of the ultraviolet absorbing resin (I) is usually 0.005 to 100% by weight, preferably 0.05 to 95% by weight, and more preferably 0.
It is 1 to 90% by weight.

If necessary, known additives such as an ultraviolet absorber, an antioxidant, a light stabilizer, a processing stabilizer, an antiaging agent and a compatibilizer are added to the water-based resin composition for artificial leather coating of the present invention. At least one of the agents can be blended. Examples of the ultraviolet absorber include, for example, 2- (2′-hydroxy-5′-methylphenyl).
Benzotriazoles such as benzotriazole, 5-chloro-2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, and 2,4-
Examples thereof include benzophenone such as dihydroxybenzophenone and 2-hydroxy-4-octyloxybenzophenone. Moreover, the thing which added the group which has a polymerizable double bond, such as a vinyl group, to the said ultraviolet absorber and superposed | polymerized this thing and made it high molecular weight is also mentioned. As the antioxidant, for example, 1,6-hexanediol-bis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester and other hindered phenolic antioxidants, dilauryl 3, Examples thereof include organic sulfur-based antioxidants such as 3′-dithiodipropionate and phosphorus-based antioxidants such as trialkylphenyl phosphate. Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-
Examples thereof include hindered amine light stabilizers such as 4-piperidyl) sebacate and nickel salt light stabilizers such as nickel dibutyldithiocarbamate. Examples of the processing stabilizer include phosphorus-based processing stabilizers such as tris (2,4-di-tert-butylphenyl) phosphate. As the antiaging agent, for example, 1,1
-Bis (4-hydroxyphenyl) cyclohexene,
N, N'-diphenyl-p-phenylenediamine etc. can be mentioned. The amount of these additives to be added is not particularly limited, but it is usually preferable to use about 0.01 to 20% by weight based on 100% by weight of the resin content in the artificial leather coating aqueous resin composition.

The water-based resin composition for coating artificial leather of the present invention can be used for coating artificial leather such as bags, shoes and clothes.

[0023]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, parts by weight and% by weight are calculated as solid content.

A synthetic polyester polyol (A) of a polyester polyol (A) having an ultraviolet absorbing group is disclosed in JP-A-10-265.
Since the same ones as in [Synthesis Example 1] and [Synthesis Example 2] described in Japanese Patent No. 557 were used, characteristics of the obtained reaction product and the like are described in JP-A-10-265557. . [Synthesis Example 1] 1,1-bis- [3- (2H was added to a glass flask equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer.
-Benzotriazol-2-yl) -4-hydroxy-
Benzene ethanol] methane (trade name “MBEP”, manufactured by Otsuka Chemical Co., Ltd.) 129.3 g, ε-caprolactone 1
70.3 g, mono-n-butyltin fatty acid salt (trade name "SCAT-24", manufactured by Sansha Kisei Co., Ltd.) 50 pp
m was added. The reaction temperature was kept at 150 ° C., and after 6 hours, the ε-caprolactone concentration in the reaction solution was measured by gas chromatography and found to be 0.43%, so the reaction was terminated. The reaction product has an acid value of 1.8 mg-KOH / g, a viscosity of 2645 cP / 60 ° C., a number average molecular weight (Mn) 1391 from GPC analysis, a weight average molecular weight (Mw) 1688,
A room temperature liquid polyester polyol (1) having Mw / Mn1.213. Further, the polyester polyol (1) exhibits a sufficiently large absorption in the ultraviolet region as described in JP-A-10-265557.

[Synthesis Example 2] 1,1-bis- [3- (2H-benzotriazol-2-yl) -4-hydroxy-benzeneethanol] methane 93 was prepared using the same equipment and raw materials as in Synthesis Example 1. 0.7 g, ε-caprolactone 206.
3 g and 50 ppm of mono-n-butyltin fatty acid salt were added. After keeping the reaction temperature at 150 ° C for 6 hours, ε-in the reaction solution
When the caprolactone concentration was measured by gas chromatography to be 0.55%, the reaction was terminated. The reaction product has an acid value of 2.5 mg-KOH / g and a viscosity of 987 cP.
/ 60 ° C, Mn2017, Mw246 from GPC analysis
5, a room temperature solid polyester polyol (2) having Mw / Mn1.222. Further, the polyester polyol (2) exhibits a sufficiently large absorption in the ultraviolet region as described in JP-A-10-265557.

Synthesis of UV Absorbing Resin Using the polyester polyol (A) having the UV absorbing group obtained in the above Synthesis Example, the UV absorbing resin (I)
Was synthesized. [Ultraviolet absorbing resin I-1] 250 parts by weight of acetone, isophorone diisocyanate (I) in a glass flask equipped with a cooling tube, a nitrogen introducing tube, a dropping funnel, a thermometer and a stirrer.
262.2 parts by weight of (PDI) was added, and 689.77 parts by weight of the ultraviolet-absorbing polyester polyol obtained in Synthesis Example 1 was added dropwise while stirring under a nitrogen atmosphere. The temperature of the flask was raised to 65 ° C., the reaction was conducted for 2 hours, 48.02 parts by weight of dimethylolbutanoic acid (DMBA) was charged, and 0.30 parts by weight of dibutyltin dilaurate was further charged, and the reaction was continued for 10 hours. did. The NCO concentration at the end of the reaction of the prepolymer is 0.452 mmol / g
(Theoretical NCO concentration was 0.44 mmol / g), the number average molecular weight by gel permeation chromatography (GPC) was 4,400, and the weight average molecular weight was 8,100. Next, 28.65 parts by weight of dimethylaminoethanol was added to neutralize the carboxylic acid content, and an acetone solution of the prepolymer was added dropwise to 1600 parts by weight of water to form an emulsion. Then, the solvent acetone was removed under reduced pressure to obtain the desired water-based ultraviolet absorbing resin. The non-volatile concentration of this water-based ultraviolet absorbing resin was 40%, and the average particle size (measured by a light scattering particle size measuring device (ELS-800, manufactured by Otsuka Electronics. The same applies hereinafter) was 95 nm.

[Ultraviolet absorbing resin I-2] 250 parts by weight of acetone and 53.8 of IPDI in a glass flask equipped with a cooling tube, a nitrogen introducing tube, a dropping funnel, a thermometer and a stirrer.
17 parts by weight of the polyester polyol obtained in Synthesis Example 1 was further added dropwise with stirring in a nitrogen atmosphere while stirring. Raise the temperature of the flask to 65 ° C and
The reaction was carried out for a time, and N-methyldiethanolamine 17.
5 parts by weight was charged, and 0.30 parts by weight of dibutyltin dilaurate was further charged, and the reaction was continued for 10 hours.
The NCO concentration at the end of the reaction of the prepolymer was 0.452.
mmol / g (theoretical NCO concentration 0.44 mmol / g)
The number average molecular weight by GPC was 4,400 and the weight average molecular weight was 8,100. Next, 8.84 parts by weight of acetic acid was added to neutralize the amine component, and an acetone solution of the prepolymer was dropped into 600 parts by weight of water to form an emulsion. Then, the solvent acetone was removed under reduced pressure to obtain the desired water-based ultraviolet absorbing resin. The nonvolatile concentration of this water-based ultraviolet absorbing resin was 40%, and the average particle size was 170 nm.

[Ultraviolet-absorbing resin I-3] The same ultraviolet-absorbing polyester polyol as in Example 1 was used, except that the polyester polyol obtained in Synthesis Example 2 was used as the ultraviolet-absorbing polyester polyol. A resin was obtained. The nonvolatile concentration of this water-based ultraviolet absorbing resin was 40%, and the average particle size was 82 nm.

[Ultraviolet absorbing resin I-4] In a glass flask equipped with a cooling tube, a nitrogen introducing tube, a dropping funnel, a thermometer and a stirrer, 225 parts by weight of methyl ethyl ketone, 262 parts by weight of dimethylaminoethyl methacrylate, 1-mercapto. -2,3-Propanediol 13 parts by weight, azobismethylbutyronitrile (Wako Pure Chemical Industries, ABN-E) 1.
5 parts by weight were charged and polymerization was carried out at 80 ° C. for 6 hours to obtain a macromonomer. The nonvolatile content of the obtained macromonomer was 53.2%, the hydroxyl value (KOHmg / g) was 25.8,
The amine value (KOHmg / g) was 181. Next, 139.8 parts by weight of methyl ethyl ketone, 0.30 parts by weight of dibutyltin dilaurate, and 20.7 parts by weight of IPDI were added, and the mixture was stirred under a nitrogen atmosphere while further stirring to 129.2 parts by weight of the polyester polyol obtained in Synthesis Example 1. Parts and 21.0 parts by weight of macromonomer were added dropwise. The temperature of the flask was raised to 75 ° C. and the reaction was continued for 6 hours. The number average molecular weight by GPC of the urethane solution at the end of the reaction was 4000, and the weight average molecular weight was 10,000.
Next, 217.4 parts by weight of the above-mentioned urethane solution was added with 9.
73 parts by weight is added to quaternize the tertiary amine part,
It was dropped into 507 parts by weight of water to form an emulsion. Then, the solvent methyl ethyl ketone was removed under reduced pressure to obtain a desired ultraviolet absorbing emulsion. This ultraviolet absorbing emulsion has a nonvolatile concentration of 35% and an average particle size of 9
It was 0 nm.

[Ultraviolet absorbing resin I-5] For comparison, a commercially available product, Tinuvin 113, is used as an ultraviolet absorbing resin.
0 (Ciba Specialty Chemicals, α [3- [3- (2H
-Benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] -1-oxopropyl] -ω-
Hydroxypoly (oxo-1,2-ethanediyl) and α [3-
[3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] -1-oxopropyl] -ω- [3- [3- (2H-benzotriazole -2-yl) -5
-(1,1-Dimethylethyl) -4-hydroxyphenyl] -1-
Oxopropyl] poly (oxo-1,2-ethanediyl) and polyethylene glycol 300 mixture) was used.

[Ultraviolet Absorbing Resin I-6] For comparison, as an ultraviolet absorbing resin, a commercially available product LX-301 (manufactured by Asahi Denka Co., Ltd., 2 (2'-hydroxy-3'-t-butyl-5'-methyl) was used. (Phenyl)
A forced emulsified emulsion of nonionic emulsifier of -5-chlorobenzotriazole, non-volatile content 30%) was used.

Water-based urethane resin (IIu) As the water-based urethane resin (IIu), the following commercial products were used. [Water-based urethane resin IIu-1] Water-based urethane resin emulsion: Superflex E-2000 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., an ether-based urethane resin forcedly emulsified with a nonionic emulsifier (the resin itself is emulsified in water with an emulsifier)) [Aqueous Urethane Resin IIu-2] Aqueous Urethane Resin Emulsion: Evaphanol AP-12 (manufactured by Nichika Chemical Co., Ltd., an ether urethane resin was forcibly emulsified with a nonionic emulsifier (the resin itself was emulsified with water by an emulsifier)). thing.)

[Example 1] As the water-based resin composition for artificial leather coating, 2% of the ultraviolet absorbing resin I-1 obtained above was used.
A mixture of 100 parts by weight of polyurethane resin IIu-1 and 100 parts by weight of polyurethane resin was used. [Examples 2-8 and Comparative Examples 1-6] As the water-based resin composition for artificial leather coating, those having the formulations shown in Table 1 were used.

The water-based resin compositions for artificial leather coating obtained in Examples and Comparative Examples were evaluated as follows. <Light resistance> After being formed into a film having a thickness of 100 μm and dried at 120 ° C. for 30 minutes, the film is a super xenon weather meter (manufactured by Suga Test Instruments, SX2-7).
50), a xenon lamp output of 180 W / m ² , a black panel temperature of 63 ° C. and a humidity of 50% were tested for 1000 hours, and the film after the test was evaluated by comparing with the film before the test. ◯: No change, ×: Tack feeling (surface decomposition) <Light resistance under dew condensation conditions> Filmed to a film thickness of 100 μm, dried at 120 ° C. for 30 minutes, and then the film was subjected to the above super xenon weather meter. With xenon lamp output 180W / m ² , black panel temperature 6
The test was conducted at 3 ° C. and 100% humidity for 1000 hours, and the film after the test was evaluated by comparing it with the film before the test. ○: No change, ×: Tack feeling (surface decomposition)

As is clear from the examples, the film made from the water-based resin composition for artificial leather coating of the present invention is excellent in light resistance, light resistance under dew condensation conditions and adhesion, and is superior to that of the plastic substrate itself. It has improved light resistance and shows excellent durability under practical conditions.

[0036]

[Table 1]

[0037]

The film made from the water-based resin composition for artificial leather coating of the present invention is excellent in light resistance and light resistance under dew condensation conditions, so that artificial leather having excellent light resistance under practical conditions is used. Can be provided.

Claims (8)

[Claims] 1. A water-based resin composition for artificial leather coating, which comprises an ultraviolet-absorbing resin (I) obtained by using a polyester polyol (A) having an ultraviolet-absorbing group and an aqueous urethane resin (IIu). 2. The water-based resin composition for artificial leather coating according to claim 1, wherein the polyester polyol (A) is represented by the following general formula (1). [Chemical 1] (R ^{1 and} R ² are H, an alkyl group having 1 to 10 carbon atoms, n and n ′ are integers of 4 to 8, m and m ′ are 1 to 20, and n.
R ¹ and R ² and n ′ R ¹ and R ² may be the same or different, and m and m ′ constituent units may be the same or different. ) 3. The ultraviolet absorbing resin (I) is a polyester polyol (A), a compound (C) containing an ionic and / or nonionic surface active group, an organic polyisocyanate (D), and, if necessary, The water-based resin composition for artificial leather coating according to claim 1 or 2, which is an ultraviolet absorbing urethane resin obtained by reacting an added polyol (B). 4. The water-based resin composition for artificial leather coating according to claim 3, wherein the compound (C) is a compound (C1) containing a carboxyl group and an active hydrogen group. 5. The compound (C) is aryl or alkyl (having 1 to 10 carbon atoms) dialkanol (having 1 to 5 carbon atoms).
The water-based resin composition for artificial leather coating according to claim 3, which is an amine (C2). 6. The artificial leather according to claim 3, wherein the compound (C) is a macromonomer (C3) having a tertiary and / or quaternary nitrogen atom in its side chain and two or more hydroxyl groups at its end. Aqueous resin composition for coating. 7. An ultraviolet-absorbing resin (I), which is obtained by reacting an ultraviolet-absorbing urethane resin solution obtained by reacting in an organic solvent with a neutralizing agent (h) and then dispersed in water to form an emulsion. The water-based resin composition for artificial leather coating according to claim 3, which is an emulsion resin. 8. The water-based resin composition for artificial leather coating according to claim 7, wherein the ultraviolet absorbing resin (I) is a water emulsion resin obtained by dispersing in water and emulsifying and then removing an organic solvent. .