JP6565309B2 - UV-absorbing polyurethane composition, coating material using the composition, and coating film - Google Patents

Description

  The present invention relates to an ultraviolet ray-absorbing polyurethane resin composition useful for various fields, in particular, electronic device members such as mobile phones, doublets, home appliances, OA equipment, home appliance members, household goods members and automobile members, and the composition. The present invention relates to a molded body using a product and a coating material.

  The polyurethane resin is obtained by reacting a polyisocyanate component and a polyol component, and polyurethane resins having various performances are provided depending on the types and combinations of the components. In particular, a molded body and a coating material using such a resin are often used for electronic equipment member supplies, furniture / home appliance use, daily miscellaneous goods use, and automobile member use. However, when such a molded product or coating material is used in contact with the human body for a long period of time, it can be used for sebum components contained in sweat, oleic acid contained in skin protection cream, and sunscreen agents (creams, lotions, etc.). There was a problem that the contained ultraviolet absorber component caused deterioration of the surface of the molded body or coating material and a phenomenon that was sticky, and could not withstand long-term use.

  In such a background, development of a polyurethane-based resin exhibiting oil resistance against oleic acid, which is a main component of sebum components, has been promoted. As a polyurethane-based resin excellent in oleic acid resistance, a polyisocyanate compound, a polycarbonate diol using 1,5-pentanediol and 1,6-hexanediol in an arbitrary composition ratio, and a polysiloxane are essential components. The curable composition which was made is proposed (for example, refer patent documents 1-4).

  However, the curable compositions described in these patent documents are not satisfactory with respect to the resistance to the ultraviolet absorber contained in the sunscreen agent.

  In other words, conventional polyurethane resin coating materials have been improved in durability against oil components such as oleic acid and beef tallow, but are not suitable for ultraviolet absorbers contained in cosmetics and sunscreens (creams, lotions, etc.). The resistance is often insufficient, and the appearance of the surface of the molded body may be deteriorated due to adhesion of the ultraviolet absorber. Therefore, there is a demand for paints that are resistant to ultraviolet absorbers.

JP 2007-112986 A JP 2008-063395 A JP 2008-075048 A JP 2008-303284 A

  The present invention has been made on the basis of the circumstances as described above, and its purpose is durability to ultraviolet absorbers contained in cosmetics, sunscreens, etc. (hereinafter referred to as “ultraviolet absorber resistance”). .) Is an excellent polyurethane composition (hereinafter referred to as “ultraviolet ray resistant polyurethane composition”), and a molded product, a coating material and a paint blending solution obtained from the composition.

  As a result of intensive studies to solve the above problems, the present inventors have found a polyurethane composition containing a polyester polyol having a specific structure and a curing agent, and have completed the present invention. That is, the present invention is shown in the following [1] to [8].

  [1] A UV absorbent polyurethane composition comprising a polyester polyol containing 3.2 mmol / g or more of at least one structure selected from the group consisting of an aromatic ring structure and an alicyclic structure, and a curing agent.

  [2] A polyester polyol having at least one structure selected from the group consisting of an aromatic ring structure and an alicyclic structure reacts a polyvalent carboxylic acid having an aromatic ring or an alicyclic ring or an acid anhydride thereof with a polyhydric alcohol. The UV-absorbing polyurethane composition as described in [1] above, wherein the polyurethane composition is obtained.

  [3] Either [1] or [2] above, wherein the average number of functional groups of the polyester polyol having at least one structure selected from the group consisting of an aromatic ring structure and an alicyclic structure is 8 to 15 A UV-absorbing polyurethane composition as described above.

  [4] UV resistance according to any one of [1] to [3], wherein at least one selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates is used as a curing agent. Absorbent polyurethane composition.

  [5] The UV-absorbing polyurethane composition according to any one of [1] to [4] above, wherein an adduct of hexamethylene diisocyanate is used as the curing agent.

  [6] A molded article obtained from the ultraviolet absorbent anti-resistant polyurethane composition according to any one of [1] to [5].

  [7] A coating material obtained from the UV-absorbing polyurethane composition according to any one of [1] to [5].

  [8] A paint blending liquid obtained from the ultraviolet ray absorbent polyurethane composition according to any one of [1] to [5].

  The UV-absorbing polyurethane composition of the present invention is excellent in durability against UV absorbers contained in cosmetics, sunscreens, etc., and is therefore used in cosmetics, sunscreens, etc. when used as a coating material for members. The durability against the ultraviolet absorber can be imparted to the member.

  Hereinafter, the present invention will be described in detail.

  The UV-absorbing polyurethane composition of the present invention comprises a polyester polyol containing 3.2 mmol / g or more of at least one structure selected from the group consisting of an aromatic ring structure and an alicyclic structure, and a curing agent. Features.

  Here, the ultraviolet absorbent used for the index of the ultraviolet absorbent resistance in the present invention will be described. As the ultraviolet absorber, for example, one or two or more selected from the group consisting of paraaminobenzoic acid, cinnamic acid, benzophenone, salicylic acid, benzoyltriazole, and other aromatic ultraviolet absorbers Mixtures are known, and when these substances are transferred to molded bodies and polyurethane-based coating materials, phenomena such as appearance deterioration and stickiness of the molded body surface are observed.

  The ultraviolet-absorbing agent-resistant polyurethane composition of the present invention is, as shown in Examples described later, of at least 2-hydroxy-4-methoxybenzophenone, 2-ethylhexyl salicylate, and 3,3,5 salicylic acid. Excellent durability against trimethylcyclohexyl, 2-ethylhexyl 3,3-diphenyl-2-cyanoacrylate, 2-ethylhexyl-4-methoxycinnamate, and 4-tert-butylbenzoyl (4-methoxybenzoyl) methane Indicates.

  Next, the polyester polyol used in the ultraviolet ray absorbent polyurethane composition of the present invention will be described. The polyester polyol of the present invention is obtained by reacting a polyvalent carboxylic acid or an acid anhydride thereof with a polyhydric alcohol. The polyvalent carboxylic acid or acid anhydride thereof preferably has at least one structure selected from the group consisting of an aromatic group and an alicyclic group from the viewpoint of ultraviolet absorber resistance. In addition, the polyhydric alcohol is not particularly limited, but it is preferable to include a trihydric or higher alcohol from the viewpoint of chemical resistance. In addition, an aromatic polyvalent carboxylic acid and an alicyclic polyvalent carboxylic acid and an aliphatic polyvalent carboxylic acid can be used in combination as long as the performance does not deteriorate.

In addition, the calculation method of aromatic ring structure and alicyclic structure content is shown by the following formula.
(Total number of moles of aromatic ring and alicyclic ring in raw material used to obtain polyester polyol) / (total mass of resin content of polyester polyol obtained).

<Aromatic polyvalent carboxylic acid>
Specific examples of the aromatic polycarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2 Examples include '-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid and the like.

  Moreover, you may use the acid anhydride of these aromatic polyhydric carboxylic acid.

<Alicyclic polycarboxylic acid>
Specific examples of the alicyclic polycarboxylic acid include 1,2,3,6 tetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, and bicyclo [2.2.1] heptane-2-3. -Dicarboxylic acid etc. are mentioned.

  Moreover, you may use the acid anhydride of these alicyclic polyhydric carboxylic acid.

<Aliphatic polycarboxylic acid>
Specific examples of the aliphatic polyvalent carboxylic acid include succinic acid, adipic acid, sebacic acid, suberic acid, azelaic acid and the like.

<Polyhydric alcohol>
Specific examples of the polyhydric alcohol include glycol and trihydric or higher polyhydric alcohol. Specific examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, methylpropanediol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol Etc. Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerystol. Further, a glycol and a trihydric or higher polyhydric alcohol can be used in combination as long as the performance does not deteriorate.

<Reaction catalyst>
A reaction catalyst may be used for the production of the polyester polyol. Examples of the catalyst include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, cerium and other metals, metal alkoxides, metals Examples thereof include salts and metal oxides. Preferred catalysts in the present invention are alkali metals, alkaline earth metals, zinc, titanium, lead carbonates, carboxylates, borates, silicates, oxides, organometallic compounds, and especially the organic titanium compounds. preferable.

  The polyester polyol constituting the ultraviolet absorbent resistant polyurethane composition of the present invention can be produced by a general method for producing a polyester polyol.

  The polyester polyol may be dissolved in an organic solvent.

  Specific examples of the organic solvent include aliphatic hydrocarbons such as octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, and isobutyl acetate. Esters such as ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, glycol ether esters such as ethyl-3-ethoxypropionate, ethers such as dioxane, iodination Polarized aprotic such as halogenated hydrocarbons such as methylene and monochlorobenzene, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide Medium, such as tertiary alcohols and diacetone alcohol and the like. These solvents can be used alone or in combination of two or more.

  Next, the curing agent that constitutes the UV-absorbing polyurethane composition of the present invention will be described.

<Curing agent>
The curing agent is preferably an aliphatic polyisocyanate or an alicyclic polyisocyanate, and a polyisocyanate obtained by combining them from the viewpoint of coating film weather resistance. More preferably, it is particularly preferable to use an adduct body obtained by partially urethane-modifying hexamethylene diisocyanate (hereinafter referred to as “HDI”) from the viewpoint of ultraviolet ray resistance.

  In addition, aromatic polyisocyanates and araliphatic polyisocyanates can be used for the curing agent as long as the performance does not deteriorate. Aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, Isocyanurate group-containing polyisocyanate, uretdione group-containing polyisocyanate, uretdione group and isocyanurate group-containing polyisocyanate, urethane group-containing polyisocyanate, allophanate group-containing polyisocyanate, buret group-containing polyis obtained from alicyclic polyisocyanate as a raw material Isocyanate, uretoimine group-containing polyisocyanate and the like can be used alone or in combination of two or more.

<Aliphatic polyisocyanate>
Specific examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, and the like. Can be mentioned.

<Alicyclic polyisocyanate>
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate.

<Aroaliphatic polyisocyanate>
Specific examples of the araliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene, ω, ω′- And diisocyanato-1,4-diethylbenzene.

<Aromatic polyisocyanate>
Specific examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4′-diisocyanate, 2,2′-diphenylpropane-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3′-dimethoxydiphenyl-4 4'-diisocyanate, and the like can be given.

  The polyester polyol obtained by the above method and the UV-absorbing polyurethane-resistant polyurethane composition may include, for example, an antioxidant, an UV absorber, a pigment, a dye, a solvent, a flame retardant, and a hydrolysis inhibitor as necessary. In addition, additives such as a lubricant, a plasticizer, a filler, an antistatic agent, a dispersant, a catalyst, a storage stabilizer, a surfactant, and a leveling agent can be appropriately blended.

  Next, a molded article using the ultraviolet absorbent polyurethane composition of the present invention and a coating material will be described.

  The UV-absorbing polyurethane composition of the present invention is used as a molded product or coating material for electronic equipment members such as mobile phones, doublets, home appliances, OA equipment, home appliance members, household goods members and automobile members. The

  As a molded object, a member, a structure, a film, and a sheet | seat are contained, for example, and it shape | molds by well-known techniques, such as casting and application | coating.

  Moreover, when using the ultraviolet-absorbing agent-resistant polyurethane composition of the present invention as a coating material, for example, the above-described curing agent and, if necessary, the above-described curing agent in the resin composition for a coating material containing the polyester polyol described above. After mixing the additives and stirring uniformly, a coating film is formed on the substrate by a known technique such as spray coating, knife coating, wire bar coating, doctor blade coating, reverse roll coating, calendar coating, and the like.

  Examples of the base material include acrylic resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene phthalate resin, polystyrene resin, AS resin, ABS resin, polycarbonate-ABS resin, 6-nylon resin, 6, 6-nylon resin, MXD6 nylon resin, polyvinyl chloride resin, polyvinyl alcohol resin, polyurethane resin, phenol resin, melamine resin, polyacetal resin, chlorinated polyolefin resin, polyolefin resin, polyamide resin, polyether ether ketone resin, polyphenylene sulfide resin , NBR resin, chloroprene resin, SBR resin, SEBS resin, polyethylene, polypropylene, etc. That.

  In order to improve the adhesiveness of these substrates, the substrate surface can be previously subjected to treatments such as corona discharge treatment, flame treatment, ultraviolet irradiation treatment, ozone treatment, primer treatment, and solvent treatment.

  Further, the coating amount of the coating material is not particularly limited, but for example, it is preferable to apply so that the dry film thickness is 20 μm or more. By setting the film thickness to 20 μm or more, the ultraviolet absorbent resistance of the coating material can be improved.

  Furthermore, when using the UV-absorbing polyurethane composition of the present invention as a coating compounding liquid, the hydroxyl group of the polyester polyol in the UV-absorbing polyurethane composition and the isocyanate group of the polyisocyanate used as a curing agent The molar ratio (R) is preferably R = isocyanate group / hydroxyl group so that R = 0.4 to 2.5, and more preferably R = 0.7 to 1.5. It is preferable to mix. Although the organic solvent used for dilution is not specifically limited, From the said organic solvent, it can use individually or in combination of 2 or more types.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Synthesis of polyester polyol>
<Production Example 1>
A reactor equipped with a stirrer, a thermometer, a heating device, and a distillation tower is charged with 112 g of phthalic anhydride, 235 g of hexahydrophthalic anhydride, 344 g of trimethylolpropane, and 0.0065 g of tetrabutyl titanate as a reaction catalyst. The reaction was conducted by heating to 150 ° C. while raising the temperature from 150 ° C. at a rate of 1 to 10 ° C./hour, and water was distilled off. When the water no longer distilled off at normal pressure, the pressure was gradually reduced to 2.6 kPa to distill off the water. The temperature in the reactor was lowered to 140 ° C. and 350 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PMA) was added to obtain a polyester polyol solution POH-1. The hydroxyl value of this prepolymer was 176 KOHmg / g.

<Production Example 2>
A reactor similar to Production Example 1 was charged with 349 g of hexahydrophthalic anhydride, 343 g of trimethylolpropane, and 0.0065 g of tetrabutyl titanate as a reaction catalyst, and a ratio of 150 ° C. to 1 ° C./hour at 150 ° C./hour at normal pressure in a nitrogen stream. The reaction was carried out by heating to 220 ° C. while raising the temperature, and water was distilled off. When the water no longer distilled off at normal pressure, the pressure was gradually reduced to 2.6 kPa to distill off the water. The reactor internal temperature was lowered to 140 ° C. and 350 g of PMA was charged to obtain a polyester polyol solution POH-2. The hydroxyl value of this prepolymer was 176 KOHmg / g.

<Production Example 3>
A reactor similar to Production Example 1 is charged with 347 g of phthalic anhydride, 299 g of trimethylolpropane, 45 g of neopentyl glycol and 0.0065 g of tetrabutyl titanate as a reaction catalyst. The reaction was conducted by heating to 220 ° C. while raising the temperature at a rate of / hour, and water was distilled off. When the water no longer distilled off at normal pressure, the pressure was gradually reduced to 2.6 kPa to distill off the water. The reactor internal temperature was lowered to 140 ° C. and 350 g of PMA was charged to obtain a polyester polyol solution POH-3. The hydroxyl value of this prepolymer was 170 KOHmg / g.

<Production Example 4>
A reactor similar to Production Example 1 was charged with 406 g of phthalic anhydride, 179 g of trimethylolpropane, 119 g of glycerin, and 0.0065 g of tetrabutyl titanate as a reaction catalyst, and from 150 ° C. to 1 to 10 ° C./hour at normal pressure under a nitrogen stream. The reaction was carried out by heating up to 220 ° C. while raising the temperature at a rate of 5%. When the water no longer distilled off at normal pressure, the pressure was gradually reduced to 2.6 kPa to distill off the water. The reactor internal temperature was lowered to 140 ° C. and 350 g of PMA was charged to obtain a polyester polyol solution POH-4. The hydroxyl value of this prepolymer was 180 KOHmg / g.

<Production Example 5>
In the same reactor as in Production Example 1, 298 g of phthalic anhydride, 389 g of trimethylolpropane, and 0.0065 g of tetrabutyl titanate as a reaction catalyst were charged at a rate of 150 ° C. to 1 ° C./hour at 150 ° C./hour under normal pressure in a nitrogen stream. The reaction was carried out by heating to 220 ° C. while raising the temperature, and water was distilled off. When the water no longer distilled off at normal pressure, the pressure was gradually reduced to 2.6 kPa to distill off the water. The reactor internal temperature was lowered to 140 ° C. and 350 g of PMA was charged to obtain a polyester polyol solution POH-5. The hydroxyl value of this prepolymer was 195 KOHmg / g.

<Production Example 6>
158 g of phthalic anhydride, 250 g of adipic acid, 274 g of trimethylolpropane, 148 g of 1,3-butanediol, and 0.0065 g of tetrabutyl titanate as a reaction catalyst were charged in a reactor similar to Production Example 1 at normal pressure under a nitrogen stream. While raising the temperature from 150 ° C. at a rate of 1 to 10 ° C./hour, the reaction was conducted by heating to 200 ° C. to distill off water. When the water no longer distilled off at normal pressure, the pressure was gradually reduced to 2.6 kPa to distill off the water. The temperature in the reactor was lowered to 60 ° C., and 350 g of ethyl acetate was charged to obtain a polyester polyol solution POH-6. The hydroxyl value of this prepolymer was 190 KOHmg / g.

  Tables 1 and 2 show the blending amounts and properties of the raw materials used for the polyester polyols POH-1 to POH-4 and POH-5 to POH-6.

<Creation of coating material>
The hydroxyl group-terminated prepolymer of POH-1 to POH-6 and the hydroxyl group of polycarbonate diol and polyisocyanate (HDI adduct, manufactured by Tosoh Corporation, trade name: Coronate HL, NCO content 12.7% by mass, solid content 75 (Mass%) of the isocyanate group so that the molar ratio of R = isocyanate group / hydroxyl group is 1.0, and further diluted with ethyl acetate so that the total solid content is 45 mass%. A blended solution was prepared. This was applied to a polyethylene terephthalate plate (manufactured by Partec Co., Ltd.) with an applicator so that the film thickness after drying was 30 μm, dried at 25 ° C. for 1 hour, and then cured at 80 ° C. for 10 hours to prepare a coating material. The polycarbonate diol shown in Comparative Example 3 is Nippon Solar 970 (hydroxyl value 224 KOHmg / g) manufactured by Tosoh Corporation.

  Tables 3 to 4 show the composition of each liquid composition and various physical properties of the resulting coating material.

Abbreviations used in Tables 3 and 4 are as follows.
(1) Compound a: 2-hydroxy-4-methoxybenzophenone (2) Compound b: 2-ethylhexyl salicylate (3) Compound c: 3,3,5-trimethylcyclohexyl salicylate (4) Compound d: 3,3-diphenyl 2-Cyanoacrylic acid 2-ethylhexyl (5) Compound e: 2-ethylhexyl-4-methoxycinnamate (6) Compound f: 4-tert-butylbenzoyl (4-methoxybenzoyl) methane (diluted solution of glycerin 3%) .

  The evaluation results shown in Tables 3 and 4 are based on the following evaluation methods.

<Crosscut tape peeling test>
The adhesion of the coating film was evaluated according to a cross-cut tape peeling test of JIS K-5600-8-5-2. The numerical values in the table mean the number of squares that remain without being peeled out of 100 squares.

<Ultraviolet absorber resistance>
0.02 g of the following compounds (1) to (5) were dropped on the coating film, left at 80 ° C. for 1 hour, wiped off the drop, and the appearance was visually evaluated.

  Since the compound (6) is a solid, it is dissolved in glycerin so as to be 3%, 0.02 g of the solution is dropped on the coating film, left to stand at 80 ° C. for 1 hour, and then the drop is wiped off, and the appearance is visually evaluated. .

<Compound>
(1) 2-hydroxy-4-methoxybenzophenone (2) 2-ethylhexyl salicylate (3) 3,3,5-trimethylcyclohexyl salicylate (4) 2-ethylhexyl 3,3-diphenyl-2-cyanoacrylate (5) 2-Ethylhexyl-4-methoxycinnamate (6) 4-tert-butylbenzoyl (4-methoxybenzoyl) methane.

<Evaluation criteria>
・ No change in coating film (Evaluation: A)
・ Coating film with slight chemical marks (Evaluation: B)
・ Coating film has significantly swollen and glossy change (Evaluation: C)
-The coating film caused dissolution (evaluation: D).

  As shown in Tables 3 and 4, it was found that the coating materials according to Examples 1 to 4 were excellent in UV-absorbing property. On the other hand, the coating materials of Comparative Examples 1 to 3 were inferior in UV-absorbing property.

Claims (7)

It contains at least one structure selected from the group consisting of an aromatic ring structure and an alicyclic structure of 3.2 mmol / g or more, and includes a polyester polyol characterized by having an average functional group number of 8 to 15, and a curing agent. UV-resistant absorbent polyurethane composition. The polyester polyol having at least one structure selected from the group consisting of an aromatic ring structure and an alicyclic structure is a reaction product of a polyvalent carboxylic acid having an aromatic ring or an alicyclic ring or an acid anhydride thereof and a polyhydric alcohol. The UV-absorbing polyurethane composition according to claim 1, wherein The UV-absorbing polyurethane composition according to claim 1 or 2 , wherein at least one selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates is used as the curing agent. The ultraviolet-absorbing polyurethane composition according to any one of claims 1 to 3 , wherein an adduct of hexamethylene diisocyanate is used as the curing agent. A molded product obtained from the ultraviolet absorbent polyurethane composition according to any one of claims 1 to 4 . The coating material obtained from the ultraviolet absorber resistant polyurethane composition in any one of Claims 1 thru | or 4 . A paint blending solution obtained from the ultraviolet absorbent anti-resistant polyurethane composition according to any one of claims 1 to 4 .