UV absorber aqueous composition

Abstract

To provide an ultraviolet absorber aqueous composition which is excellent in transparency and sufficiently shields ultraviolet rays, and a coating composition using the same.SOLUTION: The ultraviolet absorber aqueous composition is an aqueous composition in which at least an ultraviolet absorber and a dispersant are present in an aqueous medium. The ultraviolet absorber is a compound represented by the following general formula, and the aqueous composition contains a surfactant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an ultraviolet absorbent composition, a method for producing the same, and a method for producing a coating composition. [Background technology]

[0002] Benzotriazole-based UV absorbers have been widely used due to their excellent UV absorption performance and photostability. In particular, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (also known as bisoctrizole) is known as a UV absorber that can absorb long wavelengths, but it is an organic compound and is generally used in a molecular state dissolved in a volatile organic solvent. However, because of concerns about the effects of volatile organic solvents on the environment and human body, the use of aqueous solvents is desirable, but bisoctrizole is insoluble in water, and methods for dispersing the compound in water have been reported (Patent Documents 1, 2, 3, 4, 5). Dispersion in water not only allows the use of aqueous solvents and eliminates the need for organic solvents, but also improves the light resistance of the UV absorber itself because it is in a dispersed and not dissolved state, and since the dispersed state has increased absorption up to longer wavelengths than the dissolved state, the amount of UV absorber used can be reduced, which is expected to expand the range of applicable products to water-based paints, sol-gel coating liquids, in-line coating liquids, etc. Furthermore, by making it into an aqueous dispersion, it can be processed into paint forms and film forms, etc., and in particular, by making it into a transparent dispersion, it is expected to be widely applicable to products that require light resistance and transparency, such as fiber materials, inks, cosmetics, etc. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2017-95559 A [Patent Document 2] Patent No. 5270134 [Patent Document 3] WO2015 / 152057 [Patent Document 4] Patent No. 5396265 [Patent Document 5] Patent No. 5700552 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the present inventors have found that it is difficult to improve the visible light transmittance while sufficiently cutting ultraviolet light with the dispersions disclosed in these conventionally known documents. Specifically, among the above documents, Patent Documents 1 to 3 do not provide a visible light (600 nm) transmittance of more than 25% (value when the ultraviolet absorber concentration is 0.00982%) when the transmittance in the ultraviolet region (200 nm to 380 nm) is 0.0%. Therefore, it is difficult to apply the dispersions to applications that require a higher transparency than those reported above, such as glass coating.

[0005] Furthermore, in Patent Documents 4 and 5, high transmittance is maintained by undergoing a long manufacturing process, and the production efficiency cannot be said to be high due to the long manufacturing process. Therefore, there has been a demand for a dispersion composition that can be produced efficiently in a short production process while maintaining high transmittance. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above problems. As a result, they have found that the transmittance can be improved in a shorter time than ever before by using a specific ultraviolet absorber and dispersing it with a surfactant. That is, the dispersion is a dispersion in which a specific bis(octrizole)-related compound is dispersed in water, and the dispersion contains a surfactant.

[0007] That is, the present invention provides (1) An aqueous composition containing at least an ultraviolet absorbent and a dispersant in an aqueous medium, the ultraviolet absorbent being a compound represented by the following general formula (I) and containing a surfactant; General formula (I) [ka] During the ceremony, R and R 1' may be the same or different and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R3SO- group or an R3O2- group. R2 and R 2' may be the same or different and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a COH group, a phenyl group, a phenylalkyl group containing 1 to 4 carbon atoms in the alkyl moiety, or a cycloalkyl group having 5 to 8 carbon atoms. R3 is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group substituted by an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, or the above aryl group substituted by one or two alkyl groups having 1 to 4 carbon atoms, or a 1,1,2,2-tetrahydroperfluoroalkyl group (the perfluoroalkyl portion of this group consists of 6 to 16 carbon atoms). (2) The aqueous ultraviolet absorbent composition according to (1) above, wherein the ultraviolet absorbent is dispersed with an average dispersed particle size of 10 to 35 nm.

[0008] (3) The aqueous ultraviolet absorbent composition according to the above (1)1 or (2), wherein the dispersant is one or more compounds selected from acrylic copolymers of control polymerization. (4) In the compound of the general formula (I), The aqueous ultraviolet absorbent composition according to any one of the above (1) to (4), wherein R1 is chlorine and R2 is tert-octyl. (5) A method for producing a coating composition, comprising mixing the aqueous ultraviolet absorbent composition according to any one of (1) to (4) above with a resin component to prepare a coating liquid. is located. Effect of the Invention

[0009] According to the present invention, it is possible to obtain an ultraviolet absorbent composition capable of improving visible light transmittance while sufficiently blocking ultraviolet rays, and a coating composition using the same. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a graph showing the transmittance versus wavelength for the ultraviolet absorbent dispersions of the present invention obtained in Examples 1 and 4 and the ultraviolet absorbent dispersions obtained in Comparative Examples 3 and 7. [Diagram 2] FIG. 2 is a graph showing absorbance versus wavelength for the ultraviolet absorbent dispersions of the present invention obtained in Examples 1 and 4 and the ultraviolet absorbent dispersions obtained in Comparative Examples 3 and 7. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below. [UV absorbing compounds] 1. Structure of UV-absorbing compounds In the present invention, an ultraviolet absorbing compound represented by the following general formula (1) is used.

[0012] General formula (1) [ka]

[0013] During the ceremony, R and R 1'may be the same or different and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R3SO- group or an R3O2- group.

[0014] R2 and R 2' may be the same or different, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a COH group, a phenyl group, a phenylalkyl group containing 1 to 4 carbon atoms in the alkyl moiety, or a cycloalkyl group having 5 to 8 carbon atoms. An alkyl group having 1 to 12 carbon atoms is preferred.

[0015] R3 is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group substituted by an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, or the above aryl group substituted by one or two alkyl groups having 1 to 4 carbon atoms, or a 1,1,2,2-tetrahydroperfluoroalkyl group (the perfluoroalkyl portion of this group consists of 6 to 16 carbon atoms). R and R 1' is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen group. More preferably, it is a hydrogen atom or a halogen group. A chlorine atom is most preferred.

[0016] R2 and R 2' is preferably an alkyl group having 1 to 12 carbon atoms. Most preferably, R and R 2' are the following groups:

[0017] [ka]

[0018] These compounds are known and may be commercially available or may be produced by various known methods for producing benzotriazole compounds. In general, the benzotriazole compounds are produced from phenols as raw materials, and then the benzotriazole is dimerized with aldehydes. For example, the compounds may be produced by the methods described in Japanese Patent 3223377 and German Patent 1,670,951.

[0019] 2. Glass transition temperature of UV absorbing compounds The ultraviolet absorbing compound used in the present invention preferably has a glass transition point of 35° C. or higher, more preferably 60° C. or higher, and most preferably 67° C. If the glass transition point is too low, the glass transition point is exceeded due to the heat of dispersion during dispersion, and crystallinity cannot be maintained, making it difficult to proceed with dispersion. This results in an increase in particle size and a decrease in transparency.

[0020] 3. Melting point of UV absorbing compound The ultraviolet absorbing compound used in the present invention preferably has a melting point of 150° C. or higher, more preferably 190° C. or higher, and most preferably 205° C. or higher. If the melting point is too low, the glass transition point also tends to be low, resulting in the above-mentioned problems.

[0021] The melting point and glass transition point are values ​​measured by DSC, more specifically, according to the method described in JIS standard K-7121-1987 "Method of measuring transition temperature of plastics."

[0022] Molecular weight of UV absorber The ultraviolet absorbing compound used in the present invention preferably has a molecular weight of 400 to 2500, more preferably 650 to 750, and most preferably 727.76. If the molecular weight is lower than 400, the melting point and glass transition point tend to be low, and if it is higher than 2500, the compound tends to be difficult to crystallize, causing a problem that it cannot be dispersed.

[0023] [Surfactant] In the present invention, a surfactant is contained. Surfactants include, for example, ionic surfactants, nonionic surfactants and cationic surfactants.Ionic surfactants include, for example, fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfosuccinates, alkyldiphenylether disulfonates, polyoxyethylene alkyl sulfate ester salts, polyoxyethylene alkylaryl sulfate ester salts, alkanesulfonates, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl phosphate ester salts, N-methyl-oleoyl taurate salts, α-olefin sulfonates. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene derivatives, ethylene oxide-propylene oxide block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, acetylene glycols, and ethylene glycol adducts of acetylene glycols. Examples of cationic surfactants and amphoteric surfactants include alkylamine salts, quaternary ammonium salts, alkyl betaines, and amine oxides. These ionic surfactants may be used as dispersants, wetting agents, detergents, and surface tension adjusters, which will be described later.

[0024] Particularly preferred surfactants are polyoxyalkylene derivatives having an HLB of 9 to 16, preferably 11 to 15, and most preferably 13.2, containing 1 to 3 benzyl groups which may be bonded to any part of the phenyl ether ring, and the hydrophilic group may contain ethylene oxide or propylene oxide, and the ethylene oxide or propylene oxide may contain -SO3NH4, -PO3H2 or other ionic groups at the terminals.

[0025] Commercially available products include Emulgen A-60, Emulgen A-90, and Emulgen B-66 manufactured by Kao, TS1500, TS2000, and TS2600 manufactured by Toho Chemical, and Emulsogen TS160 and Dispersing agent manufactured by Clariant. LFH, LFES, Nippon Nyukazai's Newcoal 704, 706, 707, 708, 709, 710, 711, 712, 714, 714(80), 719, 610, 610(80), 2604, 2607, 2609, 2614, 707-F, 710-F, 714-F, 2608-F, 2600-FB, 2616-F, 3612-FA, 707-SF, 707-SFC, 707-SN, 714-SF, 714-SN, 723-SF, 740-SF, 780-SF, 2 607-SF, 2614-SF, New Calgen C-150, C-173, C-200, C-314, CP-50, CP-80, CP-120, CP-15-200, Paionin D-6112, D-6512, D-6414, DTD-51 manufactured by Takemoto Oils and Fat, Trimin CB#32 manufactured by Miyoshi Oils and Fat, Hitenol NF-13, Plysurf AL, Noigen EA-87, EA-137, EA-157, EA-167, EA-177 manufactured by Daiichi Kogyo Seiyaku can be used. Most preferably, Emulgen B66 is used.

[0026] [Polymer Dispersant] In addition to the above surfactants, a polymer dispersant may be used in combination. A preferred polymer dispersant is an acrylic copolymer obtained by control polymerization. As commercially available products, disperbyk-190, 2010, 2012, 2013, 2015, 2055, 2060, 2061, and 2096 manufactured by BYK can be used. Disperbyk-190 and 2015 are preferred, and disperbyk-2015 is most preferred, since they have high compatibility with the surfactant used in combination and improve dispersibility compared to the case of the surfactant alone.

[0027] [Dispersion medium] In the present invention, at least the above components are dispersed in water. If a dispersion medium other than water is contained, the ultraviolet absorber may dissolve, causing a problem that the wavelength shifts to a shorter wavelength, so it is preferable to contain as little dispersion medium other than water as possible. It is desirable to suppress the amount of dispersion medium other than water to 1% by weight or less in the dispersion liquid, and preferably the dispersion medium is 100% water.

[0028] [Content of each ingredient] The content of the ultraviolet absorber in the dispersion is preferably 5 to 20% by mass. If it is less than 5%, the shear is not applied and the dispersion does not progress easily, and if it exceeds 20% by mass, the viscosity increases and the dispersion does not progress easily. It is preferably 8 to 12% by mass, and most preferably 10% by mass. The content of the surfactant is preferably 1 to 100 parts by mass relative to 100 parts by mass of the ultraviolet absorber. If the content of this surfactant is less than 1 part by mass, it becomes difficult to crush the particles to 50 nm or less, and there are problems such as a long dispersion time. If the content of the surfactant exceeds 100 parts by mass, the viscosity becomes high and dispersion becomes difficult to proceed. It is preferably 50 to 90 parts by mass, and most preferably 70 parts by mass.

[0029] When a polymer dispersant is used in combination with a surfactant, it is preferable to use 1 to 100 parts by mass of the surfactant per 100 parts by mass of the ultraviolet absorber, within the above-mentioned surfactant content range. If the amount is less than 1 part by mass, the effect of the combination is small, and if the amount exceeds 100 parts by mass, the viscosity increases and dispersion does not proceed easily. It is preferably 5 to 20 parts by mass, and most preferably 10 parts by mass.

[0030] [Production of UV absorber dispersion] The ultraviolet absorbent dispersion of the present invention can be produced using, for example, a media-type disperser or a collision-type disperser. A media-type disperser is a disperser that disperses by moving small-diameter media such as glass, alumina, zirconia, steel, tungsten, etc., at high speed in a vessel and grinding the slurry passing between them with the shear force between the media. Specific examples of the media-type disperser include a ball mill, a sand mill, a pearl mill, a spike mill, an agitator mill, a cobo mill, and an ultravisco mill.

[0031] The collision type disperser is a disperser that disperses by crushing pigments in a fluid by colliding a fluid against one wall at high speed or by colliding fluids with each other at high speed. Examples of the collision type disperser include a jet mill that accelerates and crushes raw material particles using a high-speed jet stream, and a wet type micronization device, "Starburst" (registered trademark, manufactured by Sugino Machine Co., Ltd.). Other known dispersing devices, such as a roll mill and an ultrasonic dispersing device, may be used for production. Among the above-mentioned various dispersing devices, any device and media that can provide sufficient shear force to obtain the desired particle size may be used, and generally, various media-type dispersing devices are suitable. These devices and media are appropriately selected, and the above-mentioned components are added, and the ultraviolet absorbing compound is processed until it becomes fine particles having the above-mentioned desired particle size.

[0032] [Physical Properties of UV Absorber Dispersion] 1.Transparency The ultraviolet absorbent dispersion of the present invention can be a composition having excellent transparency while maintaining sufficient ultraviolet absorbing performance. This can be confirmed by the following two indexes. First, the ultraviolet absorber dispersion is diluted with water so that the ultraviolet absorber concentration becomes 0.0982%, and the transmission spectrum is measured at room temperature using a UV-visible spectrophotometer (Shimadzu Corporation, UV-1850) to confirm the transmittance at 600 nm.

[0033] In this case, the composition of the present invention can achieve a transmittance of 75% or more at 600 nm. Furthermore, it can be 85% or more, and even 93% or more. In this case, a dispersion with a content lower than 75% will become cloudy and have low transparency, but as shown in the comparative example described below, it is difficult to achieve a content of 75% or more using conventional technology.

[0034] Next, the ultraviolet absorber dispersion of the present invention is diluted with water so that the ultraviolet absorber concentration becomes 0.002%, and the absorption spectrum is measured at room temperature using a ultraviolet-visible spectrophotometer (Shimadzu Corporation, UV-1850). In this case, the absorbance at 380 nm (A380) can be set to 0.50 to 0.70. In addition, A380 / A600, which is the ratio of the absorbance at 380 nm (A380) to the absorbance at 600 nm (A600) in the absorption spectrum, can be 200 or more, or even 250 or more, or 600 or more, or even 650. A high A380 / A600 value means that the material can transmit enough of the visible light range while absorbing enough of the ultraviolet range. If the A380 / A600 value is lower than 200, it becomes difficult to maintain high transparency while sufficiently blocking the ultraviolet range. The relationship between wavelength and transmittance of the ultraviolet absorbent dispersion of the present invention is shown in Figure 1, and the relationship between wavelength and absorbance is shown in Figure 2. As can be seen from these figures, the ultraviolet absorbent dispersion of the present invention has high transmittance in defective areas, is excellent in transparency, and maintains high transparency while sufficiently blocking the ultraviolet region.

[0035] 2.Dispersed particle size In the dispersion of the present invention, it is preferable to adjust the particle size of the ultraviolet absorbing compound to fall within a certain range. Specifically, when the ultraviolet absorber concentration of the ultraviolet absorber dispersion of the present invention is diluted with water so that the loading index is in the range of 0.1 to 100, and the particle diameter is measured at room temperature using a particle size distribution measuring device (Microtrac UPA EX-150, manufactured by Nikkiso Co., Ltd.), the particle diameter is 10 to 35 nm, preferably 10 to 30 nm, and most preferably 13 to 20 nm. Within this range, the balance between the ultraviolet absorbing performance and transparency described above is the best. If the particle size is larger than 35 nm, the transparency tends to decrease. On the other hand, if the particle size is smaller than 10 nm, the liquid stability over time decreases and the UV absorption performance tends to decrease.

[0036] 3.Viscosity The viscosity of the ultraviolet absorber dispersion of the present invention, measured at 25°C using a viscometer (manufactured by Toki Sangyo Co., Ltd., model number "VISCOMETER TV-22"), is preferably 2.0 to 4.5 mPa·s, particularly preferably 2.0 to 3.0 mPa·s. This range is particularly preferred because it is easy to mix with other materials such as resin components and is easy to handle. By mixing the above-mentioned components in the above-mentioned ratios, the viscosity can be easily adjusted to a preferred range.

[0037] 4. pH The pH of the ultraviolet absorber dispersion of the present invention can be appropriately selected depending on the purpose and the relationship with the pH of other components such as the resin to be blended. The pH can be appropriately adjusted by selecting the functional group of the surfactant.

[0038] The aqueous ultraviolet absorbent composition described above can be further mixed with a resin component to form a coating liquid, thereby forming a coating composition. Here, the coating composition of the present invention is a composition capable of forming a coating film on a substrate. For example, it can be used for various applications such as those described in WO2015 / 152057.

[0039] According to the coating composition of the present invention, the performance of the ultraviolet absorber contained in the coating formed is high, and therefore, damage caused by sunlight or ultraviolet light can be reduced in the formed coating itself, in a substrate coated with the coating, and in a material that is exposed to sunlight or ultraviolet light through the coated substrate (coated article).

[0040] The substrate to be coated with the coating composition of the present invention is not limited, and examples thereof include glass, resin glass, metal, plastic, fiber, cloth, paper, wood, concrete, etc. These substrates may be, for example, window glass components, interior and exterior materials, building materials such as architectural structures, containers for food, medicines, cosmetics, chemicals, etc., signs, labels, solar cell components, etc. In addition, by using the coating composition of the present invention as a substrate for a printed matter, it is possible to prevent the ink from fading. The coating composition of the present invention may be an ink, and in this case, for example, the ink fading can be prevented. The coating composition of the present invention may be an adhesive, and in this case, for example, the adhesive can be prevented from deteriorating due to sunlight or ultraviolet rays. Furthermore, it is also possible to produce, for example, clothing, hats, umbrellas, etc. having an ultraviolet ray shielding effect by coating a substrate such as a fiber with the coating composition of the present invention.

[0041] The present invention will now be described more specifically with reference to examples. Example 1 R and R in general formula (I) 1' are chlorine atoms, and R and R 2' 10.0 parts by weight of compound 1 (2,2'-methylenebis[6-(5-chloro-2H-benzotriazol-2-yl)-4-tert-octylphenol]), in which all of the above are 1,1,3,3-tetramethylbutyl groups, 7.0 parts by weight of polyoxyethylene tribenzyl phenyl ether ("Emulgen B-66" manufactured by Kao Corporation, HLB 13.2) as a surfactant, and 83.0 parts by weight of water were mixed and ground in a paint conditioner using zirconia beads of φ0.1 mm for 10 hours to obtain ultraviolet absorber dispersion 1. The average particle size of the ultraviolet absorber particles in the obtained dispersion was measured at room temperature using a particle size distribution measuring device (Microtrac, manufactured by Nikkiso Co., Ltd.) and was found to be 28 nm (median diameter, D 50 ). The obtained ultraviolet absorber dispersion 1 was diluted with water so that the ultraviolet absorber concentration became 0.0982%, and the transmission spectrum was measured at room temperature using a ultraviolet-visible spectrophotometer (Shimadzu Corporation, UV-1850). As a result, the transmittance at 600 nm was 86.9%.

[0042] Example 2 The ultraviolet absorber was dispersed in the same manner as in Example 1, except that the surfactant was changed to 7.0 parts by weight of polyoxyethylene tribenzyl phenyl ether ("Emulgen B-6" manufactured by Kao Corporation, HLB 13.2), the dispersant was changed to 2.5 parts by weight of a polymer dispersant having an acid value (disperbyk-2015 manufactured by BYK-Chemie, acid value 10 mg KOH / g, active ingredient 40.0 wt%), and the water was changed to 80.5 parts by weight. The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 15 nm and 93.2%, respectively.

[0043] Example 3 The ultraviolet absorber was dispersed in the same manner as in Example 1, except that the surfactant was changed to 1.0 part by weight of polyoxyethylene tribenzyl phenyl ether ("Emulgen B-66" manufactured by Kao Corporation, HLB 13.2), the dispersant was changed to 17.5 parts by weight of a polymer dispersant having an acid value ("disperbyk-2015" manufactured by BYK-Chemie, acid value 10 mg KOH / g, active ingredient 40.0% by mass), and the water was changed to 71.5 parts by weight. The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 31 nm and 80.4%, respectively.

[0044] Example 4 As an ultraviolet absorber, R and R in the general formula (I) 1' are hydrogen atoms, and R and R 2'The ultraviolet absorber was dispersed in the same manner as in Example 1, except that all of the above were changed to compound 2 (2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (BASF "TINUVIN360")), in which all of the above were 1,1,3,3-tetramethylbutyl groups. The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 32 nm and 78.0%, respectively.

[0045] Example 5 As an ultraviolet absorber, R and R in the general formula (I) 1' are hydrogen atoms, and R and R 2' The ultraviolet absorber was dispersed in the same manner as in Example 2, except that all of the above were changed to compound 2 (2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (BASF "TINUVIN360")), in which all of the above were 1,1,3,3-tetramethylbutyl groups. The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 24 nm and 87.9%, respectively.

[0046] Example 6 As an ultraviolet absorber, R and R in the general formula (I) 1' are hydrogen atoms, and R and R 2' The ultraviolet absorbent was dispersed in the same manner as in Example 3, except that all of the above were changed to compound 2 (2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (BASF "TINUVIN360")), in which all of the above were 1,1,3,3-tetramethylbutyl groups. The average particle size and transmittance of the ultraviolet absorbent in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 30 nm in average particle size and 81.9% in transmittance.

[0047] Comparative Example 1 The ultraviolet absorbent was dispersed in the same manner as in Example 1, except that the dispersant used was changed to 17.5 parts by weight of a high molecular weight dispersant having an acid value (disperbyk-2015 manufactured by BYK-Chemie, acid value 10 mg KOH / g, active ingredient 40.0% by weight) and 72.5 parts by weight of water. The average particle size and transmittance of the ultraviolet absorbent in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 43 nm in average particle size and 68.5% in transmittance.

[0048] Comparative Example 2 As an ultraviolet absorber, R and R in the general formula (I) 1' are hydrogen atoms, and R and R 2' The ultraviolet absorber was dispersed in the same manner as in Comparative Example 1, except that all of the above were changed to compound 2 (2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (BASF "TINUVIN360")), in which all of the above were 1,1,3,3-tetramethylbutyl groups. The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 37 nm and 68.2%, respectively.

[0049] Comparative Example 3 The ultraviolet absorber was dispersed in the same manner as in Example 1, except that the ultraviolet absorber was changed to compound 3 represented by the following chemical formula (II) (2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol (BASF "TINUVIN326")).

[0050] [ka]

[0051] The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 130 nm and 1.3%, respectively.

[0052] Comparative Example 4 The ultraviolet absorber was dispersed in the same manner as in Example 2, except that the ultraviolet absorber was changed to compound 3 (2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol (BASF "TINUVIN326")) as in Comparative Example 3. The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 119 nm and 1.9%, respectively.

[0053] Comparative Example 5 The ultraviolet absorber was dispersed in the same manner as in Example 3, except that the ultraviolet absorber was changed to compound 3 (2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol (BASF "TINUVIN326")) as in Comparative Example 3. The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 155 nm and 2.1%, respectively.

[0054] Comparative Example 6 An ultraviolet absorbent was dispersed in the same manner as in Comparative Example 1, except that the ultraviolet absorbent was changed to compound 3 (2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol (BASF "TINUVIN326")) as in Comparative Example 3. The average particle size and transmittance of the ultraviolet absorbent in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 158 nm in average particle size and 4.1% in transmittance.

[0055] Comparative Example 7 The ultraviolet absorbent was dispersed in the same manner as in Example 1, except that the ultraviolet absorbent was changed to compound 4 represented by the following chemical formula (III) (2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one (manufactured by Chemipro Chemical Co., Ltd., "KEMISORB500")).

[0056] [ka]

[0057] The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 90 nm and 1.0%.

[0058] Comparative Example 8 The ultraviolet absorber was dispersed in the same manner as in Example 2, except that the ultraviolet absorber was changed to compound 4 (2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one (manufactured by Chemipro Chemical Co., Ltd., "KEMISORB500")) as in Comparative Example 7. The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 81 nm and 1.7%, respectively.

[0059] Comparative Example 9 The ultraviolet absorber was dispersed in the same manner as in Example 3, except that the ultraviolet absorber was changed to compound 4 (2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazine-4-one (manufactured by Chemipro Chemical Co., Ltd., "KEMISORB500")) as in Comparative Example 7. The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 79 nm and 9.1%, respectively.

[0060] Comparative Example 10 The ultraviolet absorber was dispersed in the same manner as in Comparative Example 1, except that the ultraviolet absorber was changed to compound 4 (2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one (manufactured by Chemipro Chemical Co., Ltd., "KEMISORB500")) as in Comparative Example 7. The average particle size and transmittance of the ultraviolet absorber in the obtained dispersion were measured in the same manner as in Example 1, and were found to be 58 nm and 25.4%, respectively.

[0061] Table 1 shows the UV absorber, activator and dispersant contained in each dispersion obtained in each of the above Examples and Comparative Examples, as well as the transmittance, absorbance, absorbance ratio, D10, D50, D90 and viscosity.

[0062] [Table 1]

[0063] Compound 1: 2,2'-methylenebis[6-(5-chloro-2H-benzotriazol-2-yl)-4-tert-octylphenol] Compound 2: 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] Compound 3: 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol Compound 4: 2,2'-(1,4-phenene)-bis[4H-3,1-benzoxazin-4-one]

[0064] Comparing the transmittance between the Examples and Comparative Examples, it can be seen that the dispersion using the compound of formula (I) as an ultraviolet absorber according to the present invention and containing a surfactant has a higher transmittance than the other dispersions and has excellent transparency. Comparing the absorbance ratios of the Examples and Comparative Examples, it can be seen that the absorbance ratio of the dispersion using the compound of formula (I) as an ultraviolet absorber according to the present invention and containing a surfactant is larger than the absorbance ratios of the other dispersions, and thus maintains high transparency while sufficiently blocking the ultraviolet region. [Industrial Applicability]

[0065] According to the present invention, it is possible to obtain an aqueous ultraviolet absorbent composition which is excellent in transparency and can sufficiently block ultraviolet rays, and a coating composition using the same.

Claims

1. The aqueous composition of an ultraviolet absorber is characterized in that at least an ultraviolet absorber and a dispersant are present in an aqueous medium, the ultraviolet absorber is a compound represented by the following general formula (I), and the aqueous composition of an ultraviolet absorber contains a surfactant, and the aqueous composition of an ultraviolet absorber is characterized in that the ultraviolet absorber is dispersed with an average dispersed particle diameter of 10 to 35 nm. General formula (I) 【Chemistry 1】 During the ceremony, R 1 and R 1' may be the same or different, and each represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, R 3 SO- group or R 3 O 2 - group. R 2 and R 2' may be the same or different, and each represents an alkyl group having 1 to 12 carbon atoms; 2 It is an alkyl group having 1 to 12 carbon atoms substituted by an H group, a phenyl group, a phenylalkyl group containing 1 to 4 carbon atoms in the alkyl portion, or a cycloalkyl group having 5 to 8 carbon atoms. R 3 is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group substituted by an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, or the above aryl groups substituted by one or two alkyl groups having 1 to 4 carbon atoms, or a 1,1,2,2-tetrahydroperfluoroalkyl group (the perfluoroalkyl portion of this group consists of 6 to 16 carbon atoms).

2. 2. The aqueous ultraviolet absorbent composition according to claim 1, wherein the dispersant is one or more compounds selected from acrylic copolymers of control polymerization.

3. In the compound of formula (I), R １ is chlorine or hydrogen, R ２ 2. The aqueous ultraviolet absorbent composition according to claim 1, wherein is tert-octyl.

4. 2. A method for producing a coating composition, comprising mixing the aqueous ultraviolet absorbent composition according to claim 1 with a resin component to form a coating liquid.

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