WO2024024866A1

WO2024024866A1 - Ultraviolet ray absorber water-based coating composition

Info

Publication number: WO2024024866A1
Application number: PCT/JP2023/027470
Authority: WO
Inventors: 康弘井手
Original assignee: 御国色素株式会社
Priority date: 2022-07-27
Filing date: 2023-07-26
Publication date: 2024-02-01

Abstract

[Problem] The present invention provides: a water-based coating composition containing an ultraviolet ray absorber, which has excellent transparency and satisfactorily blocks ultraviolet ray; and a method for producing the water-based coating composition. [Solution] Provided is a water-based coating composition containing an ultraviolet ray absorber, the water-based coating composition being characterized by comprising at least an ultraviolet ray absorber, a dispersing agent and a resin component all present in a water-based solvent, in which the ultraviolet ray absorber is a compound represented by general formula (I). In general formula (I), R1 and R1' may be the same as or different from each other and each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, a R3SO- group, or a R3O2- group; R2 and R2' may be the same as or different from each other and each independently represent an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms which is substituted by a CO2H group, a phenyl group, a phenylalkyl group in which 1 to 4 carbon atoms are contained in an alkyl group moiety, or a cycloalkyl group having 5 to 8 carbon atoms; R3 represents an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group which is 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 aryl group which is substituted by one or two alkyl groups each having 1 to 4 carbon atoms, or a 1,1,2,2-tetrahydroperfluoroalkyl group (in which a perfluoroalkyl moiety in this group is composed of 6 to 16 carbon atoms).

Description

UV absorber water-based paint composition

The present invention relates to an ultraviolet absorber aqueous coating composition and a method for producing the same.

Benzotriazole-based ultraviolet absorbers are known for their excellent properties such as ultraviolet absorption performance and photostability, and have been widely used. In particular, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (also known as bisoctrisol) is known as a UV absorber that can absorb up to long wavelengths. , is an organic compound and is generally used in a molecular state by dissolving it in a volatile organic solvent or the like.
However, since there are concerns about the effects of volatile organic solvents on the environment and the human body, it is desirable to use an aqueous solvent, but bisoctrisol is insoluble in water. Therefore, methods of dispersing the compound in water have been reported (Patent Documents 1, 2, 3, 4, and 5).
Dispersing in water not only makes it possible to use 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 state and is not dissolved. Since the absorption of UV absorbers in the solid state increases to longer wavelengths than in the dissolved state, the amount of UV absorber used can be reduced, so it is expected that the range of applicable products will expand to water-based paints, sol-gel coating liquids, in-line coating liquids, etc. can. Furthermore, by creating an aqueous dispersion, it can be processed into paint or film forms, etc. In particular, by creating a transparent dispersion, it can be used for textile materials, inks, cosmetics, food packaging, etc. that require light resistance and are transparent. It can be expected to be widely applied to products where performance is important.

Japanese Patent Application Publication No. 2017-95559 Patent No. 5270134 WO2015/152057 Patent No. 5396265 Patent No. 5700552

However, studies by the present inventors have revealed that it is difficult to improve visible light transmittance while sufficiently blocking ultraviolet rays with the dispersions disclosed in these conventionally known documents. Specifically, in Patent Documents 1 to 3 of the above-mentioned documents, the transmittance of visible light (600 nm) exceeds 25% when the transmittance of the ultraviolet region (200 nm to 380 nm) is 0.0%. This method was difficult to apply to applications that require higher transparency than the above report, such as glass coatings, because the method could not obtain a value based on the ultraviolet absorber concentration of 0.00982%.

Further, in Patent Documents 4 and 5, high transmittance is maintained through 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 need for a dispersion composition and a coating composition that maintain high transmittance and have a short manufacturing process and high production efficiency.

The present inventor has made repeated studies to solve the above problems. As a result, it was found that the transmittance could be improved in a shorter time than before by using and dispersing a specific ultraviolet absorber. That is, it is a dispersion liquid in which a specific bisoctrizole analog compound is dispersed in water. It has also been found that aqueous dispersion compositions of bisoctrisol analogs can be easily mixed with various resins and emulsions and can be provided as aqueous coating compositions for applications requiring high transparency.

That is, the present invention
(1) An aqueous coating composition in which at least an ultraviolet absorber, a dispersant, and a resin component are present in an aqueous medium, and the ultraviolet absorber is a compound represented by the following general formula (I). A water-based paint composition containing an ultraviolet absorber, characterized by
General formula (I)

During the ceremony,
R ₁ and R _1' may be the same or different from each other and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R ₃ SO- group, or R ₃ It is an O ₂ - group.
R ₂ and R _2' may be the same or different from each other, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a CO ₂ H group, a phenyl group, an alkyl group moiety is a phenylalkyl group containing 1 to 4 carbon atoms, or a cycloalkyl group containing 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 with an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms; , substituted by one or two cycloalkyl groups having 5 to 12 carbon atoms, phenylalkyl groups having 7 to 15 carbon atoms, aryl groups having 6 to 10 carbon atoms or 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 ultraviolet absorber-containing aqueous coating composition according to (1) above, wherein the ultraviolet absorber is dispersed with an average dispersed particle size of 10 to 35 nm;

(3) The ultraviolet absorber-containing aqueous coating composition according to (1) 1 or (2) above, wherein the dispersant is one or more compounds selected from controlled polymerization acrylic copolymers;
(4) The ultraviolet absorber-containing aqueous coating composition according to (1) or (2) above, which further contains a surfactant;
(5) The ultraviolet light according to (1) or (2) above, wherein the dispersant is one or more compounds selected from acrylic copolymers for controlled polymerization, and further contains a surfactant. Absorbent-containing water-based paint composition,
(6) In the compound of general formula (I),
The ultraviolet absorber-containing aqueous coating composition according to (1) or (2) above, wherein R ₁ and R _1' are chlorine, and R ₂ and R _2' are tert-octyl.
(7) In the compound of general formula (I),
R ₁ and R _1' are chlorine, R ₂ and R _2' are tert-octyl, the dispersant is one or more compounds selected from acrylic copolymers of controlled polymerization, and further a surfactant. The ultraviolet absorber-containing aqueous coating composition according to (1) or (2) above, characterized in that it contains
(8) An aqueous composition in which at least an ultraviolet absorber and a dispersant are present in an aqueous medium, the ultraviolet absorber being a compound represented by the following general formula (I), A method for producing an aqueous paint composition containing an ultraviolet absorber, the method comprising the step of blending a resin component;

General formula (I)

During the ceremony,
R ₁ and R _1' may be the same or different from each other and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R ₃ SO- group, or R ₃ It is an O ₂ - group.
R ₂ and R _2' may be the same or different from each other, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a CO ₂ H group, a phenyl group, an alkyl group moiety is a phenylalkyl group containing 1 to 4 carbon atoms, or a cycloalkyl group containing 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 with an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms; , substituted by one or two cycloalkyl groups having 5 to 12 carbon atoms, phenylalkyl groups having 7 to 15 carbon atoms, aryl groups having 6 to 10 carbon atoms or 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).
(9) The above (8) characterized in that the ultraviolet absorber in the aqueous composition in which at least the ultraviolet absorber and the dispersant are present in the aqueous medium is dispersed with an average dispersed particle size of 10 to 35 nm. The method for producing the ultraviolet absorber-containing aqueous coating composition described above,
(10) The method for producing an aqueous coating composition containing an ultraviolet absorber as described in (8) above, wherein the dispersant is one or more compounds selected from acrylic copolymers of controlled polymerization.
(11) The aqueous coating composition containing an ultraviolet absorber as described in (8) above, wherein the aqueous composition in which at least an ultraviolet absorber and a dispersant are present in the aqueous medium further contains a surfactant. manufacturing method,
(12) In the compound of general formula (I),
The method for producing an aqueous coating composition containing an ultraviolet absorber as described in (8) above, wherein R ₁ and R _1' are chlorine, and R ₂ and R _2' are tert-octyl;
It is in.

According to the present invention, it is possible to obtain an aqueous coating composition containing an ultraviolet absorber that can sufficiently block ultraviolet rays while improving visible light transmittance, and a method for producing the same.

FIG. 1 is a graph showing the transmittance versus wavelength of a glass plate coated with a resin coating using the ultraviolet absorber aqueous coating composition of the present invention obtained in Example 1. FIG. 2 is a graph showing the transmittance versus wavelength of a glass plate coated with a resin coating using the ultraviolet absorber aqueous coating composition of the present invention obtained in Example 2. FIG. 3 is a diagram showing a graph of transmittance versus wavelength of a glass plate coated with a resin coating using the ultraviolet absorber aqueous coating composition of the present invention obtained in Example 3. FIG. 4 is a diagram showing a graph of transmittance versus wavelength of a resin-coated glass plate using the ultraviolet absorber aqueous coating composition of the present invention obtained in Example 4. FIG. 5 is a diagram showing a graph of transmittance versus wavelength of a resin-coated glass plate using the ultraviolet absorber aqueous coating composition obtained in Comparative Example 1. FIG. 6 is a diagram showing a graph of transmittance versus wavelength of a resin-coated glass plate using the ultraviolet absorber aqueous coating composition obtained in Comparative Example 2. FIG. 7 is a diagram showing a graph of transmittance versus wavelength of a resin-coated glass plate using the ultraviolet absorber aqueous coating composition obtained in Comparative Example 3. FIG. 8 shows the wavelengths of the ultraviolet absorbent dispersions of the present invention obtained in Example 1, Example 2, Example 3, and Example 4 and the ultraviolet absorbent dispersions obtained in Comparative Example 1 and Comparative Example 2. It is a figure which shows the graph of the light absorbency with respect to FIG. 9 shows the wavelengths of the ultraviolet absorbent dispersions of the present invention obtained in Example 1, Example 2, Example 3, and Example 4 and the ultraviolet absorbent dispersions obtained in Comparative Example 1 and Comparative Example 2. It is a figure which shows the graph of the transmittance|permeability with respect to

The present invention will be explained in detail below.
[Ultraviolet absorber]
1. Structure of Ultraviolet Absorber In the present invention, an ultraviolet absorber represented by the following general formula (1) is used.

General formula (1)

During the ceremony,
R ₁ and R _1' may be the same or different from each other and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R ₃ SO- group, or R ₃ It is an O ₂ - group. Particularly preferred are a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R ₃ SO- group or an R ₃ O _2- group.

R ₂ and R _2' may be the same or different from each other, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a CO ₂ H group, a phenyl group, an alkyl group moiety is a phenylalkyl group containing 1 to 4 carbon atoms, or a cycloalkyl group containing 5 to 8 carbon atoms. Preferred is an alkyl group having 1 to 12 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 with an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms; , substituted by one or two cycloalkyl groups having 5 to 12 carbon atoms, phenylalkyl groups having 7 to 15 carbon atoms, aryl groups having 6 to 10 carbon atoms or 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 ₁ and R _1' are preferably an alkyl group having 1 to 4 carbon atoms or a halogen group.
More preferably, it is a halogen group.
Most preferred is a chlorine atom.

R ₂ and R _2' are preferably alkyl groups having 1 to 12 carbon atoms.
Most preferably, both R ₂ and R _2' are the following groups:

CH ₃ CH ₃
｜｜
-C-CH ₂ -C-CH ₃
｜｜
CH ₃ CH ₃
(1,1,3,3-tetramethylbutyl group)

These compounds themselves are known, and in addition to being able to use commercially available products, they can also be produced and used by various conventionally known production methods for benzotriazole compounds. Generally, after producing a benzotriazole compound of phenol as a raw material, the benzotriazole is further dimerized with an aldehyde. For example, it can be produced by the methods described in Japanese Patent No. 3223377, German Patent No. 1,670,951, etc.

2. Glass Transition Point of Ultraviolet Absorber The ultraviolet absorber 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 it is too low, the glass transition point will be exceeded due to dispersion heat during dispersion, making it impossible to maintain crystallinity and making it difficult to proceed with dispersion. For this reason, the particle size becomes large and the transparency decreases.

3. Melting Point of Ultraviolet Absorber The ultraviolet absorber 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, causing the above-mentioned problems.

The melting point and glass transition point are values measured by DSC. More specifically, the method described in JIS standard K-7121-1987 "Method for measuring transition temperature of plastics" is used.

4. Molecular Weight of Ultraviolet Absorber The ultraviolet absorber used in the present invention preferably has a molecular weight of 400 to 2,500, more preferably 650 to 750, and most preferably 727.76. When the molecular weight is lower than 400, the melting point and glass transition point tend to be low, and when it is higher than 2500, it tends to become difficult to crystallize, causing a problem that it becomes impossible to disperse.

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

Particularly preferred surfactants are polyoxyalkylene derivatives having an HLB of 9 to 16, preferably 11 to 15, most preferably 13.2, having 1 to 3 benzyl groups, and having a phenyl ether ring. The hydrophilic group may be bonded to any part, and the hydrophilic group may contain _ethylene _oxide or _propylene _oxide . It may contain a sexual group.

Commercially available products include Kao's Emulgen A-60, Emulgen A-90, and Emulgen B-66, Toho Chemical's TS1500, TS2000, and TS2600, Clariant's Emulsogen TS160, Dispersing agent LFH, LFES, Nippon Nyukazai's New Call 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 , 2607-SF, 2614-SF, New Calgen C-150, C-173, C-200, C-314, CP-50, CP-80, CP-120, CP-15-200, Pionin manufactured by Takemoto Yushi. D-6112, D-6512, D-6414, DTD-51, Trimin CB #32 manufactured by Miyoshi Oil Co., Ltd., Hitenol NF-13 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Price Surf AL, Neugen EA-87, EA-137, EA-157, EA-167, and EA-177 can be used. Most preferred is Emulgen B66.

[Polymer dispersant]
Furthermore, in addition to the above-mentioned surfactants, a polymer dispersant may be used in combination. Preferred polymer dispersants include controlled polymerization acrylic copolymers.
As commercially available products, disperbyk-190, 2010, 2012, 2013, 2015, 2055, 2060, 2061, 2096 manufactured by BYK Chemie, ZETASPERSE 3800 manufactured by EVONIC, TEGO Dispers 750W, etc. can be used. Preferably, Disperbyk-190, 2015, most preferably Disperbyk-2015, is preferred because it has high compatibility with the surfactant used in combination and improves dispersibility compared to the case of a surfactant alone.

[Dispersion medium]
In the present invention, at least each of the above components is dispersed in water. If a dispersion medium other than water is contained, the ultraviolet absorber may not be dissolved and the wavelength may shift to a shorter wavelength. Therefore, it is preferable to contain no dispersion medium other than water as much as possible. It is desirable to suppress the content to 1% by weight or less in the dispersion, and preferably the dispersion medium is 100% water.

[Content of each component]
The content of the ultraviolet absorber in the dispersion is preferably 5 to 20% by mass. If it is less than 5%, it will be difficult to apply shear and dispersion will be difficult to proceed, and if it exceeds 20% by mass, the viscosity will be high and it will be difficult to proceed to dispersion. Preferably it is 8-12% by weight, most preferably 10% by weight.
The content of the surfactant is preferably 1 to 100 parts by weight per 100 parts by weight of the ultraviolet absorber. If the content of this activator is less than 1 part by mass, it will be difficult to proceed with fragmentation of 50 nm or less, and there will be problems such as a long dispersion time; if it exceeds 100 parts by mass, the viscosity will increase and dispersion will be difficult. It becomes difficult to proceed. Preferably it is 50 to 90 parts by weight, most preferably 70 parts by weight.

When a polymer dispersant is used in combination with a surfactant, it is preferably used in an amount of 1 to 100 parts by weight per 100 parts by weight of the ultraviolet absorber within the above surfactant content range. If the amount is less than 1 part by mass, the effect of the combined use will be small, and if it exceeds 100 parts by mass, the viscosity will increase and dispersion will be difficult to proceed. Preferably it is 5 to 20 parts by weight, most preferably 10 parts by weight.

[Manufacture of ultraviolet absorber water-based paint composition]
The method for producing the ultraviolet absorber aqueous coating composition of the present invention is not particularly limited, but includes first producing an ultraviolet absorber dispersion containing at least an ultraviolet absorber, an aqueous medium, and a dispersant, and further adding a resin component. is highly desirable. In particular, it is extremely desirable to produce an ultraviolet absorber dispersion containing at least an ultraviolet absorber, an aqueous medium, a dispersant, and a surfactant, and further add a resin component. By dispersing the ultraviolet absorber to a desired particle size at the stage of forming the ultraviolet absorber dispersion, the resulting coating composition will have excellent performance. Although the method for producing the ultraviolet absorbent dispersion is not particularly limited, it can be produced using, for example, a device such as a media-type disperser or a collision-type disperser. A media-type dispersing machine moves small-diameter media such as glass, alumina, zirconia, steel, and tungsten as media at high speed in a vessel, and disperses the slurry passing between them by grinding it with the shear force between the media. This is a disperser that performs Specific examples of media-type dispersing machines include ball mills, sand mills, pearl mills, spike mills, agitator mills, Kobo mills, and Ultra Visco mills, and more specifically, for example, Ultra Apex mills manufactured by Hiroshima Metal & Machinery Co., Ltd., and wide separators. Mill, MAX Nano Getter manufactured by Ashizawa Finetech Co., Ltd., Mugen Flow MGF, Dyno Mill ECM type manufactured by Shinmaru Enterprises Co., Ltd., and the like.

A collision type dispersion machine is a dispersion machine that performs dispersion by pulverizing pigments and the like in the fluid by colliding a fluid against a single wall surface at high speed or by causing fluids to collide with each other at high speed. Examples of collision-type dispersers include jet mills that accelerate and pulverize raw material particles using high-speed jet streams, and "Starburst" (registered trademark, manufactured by Sugino Machine Co., Ltd.), which is a wet atomization device. . It may also be produced using other known dispersion equipment, such as a roll mill or an ultrasonic dispersion machine. Among the various types of dispersion equipment described above, any equipment and media that can obtain sufficient shearing force to obtain the target particle size may be used, and in general, various media type dispersion machines are suitable. be. These devices and media may be appropriately selected, the above-mentioned components may be added, and the process may be carried out until the ultraviolet absorber becomes fine particles having the above-described desired particle size.

[Physical properties of ultraviolet absorber dispersion]
1. Transparency In order to obtain a coating composition with preferable physical properties, it is desirable that the ultraviolet absorber dispersion satisfy the following indicators. By doing so, the resulting coating composition can maintain sufficient ultraviolet absorption performance. Furthermore, by using a transparent resin component, a composition with even better transparency can be obtained. That is, it can be confirmed using the following two indicators.
First, the ultraviolet absorber dispersion was diluted with water so that the ultraviolet absorber concentration was 0.0982%, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-1850). to confirm the transmittance at 600 nm.

The ultraviolet absorber dispersion containing the specific compound used in the present invention can have a transmittance of 75% or more at 600 nm as measured by the above measurement method.
Furthermore, it can also be set to 80% or more.
In addition, if the dispersion has a transmittance of 600 nm lower than 75% by the above measurement method, the turbidity will increase and the transparency will decrease, but as shown in the comparative example described later, in the conventional technology, the transmittance is 75% or higher. It is difficult to do so. Further, by setting the transmittance of the ultraviolet absorber dispersion at 600 nm as measured by the above measurement method to the above range, and using such an ultraviolet absorber dispersion, the coating composition of the present invention can maintain ultraviolet absorption performance over a long period of time. As a result, a coating film with excellent light resistance can be obtained.

In addition, the ultraviolet absorber dispersion containing the specific compound used in the present invention was diluted with water so that the ultraviolet absorber concentration was 0.002%, and the absorption spectrum was measured using an ultraviolet-visible spectrophotometer (Co., Ltd.). When measured at room temperature using UV-1850 (manufactured by Shimadzu Corporation), the absorbance at 380 nm (A380) can be 0.50 to 0.70.
In addition, A380/A600, which is the result of calculating the ratio of the absorbance at 380 nm (A380) and the absorbance at 600 nm (A600) in the absorption spectrum when the UV absorber concentration of the UV absorber dispersion is 0.002%, is 200 or more. It can be set to 250 or more, and it can also be set to 600 or more, or 650.
A high value of A380/A600 means that the visible light range can be sufficiently transmitted and ultraviolet light can be sufficiently absorbed, and when A380/A600 is lower than 200, the ultraviolet light range can be sufficiently cut and the UV range can be sufficiently absorbed. tends to be difficult to maintain.
FIG. 9 shows the relationship between wavelength and transmittance of the ultraviolet absorber dispersion containing the specific compound used in the present invention, and FIG. 8 shows the relationship between wavelength and absorbance. As can be seen from these figures, this ultraviolet absorber dispersion has high transmittance in the visible region, excellent transparency, and maintains high transparency while sufficiently shielding the ultraviolet region.
When an aqueous coating composition is prepared using such an ultraviolet absorber dispersion, the tendency of the optical properties of the ultraviolet absorber dispersion is maintained as long as it does not contain components that affect absorbance or transmittance. As shown in the examples, the ultraviolet absorber-containing aqueous coating composition of the present invention has excellent transparency and light resistance. More specifically, a UV absorber dispersion with a 600 nm transmittance of 80% or more, particularly 82.8% to 88.2%, and an A380/A600 of 200 or more as determined by the above measurement method, and a transparent styrene-acrylic as a binder. By using the acid resin emulsion, the 600 nm transmittance of the resulting coating film (when formed with bar coater #5 (approximately 1.5 μm)) is 80% or more, especially 89.9 to 90.8%, T380/T600 is 0.38 or less, and 0.37 or less, and even 0.36 or less (in other words, it can sufficiently absorb ultraviolet rays while transmitting visible light and has excellent transparency), and the transmittance change in the ultraviolet region by xenon fade meter test is 0 even after 70 hours. ～-0.7, even after 420 hours, the change is extremely small at -0.1 to -0.4, and it has high transmittance in the visible region, excellent transparency, and maintains high transparency for a long period of time while sufficiently blocking the ultraviolet region. It turns out that you can keep it.

2. Dispersed Particle Size In the dispersion, it is preferable to adjust the particle size of the ultraviolet absorber to a certain range.
Specifically, the ultraviolet absorber concentration of the ultraviolet absorber dispersion of the present invention was diluted with water so that the loading index was in the range of 0.1 to 100, and a particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Micro When the particle size is measured using a truck UPA EX-150) at room temperature, the particle size is 10 to 35 nm, preferably 10 to 30 nm, most preferably 13 to 20 nm. Within this range, the balance between the above-mentioned ultraviolet absorption performance and transparency is the best.
When it is larger than 35 nm, transparency tends to decrease when trying to obtain a transparent coating composition. On the other hand, if the particle size is smaller than 10 nm, the stability of the liquid over time tends to decrease and the ultraviolet absorption performance tends to decrease.

3. Viscosity The viscosity of the ultraviolet absorber dispersion is 2.0 to 4.5 mPa・s when measured at 25°C using a viscometer (manufactured by Toki Sangyo Co., Ltd., product number "VISCOMETER TV-22"). , particularly preferably 2.0 to 3.0 mPa·s.
This range is particularly preferable because it is easy to mix with other materials such as resin components and easy to handle.
By blending the aforementioned components in the aforementioned proportions, the viscosity can be easily adjusted to a preferred range.

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

The ultraviolet absorber dispersion described above can be further mixed with a resin component to form a paint, and in particular can be made into an aqueous paint composition using an aqueous dispersion medium.
Here, the aqueous coating composition of the present invention may be any aqueous composition as long as it can form a film on a substrate. There are two types of water-based paint compositions: one-component type, in which the curing agent and cross-linking agent coexist in the same system, and two-component type, in which the main agent and curing agent are stored separately and mixed at the time of use. However, any of them can be used in the present invention. For example, it can also be used for various purposes as described in WO2015/152057. Coated products using the ultraviolet absorber aqueous coating composition of the present invention have particularly excellent weather resistance, maintain performance for a long period of time, and exhibit almost no increase in transmittance in the ultraviolet region and no decrease in transmittance in the visible region. can not see.

[Resin component] The ultraviolet absorber-containing aqueous coating composition of the present invention contains a resin component in addition to the ultraviolet absorber, dispersant, and dispersion medium described above. The resin component is also not particularly limited, and various resins conventionally used in aqueous coating compositions can be used without limitation. Examples include various water-soluble resins, emulsion resins, disversion resins, etc., and acrylic resins, urethane resins, acrylic urethane resins, styrene acrylic resins, silicone resins, fluororesins, etc. can be used without limitation.
Commercially available products include Joncryl PDX-7630A (styrene-acrylic acid resin emulsion) manufactured by BASF, Nikazole RX-284SD (acrylic resin emulsion) manufactured by Nippon Carbide, Nikazole CL-101 (vinyl acetate emulsion) manufactured by Nippon Carbide Industries, and Nippon A&L. Smartex PA-9160 (SBR (styrene-butadiene rubber) latex emulsion), Smartex PA-2327 (styrene-butadiene copolymer latex with a continuous heterogeneous structure) manufactured by A&L Japan, Cybinol EK-61 manufactured by Saiden Chemical Co., Ltd. (emulsion type acrylic resin), Showa Denko Polysol AM-200 ((meth)acrylate copolymer emulsion), Showa Denko Polysol EVA AD-5 (ethylene/acetic acid vinyl emulsion), Shin Nakamura Chemical BR-700HN (acrylic emulsion), Mitsui Chemicals Bonlon S-1284 (acrylic (or styrene-acrylic) water-based emulsion), Mitsui Chemicals Bonlon S-415 (acrylic (or styrene-acrylic) water-based emulsion), TOYO CHEM TOCRYL W-168 (acrylic emulsion) and TOCRYL W-171 (acrylic emulsion) manufactured by TOYO CHEM can be used. Preferred is Bonron S-415 (acrylic (or styrene acrylic) aqueous emulsion), most preferred is Joncryl PDX-7630A (styrene-acrylic acid resin emulsion).
According to the ultraviolet absorber-containing aqueous coating composition of the present invention, since the ultraviolet absorber contained in the formed coating film has high performance, in the formed coating itself, on the substrate coated with the coating, Damage from sunlight or ultraviolet radiation can be reduced in materials that are exposed to sunlight or ultraviolet radiation through a coated substrate (coated article).

The ultraviolet absorber-containing aqueous coating composition of the present invention can be suitably used as a coating for various purposes in which it is desirable to have an ultraviolet absorbing function. The base material to be coated is not limited at all, and examples thereof include glass, resin glass, metal, plastic, fiber, cloth, paper, wood, concrete, and the like. These base materials constitute, for example, components for window glass, interior and exterior materials, building materials such as architectural structures, containers for containing foods, medicines, cosmetics, chemicals, etc., signboards, signs, solar cells, etc. It may be a member. Further, by using the ultraviolet absorber-containing aqueous coating composition of the present invention using printed matter as a base material, it is possible to prevent ink from fading. The ultraviolet absorber-containing aqueous coating composition of the present invention may be an ink, and in this case, it can, for example, prevent the ink from fading. The ultraviolet absorber-containing aqueous coating composition of the present invention may be an adhesive, in which case it can prevent deterioration of the adhesive due to sunlight or ultraviolet light, for example. Furthermore, by coating a base material such as fiber with the ultraviolet absorber-containing aqueous coating composition of the present invention, it is also possible to produce, for example, clothing, hats, umbrellas, etc. that have an ultraviolet shielding effect. Furthermore, it is also possible to produce a film that protects foodstuffs such as grains, vegetables, and fruits from ultraviolet rays by coating a food packaging film with the ultraviolet absorber-containing aqueous coating composition of the present invention.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
Example 1
A compound as an ultraviolet absorber in which R ₁ and R ₁ ' in general formula (I) are both chlorine atoms, and R ₂ and R ₂ ' are both 1,1,3,3-tetramethylbutyl groups. 1 (2,2'-methylenebis[6-(5-chloro-2H-benzotriazol-2-yl)-4-tert-octylphenol]) 4.0 parts by weight, a high molecular weight dispersant having an acid value as a dispersant (manufactured by BYK Chemie, disperbyk-2015, acid value 10mgKOH/g, active ingredient 40.0% by weight) 2.8 parts by weight, polyoxyethylene tribenzyl phenyl ether as a surfactant (Kao Corporation "Emulgen B-66") ", HLB13.2) 1.2 parts by weight and 32.0 parts by weight of water were mixed and ground in a paint conditioner for 7 hours using zirconia beads with a diameter of 0.1 mm to obtain UV absorber dispersion 1. Ta.
The ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 1 was diluted with water to 0.0982%, and the transmission spectrum was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-1850). As a result of measurement at room temperature, the transmittance at 600 nm was 82.1%.
As coating resin, 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200 mgKOH/g, 34.1% by weight of active ingredient), 0.66 parts by weight of ultraviolet absorber dispersion 1, water 1 .77 parts by weight was stirred to form a coating composition. The obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film. The appearance of the obtained resin-coated glass plate had good transparency, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (UV-1850, manufactured by Shimadzu Corporation). The transmittance was 30.6%, the transmittance at 450 nm was 88.7%, and the transmittance at 600 nm was 90.8%. The resulting resin-coated glass plate was irradiated with ultraviolet rays using a xenon weather meter under the conditions of a wavelength of 300 to 400 nm, an illuminance of 42 W/m ² , and a black panel temperature of 63°C. The transmission spectrum was measured every 70 hours using an ultraviolet-visible spectrophotometer (UV-1850, manufactured by Shimadzu Corporation) at room temperature, and changes in the spectrum were observed. Table 2 shows the change values.

Example 2
A compound as an ultraviolet absorber in which R ₁ and R ₁ ' in general formula (I) are both chlorine atoms, and R ₂ and R ₂ ' are both 1,1,3,3-tetramethylbutyl groups. 1 (2,2'-methylenebis[6-(5-chloro-2H-benzotriazol-2-yl)-4-tert-octylphenol]) 4.0 parts by weight, a high molecular weight dispersant having an acid value as a dispersant (manufactured by BYK Chemie, disperbyk-2015, acid value 10mgKOH/g, active ingredient 40.0% by weight) 2.8 parts by weight and 33.2 parts by weight of water in a paint conditioner using zirconia beads with a diameter of 0.1 mm. The mixture was mixed and pulverized for 20 hours to obtain an ultraviolet absorbent dispersion 2. The ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 2 was diluted to 8.8%, and 34 g of the diluted solution was placed in a centrifuge tube using a centrifuge (Suprema 25, manufactured by TOMY) at 4° C. and 16,300 rpm. Centrifugation was performed under conditions of 1 hour and 30 minutes. After centrifugation, 25 g of the supernatant was collected to obtain ultraviolet absorbent dispersion 3.
The transmittance of the obtained ultraviolet absorber dispersion 3 was measured in the same manner as in Example 1, and was found to be 82.3%.
As a coating resin, 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200mgKOH/g, 34.1% by weight of active ingredient), 0.92 parts by weight of ultraviolet absorber dispersion 3, 1 part by weight of water .51 parts by weight was stirred to form a coating composition. The obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film. The appearance of the obtained resin-coated glass plate had good transparency, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-1850). The transmittance was 31.8%, the transmittance at 450 nm was 88.8%, and the transmittance at 600 nm was 90.5%. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.

Example 3
A compound as an ultraviolet absorber in which R ₁ and R ₁ ' in general formula (I) are both hydrogen atoms, and R ₂ and R ₂ ' are both 1,1,3,3-tetramethylbutyl groups. 2 (2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (“TINUVIN360” manufactured by BASF)) 17.0 parts by weight, a high acid value having an acid value as a dispersant 10.6 parts by weight of a molecular weight dispersant (manufactured by BYK Chemie, disperbyk-2015, acid value 10 mg KOH/g, active ingredient 40.0% by weight), polyoxyethylene tribenzyl phenyl ether (manufactured by Kao Corporation, "Emulgen") as a surfactant. B-66'', HLB13.2) 4.5 parts by weight and 67.9 parts by weight of water were mixed and ground in a paint conditioner for 3 hours using zirconia beads with a diameter of 0.5 mm. The mixture was mixed and ground using zirconia beads for 14 hours to obtain an ultraviolet absorbent dispersion 4. The ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 4 was diluted to 5.6%, and 34 g of the diluted solution was placed in a centrifuge tube using a centrifuge (Suprema 25, manufactured by TOMY) at 35° C. and 16,300 rpm. Centrifugation was performed for 1 hour and 45 minutes. After centrifugation, 25 g of the supernatant was collected to obtain ultraviolet absorbent dispersion 5.
The transmittance of the obtained ultraviolet absorber dispersion 5 was measured in the same manner as in Example 1, and was found to be 88.3%.
As a coating resin, 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200 mg KOH/g, 34.1% by weight of active ingredient), 2.25 parts by weight of ultraviolet absorber dispersion 5, 0 parts by weight of water. .18 parts by weight were stirred to form a coating composition. The obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film. The appearance of the obtained resin-coated glass plate had good transparency, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (UV-1850, manufactured by Shimadzu Corporation). The transmittance was 31.9%, the transmittance at 450 nm was 89.2%, and the transmittance at 600 nm was 90.6%. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.

Example 4
A compound as an ultraviolet absorber in which R ₁ and R ₁ ' in general formula (I) are both hydrogen atoms, and R ₂ and R ₂ ' are both 1,1,3,3-tetramethylbutyl groups. 2 (2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (“TINUVIN360” manufactured by BASF)) 17.0 parts by weight, a high acid value having an acid value as a dispersant. 15.1 parts by weight of a molecular weight dispersant (manufactured by BYK Chemie, disperbyk-2015, acid value 10 mg KOH/g, active ingredient 40.0% by weight) and 67.9 parts by weight of water were added to zirconia beads of φ0.5 mm in a paint conditioner. After mixing and pulverizing for 3 hours using a zirconia beads having a diameter of 0.1 mm, the mixture was further mixed and pulverized for 20 hours to obtain an ultraviolet absorbent dispersion 6. The ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 6 was diluted to 5.6%, and 34 g of the diluted solution was placed in a centrifuge tube using a centrifuge (Suprema 25, manufactured by TOMY) at 35° C. and 16,300 rpm. Centrifugation was performed under conditions of , 2 hours. After centrifugation, 25 g of the supernatant was collected to obtain ultraviolet absorbent dispersion 7.
The transmittance of the obtained ultraviolet absorber dispersion 7 was measured in the same manner as in Example 1, and was found to be 87.8%.
As a coating resin, 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200 mgKOH/g, 34.1% by weight of active ingredient), 2.13 parts by weight of ultraviolet absorber dispersion 7, 0 parts by weight of water. .30 parts by weight were stirred to form a coating composition. The obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film. The appearance of the obtained resin-coated glass plate had good transparency, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (UV-1850, manufactured by Shimadzu Corporation). The transmittance was 34.6%, the transmittance at 450 nm was 87.2%, and the transmittance at 600 nm was 89.9. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.

Comparative example 1
4.0 parts by weight of compound 3 (2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol ("TINUVIN326" manufactured by BASF)) as a UV absorber, dispersant 2.8 parts by weight of a high molecular weight dispersant having an acid value (SOLSPERSE4600 manufactured by Lubrizol, nonionic, active ingredient 50.0% by weight) and 33.2 parts by weight of water were mixed for 23 hours using zirconia beads with a diameter of 0.1 mm. The mixture was mixed and pulverized to obtain an ultraviolet absorbent dispersion 8. The ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 8 was diluted to 8.8%, and 34 g of the diluted solution was placed in a centrifuge tube using a centrifuge (Suprema 25, manufactured by TOMY) at 4° C. and 16,300 rpm. Centrifugation was performed under conditions of , 2 hours. After centrifugation, 25 g of the supernatant was collected to obtain ultraviolet absorbent dispersion 9.
The transmittance of the obtained ultraviolet absorber dispersion 9 was measured in the same manner as in Example 1, and was found to be 71.7%.
As coating resin, 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200 mgKOH/g, 34.1% by weight of active ingredient), 2.28 parts by weight of ultraviolet absorber dispersion 9, 0 parts by weight of water. .15 parts by weight were stirred to form a coating composition. The obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film. The appearance of the obtained resin-coated glass plate was slightly cloudy, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-1850). The transmittance was 31.2%, the transmittance at 450 nm was 78.7%, and the transmittance at 600 nm was 79.1%. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.

Comparative example 2
10.0 parts by weight of compound 4 (2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one (manufactured by ChemiPro Kasei Co., Ltd., "KEMISORB500") as a UV absorber) , 1.0 parts by weight of styrene acrylic resin (manufactured by BASF, Joncryl HPD-196, acid value 200 mg KOH/g, active ingredient 36.0% by weight) as a dispersant and 89.0 parts by weight of water in a paint conditioner, After mixing and pulverizing for 4 hours using zirconia beads having a diameter of 0.5 mm, the mixture was further mixed and pulverizing for 24 hours using zirconia beads having a diameter of 0.1 mm to obtain an ultraviolet absorber dispersion 10. The ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 10 was diluted to 8.0%, and 34 g of the diluted solution was placed in a centrifuge tube using a centrifuge (Suprema 25, manufactured by TOMY) at 4° C. and 16,300 rpm. , centrifugation was performed for 10 minutes. After centrifugation, 25 g of the supernatant was collected to obtain ultraviolet absorbent dispersion 11.
The transmittance of the obtained ultraviolet absorber dispersion 11 was measured in the same manner as in Example 1, and was found to be 63.9%.
As a coating resin, 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200 mg KOH/g, 34.1% by weight of active ingredient), 1.92 parts by weight of ultraviolet absorber dispersion 11, 0 parts by weight of water. .51 parts by weight was stirred to form a coating composition. The obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film. The appearance of the resulting resin-coated glass plate was cloudy, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (UV-1850, manufactured by Shimadzu Corporation). The transmittance was 6.8%, the transmittance at 450 nm was 56.6%, and the transmittance at 600 nm was 68.4. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.

Comparative example 3
As a coating resin, 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200mgKOH/g, 34.1% by weight of active ingredient) and 1.66 parts by weight of water were stirred to form a coating composition. did. The obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film. The appearance of the obtained resin-coated glass plate had good transparency, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-1850). The transmittance at 450 nm was 90.1%, and the transmittance at 450 nm was 91.6%. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.

Table 1 shows the ultraviolet absorber, activator, and dispersant contained, as well as the transmittance and absorbance of each dispersion obtained in each of the above Examples and Comparative Examples. In addition, the appearance transparency of the glass plate with the resin coating film obtained by applying the aqueous coating composition obtained in each of the above Examples and Comparative Examples, and the change in transmittance in the visible and ultraviolet regions upon irradiation with ultraviolet rays. The values are shown in Table 2.

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-fenrene)-bis[4H- 3,1-benzoxazin-4-one]

Comparing the initial transmittance in the visible range (600 nm) of Examples and Comparative Examples, the glass plate with the resin coating film using the aqueous coating composition containing the compound of general formula (I) as an ultraviolet absorber according to the present invention, It can be seen that the transmittance is higher than that of glass plates coated with resin coatings using other ultraviolet absorbers, and the transparency is excellent.
In addition, when comparing the change values in the visible region (450 nm) and ultraviolet region (380 nm) when irradiated with ultraviolet rays in Examples and Comparative Examples, it was found that the aqueous solution containing the compound of general formula (I) as an ultraviolet absorber according to the present invention Glass plates coated with a resin coating made using a paint composition have a smaller change value than glass plates coated with a resin coating coated with other UV absorbers, and maintain high transparency even when exposed to ultraviolet light for long periods of time. It can be seen that it maintains its UV-cutting performance and has excellent light resistance.

According to the present invention, it is possible to obtain an aqueous coating composition containing an ultraviolet absorber that has excellent transparency and sufficiently blocks ultraviolet rays, and a method for producing the same.

Claims

An aqueous coating composition in which at least an ultraviolet absorber, a dispersant, and a resin component are present in an aqueous medium, characterized in that the ultraviolet absorber is a compound represented by the following general formula (I). A water-based paint composition containing an ultraviolet absorber.

General formula (I)

During the ceremony,
R 1 and R 1' may be the same or different from each other and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R 3 SO- group, or R 3 It is an O 2 - group.
R 2 and R 2' may be the same or different from each other, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a CO 2 H group, a phenyl group, an alkyl group moiety is a phenylalkyl group containing 1 to 4 carbon atoms, or a cycloalkyl group containing 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 with an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms; , substituted by one or two cycloalkyl groups having 5 to 12 carbon atoms, phenylalkyl groups having 7 to 15 carbon atoms, aryl groups having 6 to 10 carbon atoms or 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).
The ultraviolet absorber-containing aqueous coating composition according to claim 1, wherein the ultraviolet absorber is dispersed with an average dispersed particle size of 10 to 35 nm.
The ultraviolet absorber-containing aqueous coating composition according to claim 1 or 2, wherein the dispersant is one or more compounds selected from controlled polymerization acrylic copolymers.
The ultraviolet absorber-containing aqueous coating composition according to claim 1 or 2, further comprising a surfactant.
The ultraviolet absorber-containing aqueous coating composition according to claim 1 or 2, wherein the dispersant is one or more compounds selected from controlled polymerization acrylic copolymers, and further contains a surfactant. thing.
In the compound of general formula (I),
The ultraviolet absorber-containing aqueous coating composition according to claim 1 or 2, wherein R 1 and R 1' are chlorine, and R 2 and R 2' are tert-octyl.
In the compound of general formula (I),
R 1 and R 1' are chlorine, R 2 and R 2' are tert-octyl, the dispersant is one or more compounds selected from acrylic copolymers of controlled polymerization, and further a surfactant. The ultraviolet absorber-containing aqueous coating composition according to claim 1 or 2, characterized in that it contains:
A resin component is added to an aqueous composition in which at least an ultraviolet absorber and a dispersant are present in an aqueous medium, the ultraviolet absorber being a compound represented by the following general formula (I). A method for producing an aqueous paint composition containing an ultraviolet absorber, the method comprising the step of blending.

General formula (I)

During the ceremony,
R 1 and R 1' may be the same or different from each other and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R 3 SO- group, or R 3 It is an O 2 - group.
R 2 and R 2' may be the same or different from each other, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a CO 2 H group, a phenyl group, an alkyl group moiety is a phenylalkyl group containing 1 to 4 carbon atoms, or a cycloalkyl group containing 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 with an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms; , substituted by one or two cycloalkyl groups having 5 to 12 carbon atoms, phenylalkyl groups having 7 to 15 carbon atoms, aryl groups having 6 to 10 carbon atoms or 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).
The ultraviolet absorber according to claim 8, characterized in that the ultraviolet absorber in the aqueous composition in which at least the ultraviolet absorber and the dispersant are present in the aqueous medium is dispersed with an average dispersed particle size of 10 to 35 nm. A method for producing an aqueous paint composition containing a chemical agent.
9. The method for producing an ultraviolet absorber-containing aqueous coating composition according to claim 8, wherein the dispersant is one or more compounds selected from acrylic copolymers of controlled polymerization.
9. The method for producing an ultraviolet absorber-containing aqueous coating composition according to claim 8, wherein the aqueous composition in which at least an ultraviolet absorber and a dispersant are present in an aqueous medium further contains a surfactant.
In the compound of general formula (I),
9. The method for producing an aqueous coating composition containing an ultraviolet absorber according to claim 8, wherein R 1 and R 1' are chlorine, and R 2 and R 2' are tert-octyl.