JP2016069284A - Novel bisbenzotriazole phenolic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel reactive ultraviolet absorber optimal for use in a coating agent, an ink, a film, an adhesive and others.SOLUTION: A bisbenzotriazole phenolic compound is represented by the following formula, where X is a direct bond, a C1-6 alkylene group or the like; Rand Rare H, a C1-8 alkyl group, a C1-8 alkoxy group, an aryl group or a halogen atom; Rand Rare a C1-6 alkylene group; Aand Aare a group represented by formula: -(SiRRO)-SiR(OR), H, a C1-6 alkyl group or an aryl group; at least one of Aand Ais a group represented by -(SiRRO)-SiR(OR).SELECTED DRAWING: None

Description

The present invention relates to a novel bisbenzotriazole phenol compound and an ultraviolet absorber containing the compound.

Benzotriazole-based, benzophenone-based, salicylic acid-based, cyanoacrylate-based, or triazine-based compounds are used as ultraviolet absorbers useful for protecting plastics from ultraviolet rays. Most of these UV absorbers are low molecular weight compounds and are not reactive. For example, they have a high vapor pressure and transpiration at high temperatures when molding plastics. There was a problem that the ultraviolet absorber oozes out from the surface of the surface with time (bleed out). Therefore, a method is known in which a hydroxyalkyl group is introduced into a bisbenzotriazole phenol compound and copolymerized with raw material monomers such as polycarbonate, polyester, polyurethane, and polyurethane urea (Patent Documents 1 and 2).

On the other hand, in recent years, plastic materials such as acrylic resin and polycarbonate resin have been widely used as an alternative to transparent plate glass used in automobiles and building materials. These plastic materials are inferior in surface properties such as scratch resistance and weather resistance compared to glass, so they are hard-coated with thermosetting resins such as polyorganosiloxanes and melamines. Because of its properties, an ultraviolet absorber is added to the hard coating agent. However, an ultraviolet absorber that does not have low molecular reactivity has a problem that the ultraviolet absorber oozes out from the surface of the coating layer over time (bleed out). Moreover, even if the bisbenzotriazole phenol compound having the hydroxyalkyl group introduced therein is blended, the problem of bleeding out is hardly improved.

By the way, a method of blending a silicone resin with a vinyl copolymer having an organic ultraviolet absorbing group and a reactive group in the side chain is also known (Patent Document 3). However, it is necessary to separately add a large amount of components that do not directly improve the surface properties such as scratch resistance and weather resistance.

Japanese Patent Laid-Open No. 9-316060 JP-A-10-265557 JP 2012-219159 A

An object of this invention is to provide a novel reactive ultraviolet absorber. In particular, to provide reactive UV absorbers that are optimal for a wide range of applications where synthetic resins are used, such as coating agents, inks, films, and adhesives (adhesives) made of thermosetting resins such as polyorganosiloxanes. And

The inventors of the present invention have studied a reactive ultraviolet absorber, and can introduce an alkoxysilyl group into a bisbenzotriazole phenol compound, and the introduced organosilylsiloxane is a main component such as a coating agent. And the present invention was completed by finding that an ultraviolet absorbing group can be introduced into the side chain.

［式中Ｘは、直接結合、炭素数１〜６のアルキレン基、−Ｏ−基または−ＮＨ−基であり、Ｒ^１およびＲ^２は、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、アリール基またはハロゲン原子である。Ｒ^３およびＲ^４は、炭素数１〜６のアルキレン基である。Ａ^１およびＡ^２は、式：−（ＳｉＲ^５Ｒ^６Ｏ）_ｎ−ＳｉＲ^７ _ｍ（ＯＲ^８）_３−ｍ（式中、Ｒ^５、Ｒ^６、およびＲ^７は、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基またはアリール基であって、Ｒ^８は、炭素数１〜６のアルキル基またはアリール基であって同一であっても異なっていてもよい。ｍは０〜３の整数、ｎは０〜１００の整数を示す。ただし、ｍが３の場合、Ｒ^５、Ｒ^６およびＲ^７のいずれか一つ以上は、炭素数１〜６のアルコキシ基である。）で示される基、水素原子、炭素数１〜６のアルキル基またはアリール基であるが、Ａ^１およびＡ^２の少なくとも一つは−（ＳｉＲ^５Ｒ^６Ｏ）_ｎ−ＳｉＲ^７ _ｍ（ＯＲ^８）_３−ｍで表される基である。なお、Ｒ^１およびＲ^２、Ｒ^３およびＲ^４、Ａ^１およびＡ^２は、同一であっても異なっていてもよい。］
で表されるビスベンゾトリアゾールフェノール化合物に関する。 That is, the present invention provides a general formula:

[In the formula, X is a direct bond, an alkylene group having 1 to 6 carbon atoms, an —O— group or an —NH— group, and R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, carbon It is an alkoxy group, an aryl group or a halogen atom of formulas 1-8. R ³ and R ⁴ are alkylene groups having 1 to 6 carbon atoms. A ¹ and A ² are represented by the formula: — (SiR ⁵ R ⁶ O) _n —SiR ⁷ _m (OR ⁸ ) _3-m (wherein R ⁵ , R ⁶ , and R ⁷ are a hydrogen atom, a carbon number of 1 An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group, and R ⁸ may be the same or different and may be the same or different. m represents an integer of 0 to 3, and n represents an integer of 0 to 100. However, when m is 3, at least one of R ⁵ , R ⁶ and R ⁷ is an alkoxy group having 1 to 6 carbon atoms. A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, but at least one of A ¹ and A ² is — (SiR ⁵ R ⁶ O) _n —SiR ⁷ _m (OR < ⁸ >) is a group represented by _3-m . R ¹ and R ² , R ³ and R ⁴ , A ¹ and A ² may be the same or different. ]
It relates to the bisbenzotriazole phenol compound represented by these.

Moreover, this invention relates to the ultraviolet absorber which has the said bisbenzotriazole phenol compound, Furthermore, it is related with the coating agent containing the said ultraviolet absorber.

The compound of the present invention has a siloxane bond, and can provide an ultraviolet absorber excellent in compatibility with a wide range of resins, solubility in various solvents, and dispersibility in resins. In addition, it can react with various types of resins with siloxane bonds, especially polyorganosiloxane resins, and provides UV-absorbing agents within the resin skeleton, providing coating materials with long-term weather resistance that do not cause bleed-out. can do.

2 is a ¹ H-NMR chart of Compound 1 synthesized in Example 1. FIG.

［式中Ｘは、直接結合、炭素数１〜６のアルキレン基、−Ｏ−基または−ＮＨ−基であり、Ｒ^１およびＲ^２は、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、アリール基またはハロゲン原子である。Ｒ^３およびＲ^４は、炭素数１〜６のアルキレン基である。Ａ^１およびＡ^２は、式：−（ＳｉＲ^５Ｒ^６Ｏ）_ｎ−ＳｉＲ^７ _ｍ（ＯＲ^８）_３−ｍ（式中、Ｒ^５、Ｒ^６、およびＲ^７は、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基またはアリール基であって、Ｒ^８は、炭素数１〜６のアルキル基またはアリール基であって同一であっても異なっていてもよい。ｍは０〜３の整数、ｎは０〜１００の整数を示す。ただし、ｍが３の場合、Ｒ^５、Ｒ^６およびＲ^７のいずれか一つ以上は、炭素数１〜６のアルコキシ基である。）で示される基、水素原子、炭素数１〜６のアルキル基またはアリール基であるが、Ａ^１およびＡ^２の少なくとも一つは−（ＳｉＲ^５Ｒ^６Ｏ）_ｎ−ＳｉＲ^７ _ｍ（ＯＲ^８）_３−ｍで表される基である。なお、Ｒ^１およびＲ^２、Ｒ^３およびＲ^４、Ａ^１およびＡ^２は、同一であっても異なっていてもよい。］
で表される構造を有する。 The bisbenzotriazole phenolic compounds of the present invention have the general formula:

[In the formula, X is a direct bond, an alkylene group having 1 to 6 carbon atoms, an —O— group or an —NH— group, and R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, carbon It is an alkoxy group, an aryl group or a halogen atom of formulas 1-8. R ³ and R ⁴ are alkylene groups having 1 to 6 carbon atoms. A ¹ and A ² are represented by the formula: — (SiR ⁵ R ⁶ O) _n —SiR ⁷ _m (OR ⁸ ) _3-m (wherein R ⁵ , R ⁶ , and R ⁷ are a hydrogen atom, a carbon number of 1 An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group, and R ⁸ may be the same or different and may be the same or different. m represents an integer of 0 to 3, and n represents an integer of 0 to 100. However, when m is 3, at least one of R ⁵ , R ⁶ and R ⁷ is an alkoxy group having 1 to 6 carbon atoms. A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, but at least one of A ¹ and A ² is — (SiR ⁵ R ⁶ O) _n —SiR ⁷ _m (OR < ⁸ >) is a group represented by _3-m . R ¹ and R ² , R ³ and R ⁴ , A ¹ and A ² may be the same or different. ]
It has the structure represented by these.

Examples of the alkylene group having 1 to 6 carbon atoms of X, R ³ and R ⁴ include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, pentylene, isopentylene, neopentylene and hexylene.

Examples of the alkyl group having 1 to 8 carbon atoms of R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, Examples include tert-octyl, ethylhexyl and the like. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, ethylhexyloxy, cyclopentyloxy, Examples include cyclohexyloxy. Examples of the aryl group include phenyl, tolyl, xylyl, indenyl, naphthyl, furyl, thienyl and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

A ¹ and A ² have the formula:
_{^{- (SiR 5 R 6 O)}} n -SiR 7 m (OR 8) 3-m
(In the formula, R ⁵ , R ⁶ , and R ⁷ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group, and R ⁸ has 1 to 6 carbon atoms. 6 may be the same or different, and m is an integer of 0 to 3, and n is an integer of 0 to 100, provided that when m is 3, R ⁵ , one or more of R ⁶ and R ^7, a group represented by an alkoxy group having 1 to 6 carbon atoms.), a hydrogen atom, is an alkyl group or an aryl group having 1 to 6 carbon atoms, a ¹ And at least one of A ² is a group represented by — (SiR ⁵ R ⁶ O) _n —SiR ⁷ _m (OR ⁸ ) _3-m .

In the formula ^{_{:-( SiR 5 R 6 O) n}} -SiR 7 m (OR 8) 3-m, as the alkyl group having 1 to 6 carbon atoms of R 5, ^{R 6} and ^{R 7,} for example methyl, ethyl, propyl , Isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl and the like. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, cyclopentyloxy, cyclohexyloxy and the like. Can be mentioned. Examples of the aryl group include phenyl, tolyl, xylyl, indenyl, naphthyl, furyl, thienyl and the like. m is an integer of 0 to 3, and 0 is preferable.

Although n is an integer of 0-100, 0-20 are preferable. When it exceeds 20, flexibility more than necessary is imparted to the coating agent or molded product using the ultraviolet absorber, and it tends to be unsuitable for use as a material.

Regarding the alkyl group or aryl group having 1 to 6 carbon atoms in A ¹ and A ² , examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and neopentyl. Hexyl and the like. Examples of the aryl group include phenyl, tolyl, xylyl, indenyl, naphthyl and the like.

The bisbenzotriazole phenol compound of the present invention can be synthesized by reacting a silylating agent with a compound having a hydroxyalkyl group bonded to the position of R ³ and R ^{4 in} the above general formula, for example. Examples of the silylating agent include hydrosilane compounds, alkoxysilane compounds, silanol compounds, silsesquioxanes, chlorosilanes, bromosilanes, and iodosilanes.

The bisbenzotriazole phenol compound of the present invention can be used not only as a reactive ultraviolet absorber but also as a silane coupling agent having ultraviolet absorbing ability.

It does not specifically limit as resin which can mix | blend the reactive ultraviolet absorber of this invention, A conventionally well-known thing can be used widely. For example, for thermoplastic resins, polyvinyl chloride, polyvinylidene chloride, polyolefin, polycarbonate, polystyrene, acrylic resin, methacrylic resin, polyamide, polyester, acrylonitrile-butadiene-styrene (ABS) resin, polyurethane resin, vinyl chloride-vinylidene chloride-acrylonitrile. Examples include copolymers, acrylonitrile-styrene (AS) resins, vinyl acetate resins, polyphenylene ethers, polysulfones, polyether sulfones, polyether ketones (PEK), polyether ether ketones (PEEK), and liquid crystal plastics. Examples of thermosetting resins include phenolic resins, urea resins, melamine resins, unsaturated polyesters, silicone resins, alkyd resins, and epoxy resins. Especially, since the ultraviolet absorber of this invention contains silicone, a silicone resin is preferable.

The silicone resin is composed of organosiloxane and / or siloxane and / or silsesquioxane. Specific examples of the organosiloxane include R _m Si (OR ′) _n O _{(4-mn) / 2} (where R is an alkyl group substituted with an alkyl group, an alkenyl group, an epoxy group, or a phenyl group, an epoxy group, or An alkenyl group substituted with a phenyl group, R ′ is an alkyl group, m is an integer of 0 to 3, n is an integer of 0 to 3, and m + n is an integer of 1 to 3. Examples thereof include silicone oligomers containing hydrolyzable alkoxy groups in the molecule, but it is more preferable to use m = 1 since the effects such as adhesion obtained by blending are excellent. _{Moreover, Si (OR ') n O} (4-n) / 2 (R' is an alkyl group, n is a integer of 1 to 3), as represented by, tetramethoxysilane, the tetraethoxysilane Examples thereof include partial hydrolysis condensates of tetraalkoxysilane. _Also, like silsesquioxane as represented by _{(RSiO 1.5) 2n.}

Specific examples of the siloxane, such as represented by SiO _2, tetramethoxysilane, although such tetraalkoxy hydrolysis condensate or its solvent dispersion type silane such as tetraethoxysilane and the like, dispersion of ease and blending A solvent dispersion type such as an organosilica sol is more preferable because the effects such as adhesiveness obtained by doing so are excellent.

The blending amount of the ultraviolet absorber is preferably 1 to 900 parts by weight and more preferably 3 to 400 parts by weight with respect to 100 parts by weight of the silicone resin. If the blending amount is less than 1 part by weight, the weather resistance of the resin is insufficient, and if it exceeds 900 parts by weight, the physical properties of the silicone resin may be impaired.

The blending amount of the ultraviolet absorber depends on the thickness of the coating film or the molded product, but when the thickness is less than 1 μm, it is preferably 100 to 900 parts by weight with respect to 100 parts by weight of the silicone resin. -300 weight part is more preferable. When thickness is 1 micrometer or more and less than 10 micrometers, 5-100 weight part is preferable with respect to 100 weight part of silicone resins, and 10-50 weight part is more preferable. When thickness exceeds 10 micrometers, 1-5 weight part is preferable with respect to 100 weight part of silicone resins, and 3-5 weight part is more preferable.

The ultraviolet absorber of the present invention has a functional group as a terminal and contains a silicone resin. For example, when used as a coating agent, the alkoxysilyl group of the ultraviolet absorber is hydrolyzed and then the silanol group is polycondensed, so that the ultraviolet absorber can be fixed in the curing component.

In addition to the above-mentioned components, the coating agent of the present invention is appropriately mixed with commonly used components such as known additives such as antioxidants, light stabilizers, processing stabilizers, anti-aging agents, and compatibilizers. Can do. Examples of the antioxidant include sodium 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. Hindered phenol antioxidants, organic sulfur antioxidants such as di (tridecyl) 3,3′-thiodipropionate, phosphorus antioxidants such as triphenyl phosphite, and the like. Examples of the light stabilizer include hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (2-hydroxy-5-tert-butylphenyl) -2H- Examples thereof include benzotriazole-based ultraviolet absorbers such as benzotriazole. Examples of the processing stabilizer include phosphorus processing stabilizers such as tris (2,4-di-tert-butylphenyl) phosphite. Examples of the antiaging agent include nickel dibutyldithiocarbamate, N, N′-diphenyl-p-phenylenediamine, and the like. Examples of the compatibilizing agent include thermoplastic rubbers such as styrene-butadiene-styrene block copolymers and styrene-ethylene-butylene-styrene block copolymers. The blending amount of these additives is not particularly limited, but is usually preferably 0.01 to 20% by weight in the coating agent.

Examples of the filler include fine inorganic oxide particles such as silica sol, zinc oxide, titanium oxide, and aluminum oxide. Those which are dispersed in water or organic solvents such as methanol, xylene and methyl ethyl ketone are suitable for use. Other examples include calcium carbonate, glass fiber, talc, kaolin, mica, barium sulfate, carbon black, and graphite. The blending amount of these additives is not particularly limited, but is usually preferably 0.01 to 20% by weight in the coating agent.

The ultraviolet absorber of the present invention can be suitably applied to a wide range of uses in which a synthetic resin is used, such as a coating agent, an ink, a film, and an adhesive. Although there is no restriction | limiting in particular as a base material which coats these, Glass, a metal plate, a wooden board, a plastic material, paper, etc. are mentioned. In particular, it is suitably used for plastic substrates that require super-weather resistance such as acrylic resin and polycarbonate resin as an alternative to transparent glass plates used in automobiles and building materials.

Although the ultraviolet absorber of this invention can be used for various uses, it can be used conveniently especially for the use which may be exposed to the light containing sunlight or an ultraviolet-ray. Specific examples include, for example, glass substitutes and surface coating materials thereof, window glass for houses, facilities, and transportation equipment, coating materials for daylighting glass and light source protection glass, interior and exterior materials and interior and exterior materials for housing, facilities, and transportation equipment. UV coating materials, fluorescent lamps, mercury lamps and other light source components, precision machinery, materials for electronic and electrical equipment, shielding materials for electromagnetic waves generated from various displays, food and chemicals, chemical containers and packaging materials, agricultural industries Sheet or film material, anti-fading agent such as printed matter, dyed matter, dyed pigment, sunscreen cream, shampoo, rinse, hairdressing cosmetics, sportswear, stockings, textiles for clothing such as hats, fibers, curtains, Car interior items such as carpets, wallpaper, plastic lenses, contact lenses, artificial eyes, and other medical instruments, optical filters, prisms, mirrors, photos Optical articles such as the material, a tape, such as ink stationery, sign plate, and a marking device such as the surface coating material and the like.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples, Arbitrary deformation | transformation can be made within the range of the technical idea of this invention.

Example 1
11.6 g (0.022 mol) of 2,2′-methylenebis [4- (2-hydroxyethyl) -6- (2H-benzotriazol-2-yl)]-phenol (RUVA-100, manufactured by Otsuka Chemical Co., Ltd.) ), 6.6 g (0.044 mol) of dimethyldiethoxysilane was added to 11.6 g of cyclohexanone, and the atmosphere in the flask was replaced with nitrogen. After raising the temperature to 115 ° C., 0.6 g of a solution of 1.0 g (0.003 mol) of dodecylbenzenesulfonic acid dissolved in 100 ml of cyclohexanone was added and refluxed at 135 ° C. for 6 hours. After allowing to cool, the desired silicone-modified product (Compound 1) was obtained (purity 86%). The raw material 2,2′-methylenebis [4- (2-hydroxyethyl) -6- (2H-benzotriazol-2-yl)]-phenol remained at 6.3%. The compound for analysis was obtained by purifying the reaction product by column chromatography.

NMR attribution
¹ H-NMR (CDCl ₃ ): δ = 0.42 (12H, CH ₃ —Si), 1.14 (6H, CH ₃ —CH ₂ —O), 2.87 (4H, —CH ₂ —CH _{2) -O -), 3.67 (4H,} CH 3 -CH 2 -O), 3.89 (4H, -CH 2 -CH 2 -O -), 4.28 (2H, CH 2), 7.21 (2H, Ar-H), 7.47 (4H, Ar-H), 7.90 (4H, Ar-H), 8.15 (2H, Ar-H), 11.53 (2H, Ar-OH) )

Example 2
2,2'-methylenebis [4- (2-hydroxyethyl) -6- (2H-benzotriazol-2-yl)]-phenol 26.1 g (0.05 mol), silicone intermediate for modification TSR-165 ( 65.0 g (0.10 mol) of a methoxy group content of 15 wt%, manufactured by Momentive Performance Materials Japan LLC. Was added to 49.2 g of cyclohexanone, and the atmosphere in the flask was replaced with nitrogen. After raising the temperature to 115 ° C, 3.0 g of a solution of 0.653 g (0.002 mol) of dodecylbenzenesulfonic acid dissolved in 100 ml of cyclohexanone was added, and the mixture was refluxed at 135 ° C for 6 hours. After allowing to cool, the desired silicone-modified product (Compound 2) was obtained (purity 65%).

Example 3
2,2'-methylenebis [4- (2-hydroxyethyl) -6- (2H-benzotriazol-2-yl)]-phenol 26.1 g (0.05 mol), silicone alkoxy oligomer KR- for resin modification 500 (alkoxy group amount 28 wt%, manufactured by Shin-Etsu Chemical Co., Ltd.) 82.2 g was added to 49.2 g of cyclohexanone, and the atmosphere in the flask was replaced with nitrogen. After raising the temperature to 115 ° C, 3.0 g of a solution of 0.653 g (0.002 mol) of dodecylbenzenesulfonic acid dissolved in 100 ml of cyclohexanone was added, and the mixture was refluxed at 135 ° C for 6 hours. After allowing to cool, the desired silicone-modified product (Compound 3) was obtained (purity 60%).

<Solubility test>
Using hard coat agent VOC.O. # 7177 (manufactured by Buildland Co., Ltd.), 0.1%, 0.5% and 1.0% by weight of each compound with respect to 2.0 g of hard coat agent at room temperature. %, And the solubility was evaluated according to the following criteria. Table 1 shows the evaluation results using VOC · O · # 7177.
○: Hard coating agent applied to quartz disk and dried film is transparent Δ: Hard coating agent applied to quartz disk, dried film is slightly cloudy ×: Hard coating agent applied to quartz disk However, the dried film is cloudy. For comparison, 2,2′-methylenebis [4- (2-hydroxyethyl) -6- (2H-benzotriazol-2-yl)]-phenol (RUVA-100 The solubility of RUVA-100 modified with ε-caprolactone (UVA-103, manufactured by Daicel Corporation) was evaluated. Used as Comparative Examples 1 and 2, respectively.

溶解性試験の結果から、化合物１、２、３は、変性していない２，２’−メチレンビス［４−（２−ヒドロキシエチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）］−フェノールや、ε−カプロラクトンで変性したものと比較して、ハードコート剤に対する溶解性が高いことがわかる。

From the results of the solubility test, the compounds 1, 2, and 3 show that unmodified 2,2′-methylenebis [4- (2-hydroxyethyl) -6- (2H-benzotriazol-2-yl)]-phenol In addition, it can be seen that the solubility in the hard coating agent is higher than that modified with ε-caprolactone.

Example 4
To a mixture of 30.5 g of methyltrimethoxysilane and 1 g of acetic acid, 25.1 g of Ludox LS silica sol (30% colloidal silica aqueous dispersion, average particle size 12 nm, pH 8.2, manufactured by DuPont) was added and stirred at room temperature for 16 hours. . 57 g of isobutanol and 1 g of SF-1066 interfacial agent (silicone-polyether flow control agent, manufactured by General Electric Co.) were added, followed by 10% of solid content, and the resulting composition was added at 20 ° C. for 7 days. Aged.

Comparative Example 3
In Example 4, instead of Compound 1, 2,2′-methylenebis [4- (2-hydroxyethyl) -6- (2H-benzotriazol-2-yl)]-phenol (RUVA-100, Otsuka Chemical Co., Ltd.) 7) in terms of solid content so that the addition amount per 2,2′-methylenebis [4- (2-hydroxyethyl) -6- (2H-benzotriazol-2-yl)]-phenol is the same. % Was used to prepare a hard coating agent.

Comparative Example 4
In Example 4, instead of Compound 1, RUVA-100 modified with ε-caprolactone (UVA-103, manufactured by Daicel Corporation) was used as 2,2′-methylenebis [4- (2-hydroxyethyl)- 6- (2H-benzotriazol-2-yl)]-hard coat agent was prepared using 16% solids so that the addition amount per phenol was the same.

<UV irradiation wet heat cycle test>
A hard coating agent was applied to a sheet made from Lexan resin (polycarbonate resin, manufactured by sabic) without undercoating, air-dried for 60 minutes, and then cured at 125 ° C. for 60 minutes. Using an ultraviolet deterioration accelerating tester iSuper UV tester (type SUV-W131, manufactured by Iwasaki Electric Co., Ltd.), the light resistance test shown below was performed for 10 cycles.
(1) Irradiation with ultraviolet light of 130 mw / cm ² for 8 hours in an atmosphere of 60 ° C. and 50% RH (2) 8 hours in an atmosphere of 35 ° C. and 100% RH (condensation conditions) (3) 35 ° C. 8 hours in 70% RH atmosphere

(Change in color of coating film)
The color change of the coating film before and after the test was evaluated with the naked eye.
◎: No change ○: Slightly yellow △: Slightly yellow ×: Change to tan

(Coating film adhesion)
The test film was cut into 6 x 6 25 grids in an area of 1 cm x 1 cm with a cutter, and cellophane tape (manufactured by Nichiban Co., Ltd.) was applied, then peeled off vigorously. The peeled state of the coating film was evaluated.
○: No peeling at all Δ: Slight peeling ×: Severe peeling

(Coating hardness)
After the test, the coating film was observed to examine whether the film was scratched with a nail, and evaluated according to the following criteria.
○: No scratch △: Scratched ×: Tattered

From the results of the ultraviolet irradiation wet heat cycle test, the composition containing Compound 1 hardly deteriorated from the initial state in color change, adhesion, and hardness even after the weather resistance test. On the other hand, the composition containing unmodified 2,2′-methylenebis [4- (2-hydroxyethyl) -6- (2H-benzotriazol-2-yl)]-phenol is incompatible and therefore deteriorated. However, the composition containing a material modified with ε-caprolactone is soft but has low hardness.

The bisbenzotriazole phenolic compound of the present invention is useful as a reactive ultraviolet absorber, and in particular, a synthetic resin such as a coating agent, ink, film, adhesive (adhesive) made of a thermosetting resin such as polyorganosiloxane. Is ideal for a wide range of applications.

Claims (3)

General formula:

[In the formula, X is a direct bond, an alkylene group having 1 to 6 carbon atoms, an —O— group or an —NH— group, and R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, carbon It is an alkoxy group, an aryl group or a halogen atom of formulas 1-8. R ³ and R ⁴ are alkylene groups having 1 to 6 carbon atoms. A ¹ and A ² are represented by the formula: — (SiR ⁵ R ⁶ O) _n —SiR ⁷ _m (OR ⁸ ) _3-m (wherein R ⁵ , R ⁶ , and R ⁷ are a hydrogen atom, a carbon number of 1 An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group, and R ⁸ may be the same or different and may be the same or different. m represents an integer of 0 to 3, and n represents an integer of 0 to 100. However, when m is 3, at least one of R ⁵ , R ⁶ and R ⁷ is an alkoxy group having 1 to 6 carbon atoms. A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, but at least one of A ¹ and A ² is — (SiR ⁵ R ⁶ O) _n —SiR ⁷ _m (OR < ⁸ >) is a group represented by _3-m . R ¹ and R ² , R ³ and R ⁴ , A ¹ and A ² may be the same or different. ]
The bisbenzotriazole phenol compound represented by these. An ultraviolet absorber comprising the bisbenzotriazole phenol compound according to claim 1. The coating agent containing the ultraviolet absorber of Claim 2.

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