JP2019001767A - Bisbenzotriazolylphenol compound, ultraviolet absorber, and composition - Google Patents

Abstract

To provide a novel bisbenzotriazolylphenol compound that avoids bleedout even in a use environment including moisture, has excellent weather resistance, and can improve flexibility, such as tensile elongation, of a curable resin comprising the novel compound as a crosslinker, the bisbenzotriazolylphenol compound being suitable for an ultraviolet absorber.SOLUTION: A bisbenzotriazolylphenol compound is represented by a general formula (1) (where, each symbol is described in the specifications).SELECTED DRAWING: None

Description

  The present invention relates to a novel compound of benzotriazolylphenol useful as an ultraviolet absorber, an ultraviolet absorber containing the novel compound, and a composition containing the ultraviolet absorber.

  As a means for improving the weather resistance of the resin or providing the resin with ultraviolet shielding properties, an ultraviolet absorber is used.

  However, conventional UV absorbers have a high vapor pressure due to their low molecular weight, and when blended with a resin, they are volatilized, resulting in a decrease in yield, mold contamination, and health hazards to workers. Or In addition, since it bleeds out from the surface of the molded product or coating film over time or elutes with rain or water containing detergents in the usage environment, it impairs the appearance of the product and at the same time imparts long-term light stability to the product. It is known to be difficult to do.

  In order to solve such problems, UV absorbers with improved compatibility with plastics have been developed by having long-chain alkyl groups, long-chain alkenyl groups, or long-chain alkylene oxide chains of appropriate lengths. (Patent Document 1).

  Moreover, as a solution to such problems, a combination of an ultraviolet-absorbing urethane resin obtained by reacting a polyester polyol having an ultraviolet-absorbing group and a polyisocyanate with an acrylic resin and / or a urethane resin, A wood material coating resin composition having improved compatibility and bleed-out resistance over time is also disclosed (Patent Document 2).

  Furthermore, as a solution to such a problem, an ultraviolet absorber made of a bisbenzotriazolylphenol compound having two addition polymerization side chains has been developed (Patent Document 3). Since this compound has two addition polymerization side chains, it functions not only as an ultraviolet absorber but also as a crosslinking agent. Since it has a carbamoyloxy unit in the molecule, it is flexible to the cured resin used as the crosslinking agent. It is supposed to give sex.

  However, the compound described in Patent Document 3 tends to bleed out in an environment where moisture is present, which may impair the appearance of the product, and is weather resistant, that is, affected by light and moisture at the same time. There was still a problem with the long-term sustainability of light stability in the environment of use. Furthermore, the flexibility of a cured resin using the compound described in Patent Document 3 as a crosslinking agent, such as tensile elongation, is still insufficient, and further improvement in flexibility is required.

JP 2000-230077 A JP 2003-128986 A JP 2004-2317 A

  Therefore, an object of the present invention is to provide a novel compound that solves the above problems. That is, the present invention is useful as an ultraviolet absorber that is difficult to bleed out even in a use environment where moisture is present, has excellent weather resistance, and can further improve flexibility such as tensile elongation of a cured resin. It is an object of the present invention to provide a novel bisbenzotriazolylphenol compound. Moreover, it aims at providing the ultraviolet absorber containing the said novel compound, and the composition containing the said ultraviolet absorber.

  The novel bisbenzotriazolylphenol compound according to the present invention is a bisbenzotriazolylphenol compound represented by the following general formula (1).

(In General Formula (1), Q represents a methylene group, an ethylidene group, an isopropylidene group, or a sec-butylidene group. R ¹ , R ² , R ³ , and R ⁴ each independently represent 1 or more carbon atoms. 6 or less linear or branched aliphatic hydrocarbon groups, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, or Represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, n and m are each independently a number of 1 to 10 and n + m = 2 to 20; p and q are each independently 3 The number is from 5 to 5. r and s are each independently from 1 to 2.

  The present invention also provides an ultraviolet absorber containing the bisbenzotriazolylphenol compound represented by the general formula (1) of the present invention.

  The present invention also provides a composition comprising the ultraviolet absorber of the present invention and a polymerizable compound having an ethylenically unsaturated bond-containing group.

  According to the present invention, as an ultraviolet absorber that is difficult to bleed out even in a use environment where moisture exists, has excellent weather resistance, and can further improve flexibility such as tensile elongation of a cured resin. Useful novel bisbenzotriazolylphenol compounds can be provided. Moreover, the ultraviolet absorber containing the said novel compound and the composition containing the said ultraviolet absorber can be provided.

Hereinafter, embodiments of the novel bisbenzotriazolylphenol compound of the present invention and a composition containing the novel compound as an ultraviolet absorber will be described.
In the present invention, (meth) acryl represents each of acryl and methacryl, (meth) acryloyl represents each of acryloyl and methacryloyl, and (meth) acrylate represents each of acrylate and methacrylate.

I. Novel bisbenzotriazolylphenol compound The novel bisbenzotriazolylphenol compound according to the present invention is a bisbenzotriazolylphenol compound represented by the following general formula (1).

(In General Formula (1), Q represents a methylene group, an ethylidene group, an isopropylidene group, or a sec-butylidene group. R ¹ , R ² , R ³ , and R ⁴ each independently represent 1 or more carbon atoms. 6 or less linear or branched aliphatic hydrocarbon groups, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, or Represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, n and m are each independently a number of 1 to 10 and n + m = 2 to 20; p and q are each independently 3 The number is from 5 to 5. r and s are each independently from 1 to 2.

  Since the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has a large molecular absorption coefficient, the ultraviolet absorption performance is good, the vapor pressure is extremely low, and the thermal stability is high. Therefore, volatilization is suppressed even when mixed with a resin, and it can be stably mixed without being decomposed, so that it is useful as an ultraviolet absorber.

  The bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has 2 or more and 4 or less (meth) acryloyl groups in one molecule. Therefore, when it is contained in the composition together with a polymerizable compound having an ethylenically unsaturated bond-containing group, the ultraviolet absorber itself functions as a crosslinking agent, so that it has excellent weather resistance and ultraviolet shielding without reducing the crosslinking density. Sex can be imparted.

Furthermore, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) is a bisbenzotriazolphenol compound having a conventional (meth) acryloyl group as shown in Examples and Comparative Examples described later. Compared to benzotriazolylphenol compounds, it is less likely to bleed out in environments where moisture is present, and weather resistance, that is, long-term durability of photostability in environments where it is simultaneously affected by light and moisture Is excellent.
This is unclear, but is estimated as follows.
The bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) includes two aliphatic hydrocarbon chains and a caprolactone between the (meth) acryloyl group and bisbenzotriazolylphenol. And a lactone chain such as a chain. Since the bisbenzotriazolylphenol compound is bulky, it has conventionally been easy to agglomerate and to be unevenly distributed in the coating film. On the other hand, since the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has two long-chain substituents, there is an advantage that it is difficult to aggregate and unevenly distributed. In addition, since one long-chain substituent group has two aliphatic hydrocarbon chains and a lactone chain such as a caprolactone chain, compatibility with the resin is improved, and it is easily dispersed in the resin. Easily demonstrates its function as a UV absorber.
Further, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has a lactone chain such as a caprolactone chain between the (meth) acryloyl group and the bisbenzotriazolylphenol. Therefore, the degree of freedom of the (meth) acryloyl group present at the terminal is increased, and the reaction efficiency with the ethylenically unsaturated bond-containing group of other molecules is improved.
As described above, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) is less likely to aggregate, is easily dispersed in the resin, and contains other ethylenically unsaturated bonds. Since the reaction efficiency with the base is improved, it is difficult to bleed out even in an environment where moisture is present, and the UV absorption function is long-term even in environments where it is simultaneously affected by light and moisture. Presumed to be excellent in sustainability.

  Furthermore, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) is not only an aliphatic hydrocarbon chain between the (meth) acryloyl group and the bisbenzotriazolylphenol compound, It has a lactone chain such as a caprolactone chain. By incorporating the lactone chain into a crosslinked structure formed by polymerizable compounds having an ethylenically unsaturated bond-containing group, flexibility and elasticity are imparted to the crosslinked structure. Therefore, the cured product of the composition containing the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) and a polymerizable compound having an ethylenically unsaturated bond-containing group is flexible and elastic. And tensile elongation superior to that of the prior art can be achieved.

More specifically, each group represented in the general formula (1) is as follows.
Examples of the linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms in R ¹ and R ² include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, ethylidene, propylene, propylidene, and ethylethylene. , 2-butylidene, 1-methyltrimethylene, 1,1-dimethylethylene, 1,1-dimethyltrimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, and other linear or branched groups Is mentioned. As R ¹ and R ² , a linear aliphatic hydrocarbon group of 2 to 6 is preferable, and ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene are preferable.

When r and s are each 1, R ³ and R ⁴ are each a divalent straight chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, and examples thereof are R ¹ and R ² . In addition, the same as the linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms can be preferably used.
When r and s are each 2, R ³ and R ⁴ are each a trivalent straight chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, and a straight chain having 1 to 6 carbon atoms. Examples include residues obtained by removing three hydrogen atoms from a chain or branched aliphatic hydrocarbon. As R ³ and R ⁴ when r and s are 2, respectively, for example, a trivalent aliphatic hydrocarbon group represented by the following chemical structural formula is preferably used.
When r and s are each independently 2, the number of polymerizable functional groups in one molecule is 3 or 4, and the reaction efficiency with the ethylenically unsaturated bond-containing group of other molecules is improved.

R ¹ , R ² , R ³ , and R ⁴ may be the same or different from each other, but from the viewpoint of production, R ¹ and R ² are preferably the same, and R ³ and R ⁴ Are preferably the same.

R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, but a hydrogen atom is preferred from the viewpoint of improving reaction efficiency.

Examples of the halogen atom in R ⁷ and R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom and a bromine atom are preferable.
Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms in R ⁷ and R ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

  p and q are each independently a number of 3 or more and 5 or less. That is, the bisbenzotriazolylphenol compound represented by the general formula (1) is a lactone chain that is a ring-opening addition polymerization chain of at least one lactone among γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Is included. A compound with p and q of 3 is obtained by ring-opening addition polymerization of γ-butyrolactone, a compound with p and q of 4 is obtained by ring-opening addition polymerization of δ-valerolactone, and by ring-opening addition polymerization of ε-caprolactone. A compound having p and q of 5 is obtained. When a mixture of two or more lactones is used, p and q may be average values. From the viewpoint of tensile elongation, p and q are each independently preferably a number of 4 or more and 5 or less, and more preferably 5.

n and m are each independently 1 or more and 10 or less. n and m each represent the degree of polymerization (number of added moles) of the lactone, and n and m may each be an average value. n and m are appropriately determined depending on the use in consideration of whether the lactone chain needs to improve flexibility and tensile elongation or whether it is necessary to increase hardness while improving tensile elongation. You can choose. Among these, from the viewpoint of improving flexibility such as tensile elongation, n and m are each preferably preferably independently of an average of 1.5 or more, and preferably 8 or less from the viewpoint of improving hardness. It is further preferably 6 or less, and further preferably 5 or less.
Further, n + m = 2 or more and 20 or less, but similarly, it is preferably 3 or more from the viewpoint of improving flexibility such as tensile elongation, and on the other hand, 16 or less is preferable from the viewpoint of improving hardness. , 12 or less, more preferably 10 or less.

Specific examples of the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) include the following combinations of compounds.
In the following combination of compounds, p and q are each 5 and r and s are 1 respectively.
Furthermore, in the following combinations of compounds, p and q are each 5 and r and s are 2 respectively.
In the following combinations of compounds, p and q are each 4 and r and s are each 1, and p and q are 3 and r and s are 1 respectively. . However, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) is not limited to specific examples of these combinations.

  The bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) is, for example, ε-caprolactone or the like on the alcoholic hydroxyl group of the bisbenzotriazolylphenol compound represented by the general formula (2). Can be produced by ring-opening addition polymerization and reacting an alcoholic hydroxyl group of the lactone chain with an isocyanate compound having a (meth) acryloyloxy group in a solvent.

(In general formula (2), Q, R ¹ , R ² , R ⁷ and R ⁸ are the same as in general formula (1).)

As the bisbenzotriazolylphenol compound represented by the general formula (2) used here, 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (hydroxy Methyl) phenol], 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol], 2,2′-methylene-bis [6- ( 5-chloro-2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol], 2,2′-methylene-bis [6- (5-bromo-2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol], 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (3-hydroxypropyl) phenol], 2, '-Methylene-bis [6- (5-chloro-2H-benzotriazol-2-yl) -4- (3-hydroxypropyl) phenol], 2,2'-methylene-bis [6- (5-bromo- 2H-benzotriazol-2-yl) -4- (3-hydroxypropyl) phenol], 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxypropyl) ) Phenol], 2,2′-methylene-bis [6- (5-chloro-2H-benzotriazol-2-yl) -4- (2-hydroxypropyl) phenol], 2,2′-methylene-bis [ 6- (5-Bromo-2H-benzotriazol-2-yl) -4- (2-hydroxypropyl) phenol], 2,2'-methylene-bis [6- (2H-benzotriazole-2- Yl) -4- (4-hydroxybutyl) phenol], 2,2′-methylene-bis [6- (5-chloro-2H-benzotriazol-2-yl) -4- (4-hydroxybutyl) phenol] 2,2′-methylene-bis [6- (5-bromo-2H-benzotriazol-2-yl) -4- (4-hydroxybutyl) phenol], 3,3- [2,2′-bis [ 6- (2H-benzotriazol-2-yl) -1-hydroxy-4- (2-hydroxyethyl) phenyl]] propane, 2,2- [2,2′-bis [6- (2H-benzotriazole- 2-yl) -1-hydroxy-4- (2-hydroxyethyl) phenyl]] butane is preferably used.
The bisbenzotriazolylphenol compound represented by the general formula (2) can be appropriately prepared by a conventionally known method.

  As a method of ring-opening addition polymerization of a lactone such as ε-caprolactone to the alcoholic hydroxyl group of the bisbenzotriazolylphenol compound represented by the general formula (2), a conventionally known method may be appropriately selected and used. . For example, a bisbenzotriazolylphenol compound represented by the general formula (2) and a lactone such as ε-caprolactone are 90 ° C. or higher and 240 ° C. or lower, preferably 100 ° C. or higher and 200 ° C. or lower in the presence of a catalyst. By reacting, lactone such as ε-caprolactone can be subjected to ring-opening addition polymerization to the alcoholic hydroxyl group. Examples of the catalyst include organic tin compounds such as stannous octylate, dibutyltin oxide, dibutyltin dilaurate, and mono-n-butyltin fatty acid salt; stannous chloride, stannous bromide, stannous iodide, and the like. Stannous halides; organic titanium compounds such as tetraethyl titanate, tetrabutyl titanate, tetrapropyl titanate; and the like. The amount of the catalyst used is preferably 0.01 mol% or more and 2 mol% or less, more preferably 0.02 mol% or more and 1.2 mol% or less, based on the hydroxyl group in the reaction raw material. The number of moles of lactone chain added can be appropriately adjusted by adjusting the amount corresponding to the number of moles of lactone added during synthesis.

  As an isocyanate compound having a (meth) acryloyloxy group, (meth) acryloyloxymethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate 4- (meth) acryloyloxybutyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate and the like are preferably used.

  Although the solvent used when making it react with the isocyanate compound which has a (meth) acryloyloxy group with respect to the alcoholic hydroxyl group of a lactone chain | strand is not specifically limited, methyl ethyl ketone, methyl isopropyl ketone, etc. Aprotic solvents such as ketone solvents, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and ether solvents such as dibutyl ether and dioxane can be used alone or in admixture of two or more. Further, the content ratio of the solvent is not particularly limited and can be selected according to the ease of stirring, the reaction temperature, and the solubility of the substrate. Usually, the bisbenzotriazolylphenol compound represented by the general formula (2) 100 mass parts or more and 500 mass parts or less are preferable with respect to 100 mass parts. The reaction temperature is appropriately selected in the range of 20 ° C. to 150 ° C., preferably 30 ° C. to 100 ° C., depending on the type of solvent.

As described above, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has an excellent ultraviolet absorption performance, and even when mixed with a resin, volatilization is suppressed and it does not decompose. Therefore, it is useful as an additive type ultraviolet absorber.
Further, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) is for preparing an ultraviolet absorbing polymer having an ultraviolet absorbing unit in the side chain using a (meth) acryloyloxy group. You may use as a monomer.
Furthermore, since the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has two (meth) acryloyloxy groups with high reaction efficiency, it functions well as a crosslinking agent. As will be described later, it is preferably used together with a polymerizable compound having an ethylenically unsaturated bond-containing group as an ultraviolet-absorbing active ingredient in the curable composition.

II. Ultraviolet absorber The ultraviolet absorber of this invention contains the bisbenzotriazolyl phenol compound represented by the said General formula (1).
The ultraviolet absorber of the present invention preferably contains 50% by mass or more of the bisbenzotriazolylphenol compound represented by the general formula (1), more preferably 70% by mass or more, and still more. The content is preferably 90% by mass or more, and may be 100% by mass. The bisbenzotriazolylphenol compound represented by the general formula (1) contained in the ultraviolet absorber of the present invention may be one type or two or more types.
Moreover, as another component which may be contained in the ultraviolet absorber of this invention, another ultraviolet absorber etc. are mentioned, for example. Other ultraviolet absorbers include, for example, benzophenone compounds, triazine compounds, cyanoacrylate compounds, benzoxazinone compounds, benzoxazole compounds, merocyanine compounds, or a plurality of compounds obtained by arbitrarily combining these compounds Etc.

III. Composition The composition of the present invention contains an ultraviolet absorber containing the bisbenzotriazolylphenol compound represented by the general formula (1) and a polymerizable compound having an ethylenically unsaturated bond-containing group. .

Here, the polymerizable compound having an ethylenically unsaturated bond-containing group to be mixed with the ultraviolet absorber of the present invention is not particularly limited, and is a polymer (high polymer), oligomer (low polymer), And a compound such as a monomer (monomer), and may be a silane coupling agent having an ethylenically unsaturated bond-containing group.
The polymerizable compound having an ethylenically unsaturated bond-containing group is obtained by irradiating an active energy ray such as an ultraviolet ray or an electron beam with an ethylenically unsaturated bond-containing group containing a (meth) acryloyloxy group contained in the ultraviolet absorber of the present invention. And react to polymerize or crosslink to form a cured product.
Examples of the ethylenically unsaturated bond-containing group include a vinyl group, an allyl group, and a (meth) acryloyloxy group. As the polymerizable compound having an ethylenically unsaturated bond-containing group, a compound having at least one (meth) acryloyloxy group in one molecule is preferably used.

  Here, as the polymerizable compound having at least one ethylenically unsaturated bond-containing group in one molecule, known compounds can be used, but at least two (meth) acryloyloxy groups in one molecule ( At least one selected from a (meth) acrylate-based oligomer and a monomer having at least one ethylenically unsaturated bond-containing group in one molecule is preferably used. Especially, it is preferable that the compound which has at least 3 ethylenically unsaturated bond containing group is contained in 1 molecule from the point which improves a crosslinking density.

  Examples of the (meth) acrylate oligomer having at least two (meth) acryloyloxy groups in one molecule include, for example, a polyfunctional polyester (meth) having at least two (meth) acryloyloxy groups in one molecule. Examples include acrylate oligomers, polyfunctional urethane (meth) acrylate oligomers, polyfunctional epoxy (meth) acrylate oligomers, and polyfunctional ether (meth) acrylate oligomers. From the viewpoint of improving the crosslinking density, a (meth) acrylate oligomer having at least three (meth) acryloyloxy groups in one molecule is preferable as the (meth) acrylate oligomer.

  As a polyfunctional polyester (meth) acrylate oligomer having at least two (meth) acryloyloxy groups in one molecule, for example, a compound synthesized from (meth) acrylic acid, polyhydric alcohol and polybasic acid (anhydride) Etc. can be used. Moreover, as a polyfunctional urethane (meth) acrylate oligomer having at least two (meth) acryloyloxy groups in one molecule, for example, a compound obtained by reaction of polyisocyanate, polyol and hydroxy (meth) acrylate is used. it can. Moreover, as a polyfunctional epoxy (meth) acrylate oligomer having at least two (meth) acryloyloxy groups in one molecule, for example, a compound obtained by an addition reaction between polyglycidyl ether and (meth) acrylic acid, etc. Can be used. Moreover, as a polyfunctional ether (meth) acrylate oligomer having at least two (meth) acryloyloxy groups in one molecule, for example, polyether obtained by reacting polyol with ethylene oxide, propylene oxide, etc., ethyl A compound obtained by transesterification with (meth) acrylate can be used. Each of the above oligomers can be used singly or in combination of two or more. Among the above oligomers, those prepared from aliphatic or alicyclic compounds for improving weather resistance can be preferably used.

  Examples of the monomer having at least one ethylenically unsaturated bond-containing group in one molecule include, for example, vinyl monomers such as N-vinylpyrrolidone, N-vinylcaprolactone, vinylimidazole, vinylpyridine, and styrene as monofunctional monomers, phenoxyethyl (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, balacylphenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Trahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, orthophenylphenoxyethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N- Examples thereof include (meth) acrylic acid ester monomers such as dimethylaminopropyl (meth) acrylate and acryloylmorpholine, and (meth) acrylamide derivatives. Polyfunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, poly Tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 3-methyl-1 , 5-Pentanediol di (meth) acrylate, neobendyl glycol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, hydroxypivalic acid neobendyl glycol di (meth) acrylate Bisphenol A polyethoxydiol di (meth) acrylate, bisphenol A polypropoxydiol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylol brobantry ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, glyceryl tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol Ruhekisa (meth) acrylate.

Moreover, as a polymeric compound which has an ethylenically unsaturated bond containing group, the polymer which has an ethylenically unsaturated bond containing group in the side chain of a repeating unit may be used, and it represents with following General formula (3). Examples thereof include a polymer containing a repeating unit.

(In the formula, R ′ represents a hydrogen atom or a methyl group, P is a monovalent group including an ethylenically unsaturated bond-containing group, and L is a single bond or a divalent linking group.)

L is a single bond or a divalent linking group, preferably a single bond, —O—, an alkylene group, an arylene group, —COO—, —CONH—, —OCO—, or —NHCO—.
P is a monovalent group containing an ethylenically unsaturated bond-containing group such as a vinyl group or a (meth) acryloyl group. Although the specific example of the combination of L and P of the repeating unit represented by General formula (3) below is shown, this invention is not limited to these. Examples of other repeating units include the repeating units described in paragraphs 0034 to 0038 of JP-A No. 2003-147017. Preparation of a polymer containing such a repeating unit is described in JP-A No. 2003-147017. It can be prepared with reference to paragraphs 0039-0050 and the like.

Examples of the combination of L and P include the following.
-COOCH ₂ CH = CH _{2
-COOCH 2 CH 2 OC (= O} ) CH = CH 2
_{-COOCH 2 CH 2 OC (= O} ) C (CH 3) = CH 2
_{-CONHCH 2 CH 2 OC (= O} ) CH = CH 2
_{-CONHCH 2 CH 2 OC (= O} ) C (CH 3) = CH 2
_{-COOCH 2 CH 2 OC (= O} ) NHCH 2 CH 2 C (= O) CH = CH 2
_{-COOCH 2 CH 2 OC (= O} ) NHCH 2 CH 2 C (= O) C (CH 3) = CH 2
_{-COOCH 2 CH (OH) CH 2} OC (= O) CH = CH 2
_{-COOCH 2 CH (OH) CH 2} OC (= O) C (CH 3) = CH 2
_{-COOCH 2 CH 2 OCH 2 NHC (} = O) CH = CH 2

  The polymer containing the repeating unit represented by the general formula (3) may be a copolymer, and is derived from a monomer having one or more arbitrary ethylenically unsaturated bond-containing groups. You may have a repeating unit further. There is no restriction | limiting in particular as a monomer which has an ethylenically unsaturated bond containing group used in a copolymer, It can select suitably from various viewpoints, such as hardness, the solubility to a solvent, and transparency.

  For example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, allyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, etc. Vinyl esters, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, (meth) acrylates such as (meth) acryloyloxypropyltrimethoxysilane, styrene, p-hydroxymethyl Styrene derivatives such as styrene, unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid Beauty its derivatives and the like can be mentioned. The polymer containing the repeating unit represented by the general formula (3) may be an alkali-soluble resin containing an acid group.

  In the polymer containing the repeating unit represented by the general formula (3), from the viewpoint of increasing the hardness, a preferable ratio of the repeating unit represented by the general formula (3) is 30% by mass or more and 100% by mass or less. More preferably, it is 50 mass% or more and 100 mass% or less, Most preferably, it is 70 mass% or more and 100 mass% or less.

  The preferred molecular weight range of the polymer containing the repeating unit represented by the general formula (3) is 1,000 to 1,000,000, more preferably 3,000 to 200,000 in terms of mass average molecular weight. Most preferably, it is 5000 or more and 100,000 or less.

The compound having an ethylenically unsaturated bond-containing group may be a silane coupling agent having an ethylenically unsaturated bond-containing group, a vinyl group-containing silane coupling agent, and a (meth) acryloyloxy group-containing A silane coupling agent etc. are mentioned. Specific examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and styryltrimethoxysilane.
Specific examples of the silane coupling agent having a (meth) acryloyloxy group include 2- (meth) acryloyloxyethyltrimethoxysilane, 2- (meth) acryloyloxyethyltriethoxysilane, and 3- (meth) acryloyl. Oxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 4- (meth) acryloyloxy Examples include butyltrimethoxysilane.
The composition containing the silane coupling agent having an ethylenically unsaturated bond-containing group and the bisbenzotriazolylphenol compound represented by the general formula (1) is, for example, a substance that can react with an alkoxysilyl group. The ultraviolet shielding effect can be improved by applying and curing the substrate on the surface.

  As a compound which has an ethylenically unsaturated bond containing group contained in a composition, it can be used individually by 1 type or in mixture of 2 or more types.

In addition, the composition may further contain a thermoplastic resin or a thermosetting resin.
Examples of the thermoplastic resin include polyester resin, urethane resin, acrylic resin, urethane-acrylic copolymer resin, polycarbonate resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral resin, nitrocellulose resin, polyolefin resin, polystyrene resin. Known resins such as polyamide resin, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, and liquid crystal plastic can be used singly or in combination of two or more.

  In the composition of the present invention, if necessary, for example, a light stabilizer, an antioxidant, a plasticizer, a flame retardant, a surfactant, a leveling agent, a thermal polymerization inhibitor, an antistatic agent, an antifogging agent, Various additives and solvents such as antibacterial agents, fillers, pigments, dyes, and colorants can be included.

  In the composition of the present invention, the solvent is used for adjusting the viscosity of the composition, improving the smoothness and uniformity of the cured film, and the adhesion to the substrate. Known solvents can be used, such as water, ethanol, propanol, isopropanol, butanol and other alcohols, toluene, xylene and other aromatic hydrocarbons, ethyl acetate, butyl acetate and other esters, acetone, methyl ethyl ketone. And ketones such as methyl isobutyl ketone, and ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-ethoxypropanol, 2- (2-ethoxyethoxy) ethanol, 1,4-dioxane, and tetrahydrofuran. Two or more kinds of solvents may be mixed and used.

The content of the ultraviolet absorber of the present invention in the composition of the present invention is not particularly limited, and the intended use of the composition obtained, the material of the substrate to which the composition is applied, the shape of the substrate, and after the composition is cured In view of various conditions such as hardness, film thickness, long-term weather resistance after curing, metal ion resistance, degree of transparency, molar extinction coefficient of the UV-absorbing compound, etc., it may be appropriately selected from a wide range. The content ratio of the ultraviolet absorber of the present invention in the composition of the present invention is 0.1% by mass or more and 50% by mass or less, preferably 0.5% by mass or more and 30% by mass with respect to 100% by mass of the solid content of the composition. It is desirable to use in the range of mass% or less. If the use ratio of the ultraviolet absorber of the present invention is 0.1% by mass or more, it is easy to improve the weather resistance of the cured product obtained from the composition, and if it is 50% by mass or less, the curing obtained from the composition. Good basic physical properties. In the composition of the present invention, two or more ultraviolet absorbers of the present invention can be mixed and used.
The content ratio of the polymerizable compound having an ethylenically unsaturated bond-containing group in the composition of the present invention is not particularly limited, and the intended use of the resulting composition, the material of the substrate to which the composition is applied, and the shape of the substrate In view of various conditions such as hardness after curing of the composition, it may be appropriately selected from a wide range. The content of the polymerizable compound having an ethylenically unsaturated bond-containing group in the composition of the present invention is usually 10% by mass or more and 99.9% by mass or less with respect to 100% by mass of the solid content of the composition. It is preferably 30% by mass or more, and more preferably 50% by mass or more.
In addition, solid content means the component except a solvent, and a liquid monomer etc. are also contained.

The composition of the present invention can be prepared as a curable composition using the bisbenzotriazolylphenol compound represented by the general formula (1) as an ultraviolet absorber / crosslinking agent.
The composition of the present invention can be prepared, for example, as a composition that can be applied by melting or dissolving or dispersing in a solvent to form a liquid state (hereinafter sometimes referred to as a coating composition). it can. Such a coating composition is appropriately applied to a substrate to form a coating film, and after evaporating a solvent added as necessary, the coating film is cured as necessary. A composition formed by coating on the body surface can be formed. At this time, the thickness of the coating is not particularly limited as long as it is appropriately selected from a wide range according to the use of the article to be coated. The thickness of the coating can be, for example, about 0.1 to 30 μm, preferably about 1 to 20 μm.
Or the composition of this invention may be a composition which can be shape | molded, and may be used so that it may harden | cure after forming a molded object using various shaping | molding methods.

  For the application of the composition of the present invention, known methods can be employed, such as roll coating, gravure coating, flow coating, dip coating, spin coating, spray coating, die coating, micro gravure coating, gravure offset coating, slit reverse coating, screen. Examples include a method using a plate.

Moreover, hardening is performed by irradiating active energy rays, such as an ultraviolet-ray and an electron beam. A coating film formed from such a curable composition is cured to form a film when irradiated with active energy rays such as ultraviolet rays and electron beams. Active energy rays include ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps, usually electron beams extracted from particle accelerators of 20 to 2000 kV, α A line, a beta ray, a gamma ray, etc. can be used.
For example, when the electron beam is irradiated, the composition of the present invention is cured. In addition, when ultraviolet rays are used, it is preferable to add a photopolymerization initiator, a polymerization accelerator, a photoinitiator auxiliary, or the like to the composition of the present invention in order to quickly cure. Known photopolymerization initiators can be used, and examples thereof include acetophenone compounds, benzoin ether compounds, benzophenone compounds, thioxanthone compounds, and the like. A photoinitiator can be used individually by 1 type or in combination of 2 or more types. The content of the photopolymerization initiator is not particularly limited, but is usually about 0.1 to 30 parts by mass, preferably about 1 to 5 parts by mass with respect to 100 parts by mass of the total amount of oligomer and monomer components. And it is sufficient. As a polymerization accelerator and a photoinitiator aid, for example, triethanolamine, methyldiethanolamine, triisopropanolamine and the like can be used. The content ratio of the polymerization accelerator and the photoinitiator assistant is not particularly limited, but is usually about 0.01 to 10 parts by mass, preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the photoinitiator. Or less.

  In addition, in order to evaporate the solvent added as necessary, a known drying method such as hot air heating, infrared heating, far infrared heating or the like can be appropriately employed.

  The composition of the present invention can be applied to substantially all materials such as synthetic resin, wood, metal and ceramics by appropriately selecting the compound having an ethylenically unsaturated bond-containing group to be combined and other components. It can be applied as a composition. Among these, it is preferable to apply to synthetic resin, wood and the like.

Although there is no particular limitation as applicable synthetic resin, for example, polymethyl methacrylate resin, polycarbonate resin, polyallyl diglycidyl carbonate resin, ABS resin, polystyrene resin, polyester resin, acetate resin, polyvinyl chloride resin, epoxy resin, Examples thereof include thermoplastic resins such as acrylic resins, unsaturated polyester resins, and polyolefin resins, and thermosetting resins.
More specific synthetic resin molded products include, for example, glass substitutes for transportation equipment such as automobiles, trains and airplanes (windshields, rear windows, opera windows, triangular windows, sunroofs, etc.), lamps (head lamps, tail lamps). , Turn indicators, etc.), various meters, dials, bumpers, wheel caps and other vehicle applications represented by automotive interior and exterior components, refrigerators, vacuum cleaners, televisions, coolers and other electrical appliance applications, General equipment applications represented by parts such as computer equipment, printers, copiers, fax machines, optical discs, telephones, radios, etc., general goods applications represented by toys, furniture, packaging, sports equipment, game machine parts, daylighting boards, Building materials represented by window glass, window frames, wall materials, heat insulating materials, flooring materials, roofing materials, soundproof boards, etc., civil engineering and architectural applications, glasses, contours Trends, optics applications typified by a lens such as a camera, etc., medical device applications, general industrial material applications, the nuclear energy applications and the like.

  In addition, specific examples of wood molded products that can be applied include exterior wooden building materials, furniture, floors, toys, and the like.

  The applicable metal is not particularly limited, and examples thereof include simple substances such as iron, copper, nickel, chromium, zinc, lead, tin, titanium, and aluminum, and alloys containing at least one of these. More specific metal molded products include, for example, plates, bars, pillars, pipes, tanks, wire-like objects, frames of buildings and structures, window frames, automobile bodies of transportation equipment such as automobiles, trains, airplanes, Illumination lamps, displays, home appliances, general office equipment, furniture, toys, and the like.

  Since the bisbenzotriazolylphenol compound represented by the general formula (1) of the present invention and the composition of the present invention have a high degree of weather resistance and excellent flexibility such as tensile elongation, they are ultraviolet rays. Applications that are directly exposed to sunlight and moisture, and applications that require tensile elongation during manufacturing and use, such as window materials for transportation equipment such as building materials, automobiles, trains, airplanes, lamp covers for traffic lights, carports, It performs particularly well in soundproof walls, agricultural and industrial films and sheets, weather resistant paints for automobiles and outer walls, glass coatings, weather resistant fibers, and the like.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
The structure of the obtained compound was red using a 1H-NMR spectrum measured using a nuclear magnetic resonance apparatus (manufactured by Bruker Biospin, AVANCE III HD 500 MHz), a Fourier transform infrared spectrophotometer (Nicolet iS5 manufactured by ThermoFisher Scientific). Confirmed by external absorption spectrum.

(Synthesis Example 1: Synthesis of bisbenzotriazolylphenol compound 1 represented by the general formula (1))
Under a nitrogen atmosphere, 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] (RUVA-100: manufactured by Otsuka Chemical)
To 72.5 g (140 mmol), 47.5 g (416 mmol) of ε-caprolactone and 6.0 mg (0.01 mmol) of mono-n-butyltin fatty acid salt (SCAT-24: manufactured by Nitto Kasei) were added, and the reaction temperature was adjusted. By keeping the reaction at 150 ° C. for 6 hours, caprolactone-modified 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2) represented by the following chemical formula (A) -Hydroxyethyl) phenol] (m + n = 3) was obtained.

  86. Caprolactone-modified 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] represented by the chemical formula (A) (m + n = 3) 27.5 g (195 mmol) of 2-isocyanatoethyl acrylate (Karenzu AOI: manufactured by Showa Denko), 47.9 g of ethyl acetate and 0.044 g of p-methoxyphenol were mixed with 5 g (98 mmol), and the temperature was raised to 60 ° C. 0.95 g (0.046 mmol) of dioctyltin neodecanoate (Neostan U-830: manufactured by Nitto Kasei) diluted with ethyl acetate 30 times and reacted at 75 ° C. for 4 hours, is represented by the following chemical formula (B). The desired product (m + n = 3) was obtained.

1H-NMR (CDCl ₃ ): δ = 1.33 (m, 6H, CH ₂ ), 1.63 (m, 12H, CH ₂ ), 2.27 (m, 6H, CH ₂ ), 2.95 ( _{t, 4H, CH 2),} 3.47 (m, 4H, CH 2), 4.01 (m, 6H, CH 2), 4.22 (m, 4H, CH 2), 4.27 (s, _{2H, CH 2), 4.31 (} t, 4H, CH 2), 5.07 (2H, N-H), 5.85 (m, 2H, vinyl), 6.10 (m, 2H, vinyl) 6.40 (m, 2H, vinyl), 7.23 (s, 2H, Ar-H), 7.49 (m, 4H, Ar-H), 7.93 (m, 4H, Ar-H) 8.18 (s, 2H, Ar-H), 11.60 (s, 2H, Ar-OH)
Infrared absorption spectrum (KBr): 1714 cm ⁻¹ (urethane C═O), 1724 cm ⁻¹ (ester C═O)

(Synthesis Example 2: Synthesis of bisbenzotriazolylphenol compound 2 represented by the general formula (1))
Under a nitrogen atmosphere, 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] (RUVA-100: manufactured by Otsuka Chemical)
To 51.7 g (99 mmol), 68.2 g (598 mmol) of ε-caprolactone and 6.0 mg (0.01 mmol) of mono-n-butyltin fatty acid salt (SCAT-24: manufactured by Nitto Kasei) were added, and the reaction temperature was adjusted. By maintaining the reaction at 150 ° C. for 6 hours, the caprolactone-modified 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2) represented by the chemical formula (A) is obtained. -Hydroxyethyl) phenol] (m + n = 6) was obtained.

  Caprolactone-modified 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] represented by the chemical formula (A) (m + n = 6) 92. To 5 g (77 mmol), 17.5 g (153 mmol) of 2-isocyanatoethyl acrylate (Karenzu AOI: manufactured by Showa Denko), 47.9 g of ethyl acetate and 0.044 g of p-methoxyphenol were mixed, and the temperature was raised to 60 ° C. In addition, 0.95 g (0.046 mmol) of ethyl acetate 30-fold diluted solution of dioctyltin neodecanoate (Neostan U-830: manufactured by Nitto Kasei) was added and reacted at 75 ° C. for 4 hours, thereby being represented by the chemical formula (B). The desired product (m + n = 6) was obtained.

1H-NMR (CDCl ₃ ): δ = 1.33 (m, 12H, CH ₂ ), 1.62 (m, 24H, CH ₂ ), 2.27 (m, 12H, CH ₂ ), 2.95 ( _{t, 4H, CH 2),} 3.48 (m, 4H, CH 2), 4.02 (m, 12H, CH 2), 4.23 (m, 4H, CH 2), 4.27 (s, _{2H, CH 2), 4.31 (} t, 4H, CH 2), 5.06 (2H, N-H), 5.87 (m, 2H, vinyl), 6.13 (m, 2H, vinyl) 6.43 (m, 2H, vinyl), 7.24 (s, 2H, Ar-H), 7.49 (m, 4H, Ar-H), 7.94 (m, 4H, Ar-H) 8.18 (s, 2H, Ar-H), 11.60 (s, 2H, Ar-OH)
Infrared absorption spectrum (KBr): 1726 cm ⁻¹ (ester + urethane C═O)

(Synthesis Example 3: Synthesis of bisbenzotriazolylphenol compound 3 represented by the general formula (1))
Under a nitrogen atmosphere, 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] (RUVA-100: manufactured by Otsuka Chemical)
To 37.4 g (72 mmol), 82.5 g (723 mmol) of ε-caprolactone and 6.0 mg (0.01 mmol) of mono-n-butyltin fatty acid salt (SCAT-24: manufactured by Nitto Kasei) were added, and the reaction temperature was adjusted. By maintaining the reaction at 150 ° C. for 6 hours, the caprolactone-modified 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2) represented by the chemical formula (A) is obtained. -Hydroxyethyl) phenol] (m + n = 10) was obtained.

  Caprolactone-modified 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] represented by the chemical formula (A) (m + n = 10) 96. 7 g (58 mmol) was mixed with 13.3 g (116 mmol) of 2-isocyanatoethyl acrylate (Karenz AOI: Showa Denko), 47.9 g of ethyl acetate, and 0.044 g of p-methoxyphenol, and the temperature was raised to 60 ° C. In addition, 0.95 g (0.046 mmol) of ethyl acetate 30-fold diluted solution of dioctyltin neodecanoate (Neostan U-830: manufactured by Nitto Kasei) was added and reacted at 75 ° C. for 4 hours, thereby being represented by the chemical formula (B). The desired product (m + n = 10) was obtained.

1H-NMR (CDCl ₃ ): δ = 1.33 (m, 20H, CH ₂ ), 1.63 (m, 40H, CH ₂ ), 2.27 (m, 20H, CH ₂ ), 2.95 ( _{t, 4H, CH 2),} 3.48 (m, 4H, CH 2), 4.01 (m, 20H, CH 2), 4.23 (m, 4H, CH 2), 4.27 (s, _{2H, CH 2), 4.31 (} t, 4H, CH 2), 5.06 (2H, N-H), 5.87 (m, 2H, vinyl), 6.13 (m, 2H, vinyl) 6.43 (m, 2H, vinyl), 7.24 (s, 2H, Ar-H), 7.49 (m, 4H, Ar-H), 7.94 (m, 4H, Ar-H) 8.18 (s, 2H, Ar-H), 11.60 (s, 2H, Ar-OH)
Infrared absorption spectrum (KBr): 1728 cm ⁻¹ (ester + urethane C═O)

(Comparative Synthesis Example 1: Synthesis of Comparative Bisbenzotriazolylphenol Compound 1)
2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] (RUVA-100: manufactured by Otsuka Chemical Co., Ltd.) (76.6 g, 147 mmol) -31.4 g (293 mmol) of isocyanatoethyl acrylate (Karenz AOI: Showa Denko), 47.9 g of ethyl acetate and 0.044 g of p-methoxyphenol were mixed, heated to 60 ° C, and dioctyltin neodecanoate (Neostan U) -830: manufactured by Nitto Kasei Co., Ltd.) 0.95 g (0.046 mmol) of a 30-fold diluted ethyl acetate solution and reacted at 75 ° C. for 4 hours, so that no caprolactone chain was introduced. Zolylphenol compound 1 (Comparative compound 1) was synthesized.

1H-NMR (DMSO-d6) : δ = 2.93 (t, 4H, CH 2), 3.24 (t, 4H, CH 2), 4.07 (s, H, CH2), 4.18 ( _{t, 4H, CH 2),} 4.19 (t, 4H, CH 2), 5.60 (s, 2H, vinyl), 6.01 (s, 2H, vinyl), 6.46 (s, 2H, Vinyl), 7.26 (s, 2H, Ar-H), 7.53 (m, 4H, Ar-H), 8.02 (s, 2H, Ar-H), 8.07 (m, 4H, Ar-H), 11.05 (s, 2H, Ar-OH)
Infrared absorption spectrum (KBr): 1699 cm ⁻¹ (urethane C═O), 1717 cm ⁻¹ (ester C═O)

(Comparative Synthesis Example 2: Synthesis of Comparative Bisbenzotriazolylphenol Compound 2)
In Synthesis Example 2, a terminal acryloyl group using an isocyanate compound was prepared in the same manner as in Synthesis Example 2 except that 17.5 g (153 mmol) of 2-isocyanatoethyl acrylate (Karenz AOI: Showa Denko) was not reacted. Comparative bisbenzotriazolylphenol compound 2 (m + n = 6 in the following formula) (comparative compound 2) having the following chemical formula, which was not introduced, was synthesized.

1H-NMR (CDCl ₃ ): δ = 1.34 (m, 12H, CH2), 1.61 (m, 24H, CH2), 2.27 (m, 12H, CH2), 2.95 (t, 4H) , CH2), 3.59 (m, 4H, CH2), 4.02 (m, 8H, CH2), 4.27 (s, 2H, CH2), 4.31 (t, 4H, CH2), 7. 24 (s, 2H, Ar-H), 7.49 (m, 4H, Ar-H), 7.93 (m, 4H, Ar-H), 8.18 (s, 2H, Ar-H), 11.60 (s, 2H, Ar-OH)
Infrared absorption spectrum (KBr): 1725 cm ⁻¹ (ester C═O)

Example 1
(1) Preparation of Composition 1 A composition having the following composition was prepared.
Urethane acrylate (purple UV-6300B, average functional group number = 7, manufactured by Nippon Synthetic Chemical Co., Ltd.): 100 parts by mass Bisbenzotriazolylphenol compound 1 of Synthesis Example 1 10 parts by mass Solvent (ethyl acetate): 30 parts by mass

(2) Production of cured film of composition The composition 1 was applied to an easy-adhesion PET film (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm so that the film thickness after drying was 5 μm, and then dried and coated. A film was formed.
The coating film was irradiated with an electron beam under the conditions of 165 kV and 50 kGy to obtain a film having a cured film of the composition coated on the surface.

(Examples 2-3, Comparative Examples 1-2)
In each example, as shown in Table 2, the bisbenzotriazolylphenol compound to be used was changed, and the amount of the bisbenzotriazolylphenol compound used was changed to be an equimolar amount as in Example 1. Except for the above, a composition was prepared in the same manner as in Example 1, and a film having a cured film of the composition coated on the surface was obtained.

[Evaluation method]
(1) Tensile elongation A film having a surface coated with a cured film of the composition is cut into a size of 2.5 cm × 10 cm, and the sample is chucked using a tensile tester (AUTOGRAPH AG-X manufactured by Shimadzu Corporation). A tensile test was performed at a distance of 5 cm and a pulling speed of 50 mm / min. The presence or absence of cracks on the surface of the cured film was confirmed after 30% tension.
<Evaluation criteria>
○: No crack occurred ×: Crack occurred

(2) Bleed-out suppression The film by which the cured film of the composition was coat | covered was cut out to the magnitude | size of 10 cm x 10 cm, and the said sample was immersed in 40 degreeC warm water for one month. The surface of the cured film immersed for 1 month was visually observed and palpated to evaluate the presence or absence of bleed.
<Evaluation criteria>
○: Bleed-out cannot be confirmed Δ: Slightly bleed-out, but practically no problem ×: Remarkably bleed-out, appearance significantly impaired

(3) Weather resistance A film coated with a cured film of the composition was cut into a size of 5 cm × 5 cm, and the sample was subjected to a super UV weather resistance tester (Isuperki UV Tester SUV-W161, manufactured by Iwasaki Electric Co., Ltd.). The degree of discoloration of the base material (PET film) when it was put in 200 illuminance (illuminance 100 mW / cm ² ) for 200 hours was evaluated. In the super UV weather resistance tester, after 200 hours of ultraviolet irradiation, water was sprayed (shower) for 30 seconds, and a 4-hour condensation was performed as one cycle, and a 200-hour weather resistance test was performed.
<Evaluation criteria>
○: Appearance change cannot be confirmed Δ: Substrate (PET film) is slightly discolored ×: Substrate (PET film) is discolored significantly, and cracking of the substrate was confirmed

(Summary of results)
In Examples 1 to 3 using the bisbenzotriazolylphenol compound represented by the general formula (1) of the present invention, bleed-out is suppressed even in a use environment where moisture exists, and light and moisture are used. It was shown that the UV absorption function is excellent in the long-term sustainability even under the usage environment that is affected by the above. The bisbenzotriazolylphenol compound represented by the general formula (1) of the present invention includes two aliphatic hydrocarbon chains between two (meth) acryloyl groups and bisbenzotriazolylphenol, Since it has a lactone chain, the dispersibility in the cured film and the reaction efficiency of the crosslinking reaction are enhanced, and it is presumed that the above effect is exhibited. Further, Examples 1 to 3 using the bisbenzotriazolylphenol compound represented by the general formula (1) of the present invention are improved in flexibility and elasticity of the cured film, and superior in tensile elongation than before. It was shown to have sex. The bisbenzotriazolylphenol compound represented by the general formula (1) of the present invention includes not only an aliphatic hydrocarbon chain between two (meth) acryloyl groups and a bisbenzotriazolylphenol compound, Since it has a lactone chain, the lactone chain is incorporated into a crosslinked structure formed by polymerizable compounds having an ethylenically unsaturated bond-containing group, thereby imparting flexibility and elasticity to the crosslinked structure, Presumed to have excellent tensile elongation.

  On the other hand, the bisbenzotriazolylphenol compound of Comparative Example 1 corresponding to the compound of Patent Document 3 does not have a lactone chain between two (meth) acryloyl groups and bisbenzotriazolylphenol. It was shown that the tensile elongation was inferior and the bleed-out suppression and the weather resistance were inferior. It is estimated that the reaction efficiency of the (meth) acryloyl group is inferior in the bisbenzotriazolylphenol compound of Comparative Example 1. Further, Comparative Example 2 using a bisbenzotriazolylphenol compound having a lactone chain but not having a terminal (meth) acryloyl group was shown to be inferior in terms of bleed-out suppression and weather resistance.

Claims (3)

A bisbenzotriazolylphenol compound represented by the following general formula (1).
(In General Formula (1), Q represents a methylene group, an ethylidene group, an isopropylidene group, or a sec-butylidene group. R ¹ , R ² , R ³ , and R ⁴ each independently represent 1 or more carbon atoms. 6 or less linear or branched aliphatic hydrocarbon groups, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, or Represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, n and m are each independently a number of 1 to 10 and n + m = 2 to 20; p and q are each independently 3 The number is from 5 to 5. r and s are each independently from 1 to 2.   An ultraviolet absorber containing the bisbenzotriazolylphenol compound according to claim 1.   A composition comprising the ultraviolet absorber according to claim 2 and a polymerizable compound having an ethylenically unsaturated bond-containing group.