JP6910862B2 - Bisbenzotriazolylphenol compounds, UV absorbers, and compositions - Google Patents

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.

An ultraviolet absorber is used as a means for improving the weather resistance of a resin or giving the resin an ultraviolet ray shielding property.

However, conventional UV absorbers have a high vapor pressure due to their small molecule, and when they are blended with a resin and molded, the yield decreases due to volatilization, which causes mold contamination and worker health damage. Or In addition, it bleeds out from the surface of the molded product or coating film over time, or elutes with rain or water containing detergent in the usage environment, which impairs the appearance of the product and at the same time imparts long-term photostability to the product. It is known to be difficult to do.

As a solution to such a problem, an ultraviolet absorber having improved compatibility with plastics by having a long-chain alkyl group, a long-chain alkenyl group or a long-chain alkylene oxide chain having an appropriate length has been developed. (Patent Document 1).

Further, as a solution to such a problem, a base resin is obtained by combining an ultraviolet absorbing urethane resin obtained by reacting a polyester polyol having an ultraviolet absorbing group with a polyisocyanate, 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).

Further, as a solution to such a problem, an ultraviolet absorber composed 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 as an ultraviolet absorber and a cross-linking agent, and since it has a carbamoyloxy unit in the molecule, it is flexible to the cured resin used as a cross-linking agent. It is said to give sex.

However, the compound described in Patent Document 3 is likely to bleed out in a usage environment in which moisture is present, which may spoil the appearance of the product, and is also affected by weather resistance, that is, light and moisture at the same time. There was still a problem with the long-term sustainability of photostability under the usage environment. Further, the flexibility of the cured resin using the compound described in Patent Document 3 as a cross-linking agent, for example, tensile extensibility, is still insufficient, and further improvement in flexibility is required.

Japanese Unexamined Patent Publication No. 2000-230077 Japanese Unexamined Patent Publication No. 2003-128986 Japanese Unexamined Patent Publication No. 2004-2317

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 usage environment in which moisture is present, has excellent weather resistance, and can improve flexibility such as tensile elongation of a cured resin. It is an object of the present invention to provide a novel bisbenzotriazolylphenol compound. Another object of the present invention is to provide an ultraviolet absorber containing the novel compound and a composition containing the ultraviolet absorber.

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

（一般式（１）中、Ｑは、メチレン基、エチリデン基、イソプロピリデン基、又はsec-ブチリデン基を表す。Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４はそれぞれ独立に、炭素数１以上６以下の直鎖又は分岐状脂肪族炭化水素基を表し、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又はメチル基を表す。Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、ハロゲン原子、又は炭素数１以上４以下の脂肪族炭化水素基を表す。ｎ及びｍはそれぞれ独立に、１以上１０以下の数であり、ｎ＋ｍ＝２以上２０以下である。ｐ及びｑはそれぞれ独立に、３以上５以下の数である。ｒ及びｓはそれぞれ独立に、１以上２以下の数である。）

(In the 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 have 1 or more carbon atoms. Represents a linear or branched aliphatic hydrocarbon group of 6 or less, R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively. R ⁷ and R ⁸ independently represent a hydrogen atom, a halogen atom, or a halogen atom, respectively. Represents an aliphatic hydrocarbon group having 1 or more and 4 or less carbon atoms. N and m are independently numbers of 1 or more and 10 or less, and n + m = 2 or more and 20 or less. P and q are independently 3 and 3 respectively. or 5 in which .r及beauty s is the number of following each independently a number of 1 or more and 2 or less.)

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 containing 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 usage environment in which moisture is present, has excellent weather resistance, and can improve flexibility such as tensile elongation of a cured resin. A useful novel bisbenzotriazolylphenol compound can be provided. Further, it is possible to provide an ultraviolet absorber containing the novel compound and a composition containing the ultraviolet absorber.

Hereinafter, embodiments of the novel bisbenzotriazolylphenol compound of the present invention and the composition containing the novel compound as an ultraviolet absorber will be described.
In the present invention, (meth) acrylic represents each of acrylic and methacrylic, (meth) acryloyl represents each of acryloyl and methacrylic, 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).

（一般式（１）中、Ｑは、メチレン基、エチリデン基、イソプロピリデン基、又はsec-ブチリデン基を表す。Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４はそれぞれ独立に、炭素数１以上６以下の直鎖又は分岐状脂肪族炭化水素基を表し、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又はメチル基を表す。Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、ハロゲン原子、又は炭素数１以上４以下の脂肪族炭化水素基を表す。ｎ及びｍはそれぞれ独立に、１以上１０以下の数であり、ｎ＋ｍ＝２以上２０以下である。ｐ及びｑはそれぞれ独立に、３以上５以下の数である。ｒ及びｓはそれぞれ独立に、１以上２以下の数である。）

(In the 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 have 1 or more carbon atoms. Represents a linear or branched aliphatic hydrocarbon group of 6 or less, R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively. R ⁷ and R ⁸ independently represent a hydrogen atom, a halogen atom, or a halogen atom, respectively. Represents an aliphatic hydrocarbon group having 1 or more and 4 or less carbon atoms. N and m are independently numbers of 1 or more and 10 or less, and n + m = 2 or more and 20 or less. P and q are independently 3 and 3 respectively. or 5 in which .r及beauty s is the number of following each independently a number of 1 or more and 2 or less.)

The bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has a large molecular extinction coefficient, so that it has good ultraviolet absorption performance, an extremely low vapor pressure, and a high thermal stability. Therefore, volatilization is suppressed even when mixed with a resin, and stable mixing can be performed without decomposition, which 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 UV absorber itself functions as a cross-linking agent, so that it has excellent weather resistance and UV shielding without reducing the cross-linking density. Gender can be imparted.

Further, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has 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 a usage environment where moisture is present, and it is weather resistant, that is, long-term sustainability of photostability in a usage environment where it is affected by light and moisture at the same time. Is excellent.
This is unclear, but is presumed as follows.
The bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has two aliphatic hydrocarbon chains and caprolactone between the (meth) acryloyl group and bisbenzotriazolylphenol. It has a lactone chain such as a chain. Since the bisbenzotriazolylphenol compound is bulky, it has conventionally been easily aggregated and unevenly distributed in the coating film. On the other hand, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has two long-chain substituents, and therefore has an advantage that it is difficult to aggregate and unevenly distributed. Further, since one long-chain substituent 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 and is efficient. It is easy to exert its function as an ultraviolet 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 existing 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 difficult to aggregate, easily dispersed in the resin, and contains an ethylenically unsaturated bond possessed by another molecule. Since the reaction efficiency with the group is improved, it is difficult to bleed out even in a usage environment where moisture is present, and even in a usage environment where it is affected by light and moisture at the same time, the UV absorption function is long-term. It is presumed to have excellent sustainability.

Further, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) is not limited to 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 the polymerizable compound having an ethylenically unsaturated bond-containing group has flexibility and elasticity. Is improved, and it is possible to have better tensile elongation than before.

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

When r and s are 1, respectively, R ³ and R ⁴ include straight-chain or branched aliphatic hydrocarbon groups having a divalent carbon number of 1 to 6 and are listed in R ¹ and R ² , respectively. A group similar to a linear or branched aliphatic hydrocarbon group having 1 or more and 6 or less carbon atoms can be preferably used.
When r and s are 2 respectively, R ³ and R ⁴ are trivalent linear or branched aliphatic hydrocarbon groups having 1 or more and 6 or less carbon atoms, respectively, and have 1 or more and 6 or less carbon atoms. Included are residues from which three hydrogen atoms have been removed from chains or branched aliphatic hydrocarbons. ^{As R 3} and R ⁴ when r and s are 2, for example, a trivalent aliphatic hydrocarbon group listed in the following chemical structural formula is preferably used.
When r and s are 2 independently, 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 the other molecule is improved.

R ¹ , R ² , R ³ and R ⁴ may be the same or different, respectively, but from a manufacturing point of view, R ¹ and R ² are preferably the same, and R ³ and R ^{4 are the same.} Is preferably the same.

Although R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, hydrogen atoms are preferable because the reaction efficiency is improved.

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, chlorine atoms and bromine atoms are preferable.
Examples of the aliphatic hydrocarbon group having 1 or more and 4 or less carbon atoms in R ⁷ and R ⁸ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl group and the like.

p and q are independently numbers of 3 or more and 5 or less. That is, the bisbenzotriazolylphenol compound represented by the general formula (1) is a lactone chain which is a ring-opening addition polymerization chain of at least one lactone of γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Includes. Ring-opening addition polymerization of γ-butyrolactone gives compounds with p and q of 3, ring-opening addition polymerization of δ-valerolactone gives compounds with p and q of 4, and ring-opening addition polymerization of ε-caprolactone. A compound having p and q of 5 is obtained. When two or more kinds of lactones are mixed and 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 independently 1 or more and 10 or less. n and m represent the degree of polymerization (number of moles added) of the lactone, respectively, and n and m may be average values, respectively. n and m are appropriately determined depending on the application, considering whether it is necessary to further improve the flexibility and tensile extensibility by the lactone chain, or whether it is necessary to increase the hardness while improving the tensile extensibility. You can choose. Above all, from the viewpoint of improving flexibility such as tensile elongation, n and m are each independently preferably having an average of 1.5 or more, and on the other hand, from the viewpoint of improving hardness, it is preferably 8 or less. It is more preferably 6 or less, and even more 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, it is preferably 16 or less from the viewpoint of improving hardness. , 12 or less is more preferable, and 10 or less is even more preferable.

Specific examples of the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) include compounds in the following combinations.
In the compounds of the following combinations, there are cases where p and q are 5 and r and s are 1 respectively.
Further, in the compounds of the following combinations, there are cases where p and q are 5 and r and s are 2 respectively.
Further, in the compounds of the following combinations, there are cases where p and q are 4 and r and s are 1 each, and cases where 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, an alcoholic hydroxyl group of the bisbenzotriazolylphenol compound represented by the general formula (2), ε-caprolactone or the like. The lactone can be produced by ring-opening addition polymerization and further reacting the alcoholic hydroxyl group of the lactone chain with an isocyanate compound having a (meth) acryloyloxy group in a solvent.

（一般式（２）中、Ｑ、Ｒ^１、Ｒ^２、Ｒ^７及びＲ^８は、一般式（１）と同じである。）

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

Examples of the bisbenzotriazolylphenol compound represented by the general formula (2) used here include 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (hydroxy). Methyl) phenol], 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2-hydroxyethyl) phenol], 2,2'-methylene-bis [6-( 5-Chloro-2H-benzotriazole-2-yl) -4- (2-hydroxyethyl) phenol], 2,2'-methylene-bis [6- (5-bromo-2H-benzotriazole-2-yl) -4- (2-Hydroxyethyl) phenol], 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (3-hydroxypropyl) phenol], 2,2'- Methylene-bis [6- (5-chloro-2H-benzotriazole-2-yl) -4- (3-hydroxypropyl) phenol], 2,2'-methylene-bis [6- (5-bromo-2H-) Benzotriazole-2-yl) -4- (3-hydroxypropyl) phenol], 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2-hydroxypropyl) phenol ], 2,2'-Methylene-bis [6- (5-chloro-2H-benzotriazole-2-yl) -4- (2-hydroxypropyl) phenol], 2,2'-methylene-bis [6-- (5-Bromo-2H-benzotriazole-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-benzotriazole-2-yl) -4- (4-hydroxybutyl) phenol], 2,2' -Methylene-bis [6- (5-bromo-2H-benzotriazole-2-yl) -4- (4-hydroxybutyl) phenol], 3,3- [2,2'-bis [6- (2H-) Benzotriazole-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 and the like are preferably used.
The bisbenzotriazolylphenol compound represented by the general formula (2) can be appropriately prepared by a conventionally known method.

As a method for 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 mixed at 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, a lactone such as ε-caprolactone can be ring-opened and addition-polymerized on 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 salts; stannous chloride, stannous bromide, stannous iodide, and the like. Stannous halides; organic titanium compounds such as tetraethyl titanate, tetrabutyl titanate, and tetrapropyl titanate; and the like. The amount of the catalyst used is preferably 0.01 mol% or more and 2 mol% or less, and more preferably 0.02 mol% or more and 1.2 mol% or less with respect to 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.

Examples of the isocyanate compound having a (meth) acryloyloxy group include (meth) acryloyloxymethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl isocyanate, and 2- (meth) acryloyloxypropyl isocyanate. , 4- (Meta) acryloyloxybutyl isocyanate, 1,1- (bis-acryloyloxymethyl) ethyl isocyanate and the like are preferably used.

The solvent used when reacting the alcoholic hydroxyl group of the lactone chain with the isocyanate compound having a (meth) acryloyloxy group in the solvent is not particularly limited, but is not particularly limited, such as methyl ethyl ketone and methyl isopropyl ketone. A ketone solvent, an aromatic hydrocarbon solvent such as benzene, toluene and xylene, and an aproton solvent such as an ether solvent such as dibutyl ether and dioxane can be appropriately used alone or in combination of two or more. 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, but is usually a bisbenzotriazolylphenol compound represented by the general formula (2). It is preferably 100 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass. The reaction temperature is appropriately selected in the range of 20 ° C. or higher and 150 ° C. or lower, preferably 30 ° C. or higher and 100 ° C. or lower, depending on the type of solvent.

As described above, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has good ultraviolet absorption performance, volatilization is suppressed even when mixed with a resin, and it does not decompose. It is useful as an additive-type ultraviolet absorber because it can be stably mixed with.
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 a side chain by utilizing a (meth) acryloyloxy group. It may be used as a monomer of.
Further, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) has two (meth) acryloyloxy groups in a state of high reaction efficiency, and therefore functions well as a cross-linking agent. As will be described later, it is preferable to use it together with a polymerizable compound having an ethylenically unsaturated bond-containing group to obtain an ultraviolet-absorbing active ingredient in a curable composition.

II. Ultraviolet absorber The ultraviolet absorber of the present invention contains a bisbenzotriazolylphenol compound represented by the general formula (1).
The ultraviolet absorber of the present invention preferably contains the bisbenzotriazolylphenol compound represented by the general formula (1) in an amount of 50% by mass or more, more preferably 70% by mass or more, and even more. It is preferably contained in an amount of 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 kind or two or more kinds.
In addition, other components that may be contained in the ultraviolet absorber of the present invention include, for example, other ultraviolet absorbers. Examples of other ultraviolet absorbers include benzophenone compounds, triazine compounds, cyanoacrylate compounds, benzoxazine compounds, benzoxazole compounds, merocyanine compounds, or a plurality of compounds in which these compounds are arbitrarily combined. And so on.

III. Composition The composition of the present invention contains an ultraviolet absorber containing a 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 a polymer (high polymer), an oligomer (low polymer), and the like. 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 an ethylenically unsaturated bond-containing group containing a (meth) acryloyloxy group possessed by the ultraviolet absorber of the present invention by irradiation with an active energy ray such as an ultraviolet ray or an electron beam. Reacts with, polymerizes or crosslinks to form a cured product.
Examples of the ethylenically unsaturated bond-containing group include a vinyl group, an allyl group, a (meth) acryloyloxy group and the like. 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 a polymerizable compound having at least one ethylenically unsaturated bond-containing group in one molecule, known ones can be used, but one molecule has at least two (meth) acryloyloxy groups ( Meta) At least one selected from an acrylate-based oligomer and a monomer having at least one ethylenically unsaturated bond-containing group in one molecule is preferably used. Above all, from the viewpoint of improving the crosslink density, it is preferable that one molecule contains a compound having at least three ethylenically unsaturated bond-containing groups.

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

Examples of the polyfunctional polyester (meth) acrylate-based oligomer having at least two (meth) acryloyloxy groups in one molecule include compounds synthesized from (meth) acrylic acid, polyhydric alcohols and polybasic acids (anhydrous). Etc. can be used. Further, as the polyfunctional urethane (meth) acrylate-based oligomer having at least two (meth) acryloyloxy groups in one molecule, for example, a compound obtained by the reaction of polyisocyanate, polyol and hydroxy (meth) acrylate is used. can. Further, as the polyfunctional epoxy (meth) acrylate-based 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 and the like can be used. Can be used. Further, as the polyfunctional ether (meth) acrylate-based oligomer having at least two (meth) acryloyloxy groups in one molecule, for example, a polyether obtained by reacting a polyol with ethylene oxide, propylene oxide or the like, and ethyl. A compound or the like obtained by an ester exchange reaction with (meth) acrylate can be used. Each of the above oligomers can be used alone or in admixture of two or more. In particular, 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 vinyl monomers such as N-vinylpyrrolidone, N-vinylcaprolactone, vinylimidazole, vinylpyridine, and styrene as monofunctional monomers, and phenoxyethyl. (Meta) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxydi Propropylene glycol (meth) acrylate, baracmilphenoxyethyl (meth) acrylate, nonylphenoxyboliethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) Acrylate, (meth) acrylic acid ester monomers such as orthophenylphenoxyethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylate, acryloylmorpholin, and (meth) acrylamide. Derivatives can be mentioned. Examples of the polyfunctional monomer 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, and 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, neoventyl glycol di (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, neoventyl glycol di (meth) acrylate of hydroxypivalate, bisphenol A polyethoxy Didioldi (meth) acrylate, bisphenol A polypropoxydiol di (meth) acrylate, trimethylolpropoxydiol di (meth) acrylate, trimethylolytic propanetri (meth) acrylate, propoxylated trimethylol brobantry (meth) acrylate, penta Erislithol tri (meth) acrylate, glyceryl tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra Examples thereof include (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Further, as the polymerizable compound having an ethylenically unsaturated bond-containing group, a polymer having an ethylenically unsaturated bond-containing group in the side chain of the repeating unit may be used, and is represented by the following general formula (3). Polymers containing repeating units can be mentioned.

（式中Ｒ’は水素原子又はメチル基を表し、Ｐはエチレン性不飽和結合含有基を含む一価の基であり、Ｌは単結合又は二価の連結基である。）

(In the formula, R'represents a hydrogen atom or a methyl group, P is a monovalent group containing 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-, -NHCO-.
Further, P is a monovalent group containing an ethylenically unsaturated bond-containing group such as a vinyl group and a (meth) acryloyl group. Specific examples of combinations of the repeating units L and P represented by the general formula (3) are shown below, but the present invention is not limited thereto. Examples of other repeating units include the repeating units described in paragraphs 0034 to 0038 of JP-A-2003-147017, and the preparation of a polymer containing such repeating units is described in JP-A-2003-147017. It can be prepared with reference to paragraphs 0039 to 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. It may have more repeating units. The monomer having an ethylenically unsaturated bond-containing group used in the copolymer is not particularly limited, and can be appropriately selected from various viewpoints such as hardness, solubility in 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 and the like. Vinyl esters, methyl (meth) acrylates, ethyl (meth) acrylates, hydroxyethyl (meth) acrylates, glycidyl methacrylates, (meth) acrylates such as (meth) acryloyloxypropyltrimethoxysilane, styrene, p-hydroxymethyl Examples thereof include styrene derivatives such as styrene, unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, and itaconic acid, and derivatives thereof. The polymer containing the repeating unit represented by the general formula (3) may be an alkali-soluble resin containing an acid group.

From the viewpoint of increasing the hardness of the polymer containing the repeating unit represented by the general formula (3), the 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 50% by mass or more and 100% by mass or less, and particularly preferably 70% by mass or more and 100% by mass or less.

The preferable molecular weight range of the polymer containing the repeating unit represented by the general formula (3) is 1000 or more and 1 million or less in terms of mass average molecular weight, and more preferably 3000 or more and 200,000 or less. Most preferably, it is 5,000 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. Examples include silane coupling agents. 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 capable of reacting with an alkoxysilyl group. By applying it to a substrate having a surface and curing it, the ultraviolet shielding effect can be improved.

As the compound having an ethylenically unsaturated bond-containing group contained in the composition, one kind alone or two or more kinds can be used together.

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, and polystyrene resin. , Polyene resin, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone, liquid crystal plastic and other known resins can be used alone or in admixture of two or more.

Further, in the composition of the present invention, 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, etc. Various additives and solvents such as antibacterial agents, fillers, pigments, dyes and colorants can be contained.

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

The content ratio of the ultraviolet absorber of the present invention in the composition of the present invention is not particularly limited, and the purpose of use of the obtained composition, the material of the base material to which the composition is applied, the shape of the base material, and after curing of the composition It may be appropriately selected from a wide range in consideration of various conditions such as hardness, film thickness, long-term weather resistance after curing, metal ionic resistance, degree of transparency, and molar absorption coefficient of an ultraviolet absorbing compound. 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, based on 100% by mass of the solid content of the composition. It is desirable to use it in the range of mass% or less. When the ratio of the ultraviolet absorber of the present invention used is 0.1% by mass or more, the weather resistance of the cured product obtained from the composition can be easily improved, and when it is 50% by mass or less, the curing obtained from the composition can be easily improved. The basic physical properties of the object are good. Further, 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 obtained composition, the material of the base material to which the composition is applied, and the shape of the base material , The composition may be appropriately selected from a wide range in consideration of various conditions such as hardness after curing. The content ratio 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 used, and is preferably 30% by mass or more, and more preferably 50% by mass or more.
The solid content refers to a component excluding the solvent, and also includes a liquid monomer and the like.

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 and a cross-linking agent.
The composition of the present invention can be prepared as a composition that can be applied (hereinafter, may be referred to as a coating composition) by, for example, melting or dissolving or dispersing in a solvent to make it in a liquid state. can. Such a coating composition is appropriately applied to an object to be coated to form a coating film, and after evaporating the solvent added as necessary, the coating film is cured as necessary to be coated. A composition formed by coating on the body surface can be formed. At this time, the thickness of the coating film may be appropriately selected from a wide range according to the intended use of the object to be coated, and is not particularly limited. The thickness of the coating film can be, for example, about 0.1 μm or more and 30 μm or less, preferably about 1 μm or more and 20 μm or less.
Alternatively, the composition of the present invention may be a moldable composition, or may be used so as to be cured after forming a molded product using various molding methods.

Known methods can be adopted for applying the composition of the present invention, for example, roll coating, gravure coating, flow coating, dip coating, spin coating, spray coating, die coating, micro gravure coating, gravure offset coating, slit reverse coating, screen. The method by the plate can be mentioned.

Further, curing is performed by irradiating with active energy rays such as ultraviolet rays and electron beams. The coating film formed from such a curable composition is cured and formed into 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, electron beams usually extracted from particle accelerators of 20 to 2000 kV, and α. Lines, β-rays, γ-rays and the like can be used.
For example, when irradiated with an electron beam, the composition of the present invention is cured. When ultraviolet rays are used, it is preferable to add a photopolymerization initiator, a polymerization accelerator, a photoinitiator aid, or the like to the composition of the present invention in order to carry out curing quickly. As the photopolymerization initiator, known ones can be used, and examples thereof include acetophenone-based compounds, benzoin ether-based compounds, benzophenone-based compounds, and thioxanthone-based compounds. The photopolymerization initiator may be used alone or in combination of two or more. The content ratio of the photopolymerization initiator is not particularly limited, but is usually about 0.1 part by mass or more and 30 parts by mass or less, preferably about 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of the oligomer and the monomer component. And it is sufficient. As the polymerization accelerator and photoinitiator, for example, triethanolamine, methyldiethanolamine, triisopropanolamine and the like can be used. The content ratio of the polymerization accelerator and the photoinitiator is not particularly limited, but is usually about 0.01 part by mass or more and 10 parts by mass or less, preferably 0.5 parts by mass or more and 3 parts by mass with respect to 100 parts by mass of the photopolymerization initiator. The number may be less than or equal to the number of copies.

Further, in order to evaporate the solvent added as needed, known drying methods such as hot air heating, infrared heating, and far infrared heating can be appropriately adopted.

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

The synthetic resin that can be applied is not particularly limited, and for example, polymethylmethacrylate resin, polycarbonate resin, polyallyl diglycidyl carbonate resin, ABS resin, polystyrene resin, polyester resin, acetate resin, polyvinyl chloride resin, epoxy resin, etc. 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 (front glass, rear window, opera window, triangular window, sun roof, etc.), lamps (head lamps, tail lamps, etc.). , Direction indicators, etc.), vehicle applications such as interior and exterior parts for automobiles such as various meters, dials, bumpers, wheel caps, electric appliances such as refrigerators, vacuum cleaners, televisions, coolers, etc. General equipment applications such as computer equipment, printers, copying machines, fax machines, optical disks, telephones, radios, etc., miscellaneous goods applications such as toys, furniture, packaging, sports equipment, game machine parts, etc. Building materials such as window glass, window frames, wall materials, heat insulating materials, flooring materials, roofing materials, soundproof boards, etc. Examples include equipment applications, general industrial material applications, and nuclear-related applications.

Specific examples of applicable wood molded products include exterior wood 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, rods, pillars, pipes, tanks, wire-like objects, frames of buildings and structures, window frames, car bodies of transportation equipment such as automobiles, trains, and airplanes. Examples include lighting, indicators, home appliances, general office equipment, furniture, toys, and the like.

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 have excellent flexibility such as tensile elongation, so that 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 building materials, window materials for transportation equipment such as automobiles, trains, and airplanes, lamp covers for traffic lights, carports, etc. It is particularly effective in soundproof walls, agricultural and industrial films and sheets, weather-resistant paints for automobiles and outer walls, glass coatings, weather-resistant fibers, etc.

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 is red using a 1H-NMR spectrum measured using a nuclear magnetic resonance apparatus (Bruker Biospin, AVANCE III HD500 MHz) and 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-benzotriazole-2-yl) -4- (2-hydroxyethyl) phenol] (RUVA-100: manufactured by Otsuka Chemical Co., Ltd.)
To 72.5 g (140 mmol), add 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) to adjust the reaction temperature. Caprolactone-modified 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2) represented by the following chemical formula (A) by keeping the temperature at 150 ° C. and reacting for 6 hours. -Hydroxyethyl) phenol] (m + n = 3) was obtained.

Caprolactone-modified 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2-hydroxyethyl) phenol] represented by the chemical formula (A) (m + n = 3) 87. 27.5 g (195 mmol) of 2-isocyanatoethyl acrylate (Carens AOI: Showa Denko), 47.9 g of ethyl acetate, and 0.044 g of p-methoxyphenol were mixed with 5 g (98 mmol) and heated to 60 ° C. , Dioctyl tin neodecanoate (Neostan U-830: manufactured by Nitto Kasei), added 0.95 g (0.046 mmol) of ethyl acetate 30-fold diluted solution, and reacted at 75 ° C. for 4 hours, represented by the following chemical formula (B). Of the compounds, the target 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, NH), 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-benzotriazole-2-yl) -4- (2-hydroxyethyl) phenol] (RUVA-100: manufactured by Otsuka Chemical Co., Ltd.)
To 51.7 g (99 mmol), add 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) to adjust the reaction temperature. Caprolactone-modified 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2) represented by the chemical formula (A) by keeping the temperature at 150 ° C. and reacting for 6 hours. -Hydroxyethyl) phenol] (m + n = 6) was obtained.

Caprolactone-modified 2,2'-methylene-bis [6- (2H-benzotriazole-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 (Kalens AOI: manufactured by Showa Denko), 47.9 g of ethyl acetate, and 0.044 g of p-methoxyphenol were mixed and heated to 60 ° C. , Dioctyl tin neodecanoate (Neostan U-830: manufactured by Nitto Kasei) added 0.95 g (0.046 mmol) of ethyl acetate 30-fold diluted solution, and reacted at 75 ° C. for 4 hours to be represented by the above chemical formula (B). The target compound (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, NH), 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 General Formula (1))
Under a nitrogen atmosphere, 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2-hydroxyethyl) phenol] (RUVA-100: manufactured by Otsuka Chemical Co., Ltd.)
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. Caprolactone-modified 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2) represented by the chemical formula (A) by keeping the temperature at 150 ° C. and reacting for 6 hours. -Hydroxyethyl) phenol] (m + n = 10) was obtained.

Caprolactone-modified 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2-hydroxyethyl) phenol] represented by the chemical formula (A) (m + n = 10) 96. 7 g (58 mmol) is mixed with 13.3 g (116 mmol) of 2-isocyanatoethyl acrylate (Carens AOI: Showa Denko), 47.9 g of ethyl acetate, and 0.044 g of p-methoxyphenol, and the temperature is raised to 60 ° C. , Dioctyl tin neodecanoate (Neostan U-830: manufactured by Nitto Kasei) added 0.95 g (0.046 mmol) of ethyl acetate 30-fold diluted solution, and reacted at 75 ° C. for 4 hours to be represented by the above chemical formula (B). The target compound (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, NH), 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 Bisbenzotriazolyl Phenol Compound 1)
2,2'-Methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] (RUVA-100: manufactured by Otsuka Chemical Co., Ltd.) in 76.6 g (147 mmol), 2 -Isocyanatoethyl acrylate (Karenzu AOI: Showa Denko) 33.4 g (293 mmol), ethyl acetate 47.9 g, p-methoxyphenol 0.044 g are mixed and heated to 60 ° C., dioctyltin neodecanoate (Neostan U). −830: A 30-fold diluted solution of ethyl acetate (manufactured by Nitto Kasei) was added in an amount of 0.95 g (0.046 mmol) and reacted at 75 ° C. for 4 hours. 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 Bisbenzotriazolyl Phenol Compound 2)
In Synthesis Example 2, a terminal acryloyl group using an isocyanate compound was used in the same manner as in Synthesis Example 2, except that 17.5 g (153 mmol) of 2-isocyanatoethyl acrylate (Karenzu AOI: manufactured by Showa Denko) was not reacted. A comparative bisbenzotriazolylphenol compound 2 (m + n = 6 of the following formula) (comparative compound 2) having the following chemical formula, which had not been 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 (Shikou UV-6300B, average number of functional groups = 7, manufactured by Nippon Synthetic Chemical Co., Ltd.): 100 parts by mass-The bisbenzotriazolylphenol compound 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 is applied to an easily adhesive PET film (Cosmoshine A4100 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm so that the film thickness after drying is 5 μm, and then dried and applied. 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 and 3, Comparative Examples 1 and 2)
In each example, as shown in Table 2, the bisbenzotriazolylphenol compound used was changed, and the amount of the bisbenzotriazolylphenol compound used was changed so as to be the same molar amount as in Example 1. A composition was prepared in the same manner as in Example 1 except for the above, 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 cured film of the composition coated on the surface was cut into a size of 2.5 cm × 10 cm, and the sample was chucked using a tensile tester (AUTOGRAPH AG-X manufactured by Shimadzu Corporation). A tensile test was carried out at a distance of 5 cm and a tensile speed of 50 mm / min. After 30% tension, the presence or absence of cracks on the surface of the cured film was confirmed.
<Evaluation criteria>
◯: No cracks occurred ×: Cracks occurred

(2) Bleedout Suppression A film having a cured film of the composition coated on the surface was cut into a size of 10 cm × 10 cm, and the sample was immersed in warm water at 40 ° C. for 1 month. The surface of the cured film soaked for 1 month was visually observed and palpated to evaluate the presence or absence of bleeding substances.
<Evaluation criteria>
◯: Bleedout cannot be confirmed △: There is a slight bleedout, but there is no problem in practical use. ×: There is a remarkable bleedout and the appearance is significantly impaired.

(3) Weather resistance A film having a cured film of the composition coated on the surface was cut out to a size of 5 cm × 5 cm, and the sample was subjected to a super UV weather resistance tester (Iwasaki Electric Co., Ltd. Eye Super UV Tester SUV-W161, The degree of discoloration of the base material (PET film) when it was put into an illuminance of 100 mW / cm ^{2) for 200 hours was evaluated.} In the super UV weathering tester, after irradiation with ultraviolet rays for 20 hours, watering (shower) was performed for 30 seconds, and a weathering test was conducted for 200 hours with dew condensation for 4 hours as one cycle.
<Evaluation criteria>
◯: Appearance change cannot be confirmed Δ: Slight discoloration of the base material (PET film) ×: Remarkable discoloration of the base material (PET film), cracking of the base material 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 usage environment in which moisture is present, and light and moisture are also suppressed. It was shown that the long-term sustainability of the ultraviolet absorbing function is excellent even in a usage environment that is simultaneously affected by. The bisbenzotriazolylphenol compound represented by the general formula (1) of the present invention has two aliphatic hydrocarbon chains between two (meth) acryloyl groups and bisbenzotriazolylphenol. Since it has a lactone chain, it is presumed that the dispersibility in the cured film and the reaction efficiency of the cross-linking reaction are enhanced, and the above effects are exhibited. Further, in Examples 1 to 3 using the bisbenzotriazolylphenol compound represented by the general formula (1) of the present invention, the flexibility and elasticity of the cured film are improved, and the tensile elongation is superior to that of the conventional one. 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 the bisbenzotriazolylphenol compound, but also an aliphatic hydrocarbon chain. 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. It is presumed to have excellent tensile elongation.

On the other hand, the bisbenzotriazolylphenol compound of Comparative Example 1, which corresponds to the compound of Patent Document 3, does not have a lactone chain between the two (meth) acryloyl groups and the bisbenzotriazolylphenol. It was shown that the tensile elongation was inferior, and the bleed-out suppression and weather resistance were also inferior. It is presumed that the bisbenzotriazolylphenol compound of Comparative Example 1 is inferior in the reaction efficiency of the (meth) acryloyl group. Further, in Comparative Example 2 using a bisbenzotriazolylphenol compound having a lactone chain but not a terminal (meth) acryloyl group, it 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 the 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 have 1 or more carbon atoms. Represents a linear or branched aliphatic hydrocarbon group of 6 or less, R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively. R ⁷ and R ⁸ independently represent a hydrogen atom, a halogen atom, or a halogen atom, respectively. Represents an aliphatic hydrocarbon group having 1 or more and 4 or less carbon atoms. N and m are independently numbers of 1 or more and 10 or less, and n + m = 2 or more and 20 or less. P and q are independently 3 and 3 respectively. or 5 in which .r及beauty s is the number of following each independently a number of 1 or more and 2 or less.) 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.