JP2018172623A - Uv-a absorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a UV-A absorber that can block a blue light beam from a near-ultraviolet region, and a cut film.SOLUTION: The present invention provides a UV-A absorber, which is an anthracene compound represented by a formula (1) (R1 and R 2 independently represent C1-12 alkyl, C6-13 aryl, C1-13 alkoxy or C6-13 aryloxy; X and Y independently represent C1-8 alkyl).SELECTED DRAWING: None

Description

The present invention relates to an ultraviolet absorber, and particularly to a compound having excellent absorbability in the UV-A region and a UV-A cut film.

 Electromagnetic radiation from the sun falling on the earth includes radio waves, millimeter waves, microwaves, infrared rays, visible rays, ultraviolet rays (UV-A and UV-B), X-rays and gamma rays. Among them, visible light has a wavelength in the range of 400 nm to 700 nm, and ultraviolet light refers to light in the range of 10 to 400 nm. Of the ultraviolet rays, light having a wavelength of 10 to 286 nm is absorbed by the ozone layer of the earth, so that the ultraviolet rays reaching the earth have a wavelength of 286 nm or more. On the other hand, from the viewpoint of influence on human health and the environment, the classification of near-ultraviolet band as UV-A, UV-B, and UV-C is used. In general, a wavelength of 10 to 280 nm is referred to as UV-C, a wavelength of 280 to 320 nm is referred to as UV-B, and a wavelength of 320 to 400 nm is referred to as UV-A. Of these, as mentioned earlier, the Earth's ozone layer absorbs wavelengths up to 286 nm, so UV-C is almost cut by this ozone layer and does not reach the ground. Uncut UV-A and UV-B longer than 286 nm reach the ground and affect the human body.

Further, since the energy of light increases in proportion to the wave number, the danger to the human body increases as the wavelength becomes shorter. That is, it can be said that ultraviolet rays have a greater influence on the human body than visible light. UV-B is said to act on the epidermis layer of human skin. At this time, pigment cells produce melanin and take a protective reaction. So-called sunburn. On the other hand, although UV-A has a smaller energy than UV-B, it is said to act on the dermis layer of the skin because of its long wavelength, denature proteins, lose skin elasticity and promote aging. It is also said that the melanin pigment produced by UV-B is oxidized to turn brown.

And many sunscreen creams, films, and the like that cut UV-B have been developed as measures against sunburn of the skin by UV-B. However, the danger of UV-A having a long wavelength has not been regarded as important until recently. The risk of aging skin, DNA damage, and skin cancer due to UV-A is not zero. In addition, since UV-A has a longer wavelength than UV-B as described above, it penetrates deeper into the skin than UV-B, and gradually breaks elastic fibers that keep the skin tight, reducing tension and wrinkles. It is said to cause. Furthermore, UV-A is less attenuated in the atmosphere than UV-B, and it is said that it is falling more and more in the winter and morning and evening when UV-B decreases. Also has the property of entering. Therefore, the influence of UV-A on the human body cannot be ignored.

Therefore, as a countermeasure against UV-A, a UV-A absorber is blended in a window glass or a car window, or is blended in a sunscreen cream to be applied to the skin. Various compounds such as benzotriazine-based and benzophenone-based ultraviolet absorbers have been studied as compounds that cut this UV-A. For example, Patent Documents 1 to 3 disclose trisaryl-s-triazine compounds that cut the near ultraviolet region. However, the compound disclosed in the document has an absorption around 350 nm, but the absorption around 380 to 400 nm is weak and cannot cut all of the wavelength region of UV-A. It was colored because the wavelength included the visible light region, and was not practical.

Patent Document 4 discloses Tinuvin 327 (Tinuvin is a registered trademark of BASF), Tinuvin P, CGL777, and the like as ultraviolet absorbers that also absorb in the UV-A region. Although these ultraviolet absorbers all have a maximum absorption around 350 nm, there is a disadvantage that the absorption around 380 to 400 nm is weak. Therefore, a UV-A absorber capable of efficiently cutting wavelengths from 380 to 400 nm has been desired.

Furthermore, 4-tert-butyl-4'-methoxydibenzoylmethane and the like are known as compounds capable of cutting UV-A from 380 to around 400 nm (Patent Document 5, etc.). However, since part of the visible light region also has absorption, it is colored pale yellow, and is limited to some uses where coloring is allowed.

Japanese Patent Laid-Open No. 8-53427 JP-A-11-71356 JP 2011-164286 A JP 2009-523625 A JP 2012-180290 A

Therefore, the object of the present invention is to absorb ultraviolet rays in the UV-A region, in particular, efficiently absorb ultraviolet rays in the wavelength range of 380 to 400 nm and shield them, and have no absorption in the visible light region, An object of the present invention is to provide a UV-A absorber having excellent transparency to visible light.

As a result of intensive studies on the structure and properties of anthracene compounds for many years, the present inventors have found that anthracene compounds having a specific structure have ultraviolet absorption in the UV-A region, particularly 380 to 400 nm. It has been found that the compound has an absorption peak in the wavelength range, and can be used as an excellent UV-A absorber. Furthermore, the compound is colorless because it has almost no absorption at 400 nm or more, and has excellent transparency to visible light.

That is, 1st invention exists in the UV-A absorber containing the anthracene compound represented by following General formula (1).

In General Formula (1), R ¹ and R ² may be the same or different, and are an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 13 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Alternatively, it represents an aryloxy group having 6 to 13 carbon atoms, and X and Y may be the same or different, and represent an alkyl group having 1 to 8 carbon atoms.

According to a second invention, in the general formula (1), R ¹ and R ² are an alkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 13 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or an aryl group having 6 carbon atoms. It exists in the UV-A absorber as described in 1st invention characterized by being 13 aryloxy groups.

3rd invention exists in the ultraviolet absorber composition characterized by containing the UV-A absorber which is an anthracene compound represented by the said General formula (1), and a UV-B absorber.

4th invention contains UV-A absorber other than the anthracene compound represented by the said Formula (1), and the UV-A absorber which is an anthracene compound represented by the said General formula (1). It exists in the ultraviolet absorber composition characterized by these.

According to a fifth invention, in the general formula (1), R ¹ and R ² are an alkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 13 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a carbon number 6 To the ultraviolet absorber composition according to the third or fourth aspect of the invention.

6th invention exists in the ultraviolet absorber composition characterized by containing the hindered amine stabilizer further in the UV-A absorber as described in 1st invention or 2nd invention.

7th invention exists in the ultraviolet absorber composition characterized by containing the hindered amine stabilizer further in the ultraviolet absorber composition as described in any one of 3rd invention thru | or 5th invention. .

An eighth invention is characterized in that the UV-A absorber described in the first invention or the second invention further contains an antioxidant and / or a singlet oxygen quencher. Present in the composition.

A ninth invention is characterized in that the ultraviolet absorber composition according to any one of the third to seventh inventions further contains an antioxidant and / or a singlet oxygen quencher. In the ultraviolet absorber composition.

The tenth invention resides in a UV-A cut film containing the UV-A absorber described in the first invention or the second invention as an active ingredient.

The eleventh invention resides in a UV-A cut film containing as an active ingredient the ultraviolet absorbent composition according to any one of the third to ninth inventions.

The twelfth invention is the UV-A absorbent according to the first invention or the second invention or the third invention to the ninth invention on the glass substrate, metal substrate or oxygen barrier film. A polymerized film obtained by applying a photopolymerizable composition containing the ultraviolet absorbent composition according to any one of the above, and further covering the coated film with an oxygen barrier film, and then polymerizing and curing the film by irradiation with light. It exists in the UV-A cut film characterized by being.

The thirteenth invention is the UV-A cut film according to the twelfth invention, wherein the oxygen permeability of the oxygen barrier film is 100 cm ³ / (m ² · day · atm) or less at 20 ° C. under dry conditions. Exist.

A fourteenth invention is a laminate including a UV-A cut film, the laminate having two advanced oxygen barrier film layers, and the tenth invention to tenth invention between the advanced oxygen barrier film layers. It exists in the UV-A cut film laminated body characterized by including the UV-A cut film as described in any one of three inventions.

A fifteenth aspect of the invention is a laminate including a UV-A cut film, the laminate having a glass substrate and a high oxygen barrier film layer. It exists in the UV-A cut film laminated body characterized by including the UV-A cut film as described in any one of 10th invention thru | or 13th invention.

The sixteenth invention is the fourteenth invention or the fifteenth invention, wherein the oxygen permeability of the advanced oxygen barrier film is 10 cm ³ / (m ² · day · atm) or less at 20 ° C. under dry conditions. It exists in the described UV-A cut film laminated body.

The anthracene compound having a specific structure of the present invention has UV absorption in the UV-A region, and has one absorption maximum particularly in the wavelength range of 380 to 400 nm, and as an excellent UV-A absorber. Can be used. Further, the compound is colorless and has excellent permeability to visible light. And the composition and film containing the said compound also show the outstanding UV-A absorption characteristic.

It is a UV absorption curve of 9,10-bis (n-octanoyloxy) anthracene (AHQ-n-octanoyl) which is an example of the UV-A absorber of this invention. It is a UV absorption curve of 9,10-bis (phenoxycarbonyloxy) anthracene (AHQ phenyl carbonate) which is an example of the UV-A absorber of this invention. The figure which showed the shape of the light resistance test test sample of Example 13 and Comparative Example 5. FIG.

<UV-A absorber>
The UV-A absorber of the present invention is an anthracene compound represented by the following general formula (1).

In General Formula (1), R ¹ and R ² may be the same or different, and are an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 13 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Alternatively, it represents an aryloxy group having 6 to 13 carbon atoms, and X and Y may be the same or different, and represent an alkyl group having 1 to 8 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹ and R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and n-pentyl group. N-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group, etc., and examples of the aryl group having 6 to 13 carbon atoms include , Phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 1-naphthyl group, 2-naphthyl group and the like. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, n-pentyloxy group, n-hexyloxy group, n -Heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-dodecyloxy group and the like. Examples of the aryloxy group having 6 to 13 carbon atoms include phenoxy group, tolyloxy group, naphthoxy group, and methylnaphthoxy group. Examples of the alkyl group having 1 to 8 carbon atoms represented by X or Y include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, etc. are mentioned.

Specific examples of the compound represented by the general formula (1) when R ¹ and R ² are alkyl groups having 1 to 12 carbon atoms include the following compounds. That is, examples where X and Y are both hydrogen atoms include 9,10-bis (acetyloxy) anthracene, 9,10-bis (propionyloxy) anthracene, and 9,10-bis (n-butyryloxy) anthracene. 9,10-bis (i-butyryloxy) anthracene, 9,10-bis (n-pentanoyloxy) anthracene, 9,10-bis (n-hexanoyloxy) anthracene, 9,10-bis (n-hepta) Noyloxy) anthracene, 9,10-bis (n-octanoyloxy) anthracene, 9,10-bis (2-ethylhexanoyloxy) anthracene, 9,10-bis (n-nonanoyloxy) anthracene, 9,10- Bis (n-decanoyloxy) anthracene, 9,10-bis (n-undecanoyl) Alkoxy) anthracene, 9,10-bis (n- dodecanoyloxy) anthracene, and the like.

Next, when X and / or Y is an alkyl group, 2-methyl-9,10-bis (acetyloxy) anthracene, 2-methyl-9,10-bis (propionyloxy) anthracene, 2-methyl -9,10-bis (n-butyryloxy) anthracene, 2-methyl-9,10-bis (i-butyryloxy) anthracene, 2-methyl-9,10-bis (n-pentanoyloxy) anthracene, 2-methyl -9,10-bis (n-hexanoyloxy) anthracene, 2-methyl-9,10-bis (n-heptanoyloxy) anthracene, 2-methyl-9,10-bis (n-octanoyloxy) anthracene 2-methyl-9,10-bis (2-ethylhexanoyloxy) anthracene, 2-methyl-9,10-bis (n-nona) Noyloxy) anthracene, 2-methyl-9,10-bis (n-decanoyloxy) anthracene, 2-methyl-9,10-bis (n-undecanoyloxy) anthracene, 2-methyl-9,10-bis (N-dodecanoyloxy) anthracene, 2-ethyl-9,10-bis (acetyloxy) anthracene, 2-ethyl-9,10-bis (propionyloxy) anthracene, 2-ethyl-9,10-bis (n -Butyryloxy) anthracene, 2-ethyl-9,10-bis (i-butyryloxy) anthracene, 2-ethyl-9,10-bis (n-pentanoyloxy) anthracene, 2-ethyl-9,10-bis (n -Hexanoyloxy) anthracene, 2-ethyl-9,10-bis (n-heptanoyloxy) anthracene 2-ethyl-9,10-bis (n-octanoyloxy) anthracene, 2-ethyl-9,10-bis (2-ethylhexanoyloxy) anthracene, 2-ethyl-9,10-bis (n-nonanoyloxy) ) Anthracene, 2-ethyl-9,10-bis (n-decanoyloxy) anthracene, 2-ethyl-9,10-bis (n-undecanoyloxy) anthracene, 2-ethyl-9,10-bis ( n-dodecanoyloxy) anthracene and the like.

Specific examples of the compound represented by the general formula (1) where R ¹ and R ² are aryl groups having 6 to 13 carbon atoms include the following compounds. That is, examples in which both X and Y are hydrogen atoms include 9,10-bis (benzoyloxy) anthracene, 9,10-bis (4-methylbenzoyloxy) anthracene, 9,10-bis (2- Naphthoyloxy) anthracene and the like.

Next, when X and / or Y is an alkyl group, 2-methyl-9,10-bis (benzoyloxy) anthracene, 2-methyl-9,10-bis (4-methylbenzoyloxy) anthracene, 2-methyl-9,10-bis (2-naphthoyloxy) anthracene, 1-methyl-9,10-bis (benzoyloxy) anthracene, 1-methyl-9,10-bis (4-methylbenzoyloxy) anthracene 1-methyl-9,10-bis (2-naphthoyloxy) anthracene, 2-ethyl-9,10-bis (benzoyloxy) anthracene, 2-ethyl-9,10-bis (4-ethyl-benzoyloxy) ) Anthracene, 2-ethyl-9,10-bis (2-naphthoyloxy) anthracene, 1-ethyl-9,10-bis (ben Zoyloxy) anthracene, 1-ethyl-9,10-bis (4-ethyl-benzoyloxy) anthracene, 1-ethyl-9,10-bis (2-naphthoyloxy) anthracene and the like.

Specific examples of the compound represented by the general formula (1) when R ¹ and R ² are an alkoxy group having 1 to 12 carbon atoms include the following compounds. That is, examples where X and Y are both hydrogen atoms include 9,10-bis (methoxycarbonyloxy) anthracene, 9,10-bis (ethoxycarbonyloxy) anthracene, and 9,10-bis (n-propoxy). Carbonyloxy) anthracene, 9,10-bis (i-propoxycarbonyloxy) anthracene, 9,10-bis (n-butoxycarbonyloxy) anthracene, 9,10-bis (n-pentoxycarbonyloxy) anthracene, 9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 9,10-bis (n-heptyloxycarbonyloxy) anthracene, 9,10-bis (n-octyloxycarbonyloxy) anthracene, 9,10-bis (2 -Ethylhexyloxycarbonyloxy ) Anthracene, 9,10-bis (n-nonyloxycarbonyloxy) anthracene, 9,10-bis (n-decyloxycarbonyloxy) anthracene, 9,10-bis (n-undecyloxycarbonyloxy) anthracene, 9 , 10-bis (n-dodecyloxycarbonyloxy) anthracene and the like.

Next, when X and / or Y is an alkyl group, 2-methyl-9,10-bis (methoxycarbonyloxy) anthracene, 2-methyl-9,10-bis (ethoxycarbonyloxy) anthracene, -Methyl-9,10-bis (n-propoxycarbonyloxy) anthracene, 2-methyl-9,10-bis (i-propoxycarbonyloxy) anthracene, 2-methyl-9,10-bis (n-butoxycarbonyloxy) ) Anthracene, 2-methyl-9,10-bis (n-pentoxycarbonyloxy) anthracene, 2-methyl-9,10-bis (n-hexyloxycarbonyloxy) anthracene, 2-methyl-9,10-bis (N-Heptyloxycarbonyloxy) anthracene, 2-methyl-9,10-bis (n -Octyloxycarbonyloxy) anthracene, 2-methyl-9,10-bis (2-ethylhexyloxycarbonyloxy) anthracene, 2-methyl-9,10-bis (n-nonyloxycarbonyloxy) anthracene, 2-methyl- 9,10-bis (n-decyloxycarbonyloxy) anthracene, 2-methyl-9,10-bis (n-undecyloxycarbonyloxy) anthracene, 2-methyl-9,10-bis (n-dodecyloxycarbonyl) Oxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonyloxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-propoxycarbonyl) Oxy) anthracene, 2-ethyl-9 10-bis (i-propoxycarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-pentoxycarbonyloxy) anthracene, 2 -Ethyl-9,10-bis (n-hexyloxycarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-heptyloxycarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-octyl) Oxycarbonyloxy) anthracene, 2-ethyl-9,10-bis (2-ethylhexyloxycarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-nonyloxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-decyloxycarbonyloxy) an Spiral, 2-ethyl-9,10-bis (n- undecyloxy carbonyloxy) anthracene, 2-ethyl-9,10-bis (n- dodecyloxy-carbonyloxy) anthracene, and the like.

Specific examples of the compound represented by the general formula (1) where R ¹ and R ² are aryl groups having 6 to 13 carbon atoms include the following compounds. That is, as an example in which both X and Y are hydrogen atoms, 9,10-bis (phenoxycarbonyloxy) anthracene, 9,10-bis (4-methylphenoxycarbonyloxy) anthracene, 9,10-bis ( 2-naphthyloxycarbonyloxy) anthracene and the like.

Next, when X and / or Y is an alkyl group, 2-methyl-9,10-bis (phenoxycarbonyloxy) anthracene, 2-methyl-9,10-bis (4-methylphenoxycarbonyloxy) Anthracene, 2-methyl-9,10-bis (2-naphthoyloxycarbonyloxy) anthracene, 1-methyl-9,10-bis (phenoxycarbonyloxy) anthracene, 1-methyl-9,10-bis (4- Methylphenoxycarbonyloxy) anthracene, 1-methyl-9,10-bis (2-naphthyloxycarbonyloxy) anthracene, 2-ethyl-9,10-bis (phenoxycarbonyloxy) anthracene, 2-ethyl-9,10- Bis (4-methylphenoxycarbonyloxy) anthracene, 2-ethyl Ru-9,10-bis (2-naphthyloxycarbonyloxy) anthracene, 1-ethyl-9,10-bis (phenoxycarbonyloxy) anthracene, 1-ethyl-9,10-bis (4-methylphenoxycarbonyloxy) Anthracene, 1-ethyl-9,10-bis (2-naphthyloxycarbonyloxy) anthracene and the like can be mentioned.

The anthracene compound represented by the general formula (1) can be produced by acylating or carbonylating the corresponding 9,10-dihydroxyanthracene compound by a known method.

Among the above-mentioned compounds, 9,10-bis (propionyloxy) anthracene, 9, 10-bis (n-butyryloxy) anthracene, 9,10-bis (i-butyryloxy) anthracene, 9,10-bis (n-valeryloxy) anthracene, 9,10-bis (i-valeryloxy) anthracene, 9,10- Bis (n-hexanoyloxy) anthracene, 9,10-bis (n-heptanoyloxy) anthracene, 9,10-bis (n-octanoyloxy) anthracene, 9,10-bis (2-ethylhexanoyloxy) Anthracene, 9,10-bis (n-nonanoyloxy) anthracene, 9,10-bis ( -Lauroyloxy) anthracene, 9,10-bis (methoxycarbonyloxy) anthracene, 9,10-bis (ethoxycarbonyloxy) anthracene, 9,10-bis (n-propoxycarbonyloxy) anthracene, 9,10-bis ( i-propoxycarbonyloxy) anthracene, 9,10-bis (n-butoxycarbonyloxy) anthracene, 9,10-bis (i-butoxycarbonyloxy) anthracene, 9,10-bis (2-ethylhexyloxycarbonyloxy) anthracene 9,10-bis (phenoxycarbonyloxy) anthracene is preferred, and 9,10-bis (n-octanoyloxy) anthracene and 9,10-bis (2-ethylhexanoyloxy) are more preferable in terms of high whiteness. Ant Sen, 9,10-bis (n-propoxycarbonyloxy) anthracene, 9,10-bis (i-propoxycarbonyloxy) anthracene, 9,10-bis (n-butoxycarbonyloxy) anthracene, 9,1 0-bis (i-butoxycarbonyloxy) anthracene and 9,10-bis (phenoxycarbonyloxy) anthracene are preferred. In particular, 9,10-bis (n-octanoyloxy) anthracene and 9,10-bis (2-ethylhexanoyloxy) anthracene are preferable.

The anthracene compound represented by the general formula (1) of the present invention has several absorption peaks in the wavelength range of 320 nm to 400 nm, and absorbs at least a part of light in the wavelength region to reduce its intensity. Is a possible compound. In particular, it has a strong absorption peak from 380 to 400 nm and is characterized by being able to reduce light having a wavelength that is difficult to cut with conventional ultraviolet absorbers. Further, usually, there is a problem that the yellowishness of light becomes strong when light rays in a wavelength range close to the visible light are cut. However, when the anthracene compound represented by the general formula (1) of the present invention is used, the problem arises. It has the feature of being reduced.

Although this detail is not clear, the anthracene compound represented by the general formula (1) has a function of cutting the ultraviolet region, but the yellowness does not become strong even though the light in the region is cut. The point that it has almost no absorption in the visible light region, and after the anthracene compound absorbs light, some excited anthracene compounds emit in the visible light region a fluorescence spectrum that is mirror image Therefore, it is considered that it has a so-called fluorescent whitening effect, and therefore it is possible to alleviate the problem that the yellowness becomes strong.

<Ultraviolet absorber composition-1>
One of the characteristics of the anthracene compound represented by the general formula (1) of the present invention is that it absorbs only in the wavelength range of 320 to 400 nm of UV-A and has a wavelength range of 280 to 320 nm in UV-B and 400 nm or more. It has almost no absorption in the visible light wavelength range. Therefore, when it is desired to cut light in the wavelength range of UV-B, a UV-A absorber that is an anthracene compound represented by the general formula (1) of the present invention and a known UV-B absorber are used in combination. It can be used as an ultraviolet absorber composition that cuts both -A and UV-B.

The UV-B absorber that can be used in combination with the UV-A absorber that is an anthracene compound represented by the general formula (1) of the present invention is particularly limited as long as it is a compound having absorption in the UV-B wavelength region. Although not, the following may be mentioned. For example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“Tinuvin P” manufactured by Ciba Geigy), 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzo Triazole ("Tinuvin 320" manufactured by Ciba Geigy), 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole ("Cinuvin 326" manufactured by Ciba Geigy), 2- Benzotriazole ultraviolet absorbers such as (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl -2,4-diisopropylcinnamate, 2-ethylhexyl-p-methoxycinnamate, cyclohex Ru-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, etc. Cinnamic acid UV absorber, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetra Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone UV absorber, para-aminobenzoic acid Acid monoglycerin ester, N, N-dipropoxyparaaminobenzoic acid ethyl ester, N, N-diethoxyparaaminobenzoic acid ethyl ester and other paraaminobenzoic acid UV absorbers, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate , Salicylic acid ultraviolet absorbers such as phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, 3- (4-methylbenzylidene) camphor, 3-benzylidene-d1-camphor, urocanic acid, urocanic acid ethyl ester, octyltriazone, Examples include ultraviolet absorbers such as 4-methoxy-4′-t-butyldibenzoylmethane. These ultraviolet absorbers in the UV-B region can be used singly or in combination of two or more.

The amount of UV-B absorber used in combination with the UV-B absorber can be arbitrarily set, but the amount used is UV-A absorption which is an anthracene compound represented by the general formula (1) of the present invention. It is preferable to use it in the ratio of 1 to 0.1 to 1 to 5 by mass ratio of the agent and the UV-B absorber.

<Ultraviolet absorber composition-2>
Moreover, it is also possible to use together the UV-A absorber which is an anthracene compound represented by General formula (1) of this invention, and another well-known UV-A absorber. By using a known UV-A absorber in combination with a UV-A absorber that is an anthracene compound represented by the general formula (1) of the present invention, in particular, the known UV-A absorber was difficult to cut at 380 nm. Therefore, the cut rate of 400 nm light can be improved.

Although it does not specifically limit as another UV-A absorber which can be used together with the UV-A absorber which is an anthracene compound represented by General formula (1) of this invention, The following are mentioned. For example, 2-hydroxy-4-methoxybenzophenone, 4-tert-butyl-4'-methoxydibenzoylmethane, diethylaminohydroxybenzoyl hexyl benzoate, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, methylenebisbenzotriazolyl Tetramethylbutylphenol, bisethylhexyloxyphenol methoxyphenyl triazine, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4- (4,6-bis- {2-hydroxy-4- [1- (6-methyl-heptyloxycarbonyl) -ethoxy] -phenyl}-[1,3,5] triazin-2-yl)- 3-hydroxy-phenoxy] -propi Phosphate 6-methyl - heptyl ester. These ultraviolet absorbers in the UV-A region can be used alone or in combination of two or more.

When the UV-A absorber other than the anthracene compound represented by the general formula (1) of the present invention is used in combination, the amount of the UV-A absorber used can be arbitrarily set. The mass ratio of the UV-A absorber which is an anthracene compound represented by the general formula (1) and the UV-A absorber other than the anthracene compound represented by the general formula (1) is 1 to 0.1 to 1 to 5 It is preferable to use in the ratio.

<Light stabilizer>
The UV-A absorber which is an anthracene compound represented by the general formula (1) of the present invention, or the UV absorber which contains the UV-A absorber which is an anthracene compound represented by the general formula (1) of the present invention The composition may further contain a light stabilizer.

By further containing a light stabilizer, decomposition of the UV-A absorber, which is an anthracene compound represented by the general formula (1) of the present invention, by light can be suppressed, and its stability can be enhanced.

The light stabilizer used is not particularly limited, but a hindered amine stabilizer is preferable. Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2,2,6. , 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl]- 1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) Amino) -s-to Azin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl) -4-piperidyl) amino) -s-triazin-6-ylaminoundecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl) -4-piperidyl) amino) -s-triazin-6-ylaminoundecane, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-undecyloxy) -2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,6-diaminohexane and 2,4,6-trichloro-1,3,5-triazine and N, N-dibutylamine and 4 -Butylamino- , 2,6,6-hindered amine compounds of condensates of tetramethyl piperidine.

Although the content of the light stabilizer can be arbitrarily set, the UV-A absorber which is an anthracene compound represented by the general formula (1) of the present invention or the UV- which is an anthracene compound represented by the general formula (1). It is preferably used in a mass ratio of 1 to 0.1 to 1 to 5 with respect to the ultraviolet absorber composition containing the A absorber.

<Antioxidant, singlet oxygen quencher>
The UV-A absorber which is an anthracene compound represented by the general formula (1) of the present invention, or the UV absorber which contains the UV-A absorber which is an anthracene compound represented by the general formula (1) of the present invention The composition can further contain an antioxidant and / or a singlet oxygen quencher.

Examples of the antioxidant used in the present invention include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and pentaerythritol antioxidants.

  Examples of phenolic antioxidants include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, hydroxyphenylpropionate compounds, hydroxybenzyl compounds, thiophenol compounds, alkanediylphenol compounds, and the like. be able to.

Specific examples of hydroxyphenylpropionate compounds include 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethoxy. ] -2,4,8,10-terolaoxaspiro [5.5] undecane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadec -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5′-di-tert-butyl-4′-hydroxyphenylpropionate)] methane Etc.

  Specific examples of hydroxybenzyl compounds include 1,3,5, -trimethyl-2,4,6, -tris (3 ′, 5′-di-t-butyl-4-hydroxybenzyl) benzene, 1,3. , 5-tris (4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (4-t-butyl-3) -Hydroxy-2,6-dimethylbenzyl) -isocyanurate and the like.

  Specific examples of thiophenol compounds include 4,4′-thiobis (6-tert-butyl-3-methylphenol), and specific examples of thiomethylphenol compounds include 2,4-bis [(octylthio) methyl. ] -O-cresol etc. can be mentioned.

  Specific examples of alkanediylphenol compounds include N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2′-methylenebis (4-methyl). -6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane and the like.

Specific examples of phosphorus antioxidants include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate. , Triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4 8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, diisodecylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2,2′-methyle Bis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2 , 4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4 ′ -Butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite, octadecyl phosphite, tris (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2,4-di-t-butylphenyl) ) Phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2,6-di-t-butylphenyl) phosphite, 2, 2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite Bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester, phosphonic acid, etc. be able to.

Examples of the sulfur-based antioxidant include thiopropionate compounds and mercaptobenzimidazole compounds. Specific examples of thiopropionate compounds include 2,2-bis ({[3- (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl-bis [3- (dodecylthio) propionate], dilauryl. −3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), etc. Can be mentioned. Specific examples of mercaptobenzimidazole compounds include 2-mercaptobenzimidazole.

Examples of commercially available antioxidants having a phenol structure include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, and AO-80. AO-330 (above, ADEKA), sumilizer GM, GS, MDP-S, BBM-S, WX-R, GA-80 (above, Sumitomo Chemical), IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 565, IRGAMOD295 (above, BSF Corporation), Yoshinox BHT, BB, 2246G, 425, 250, 930, SS, TT, 917, 314 (above, API Corporation) Deployment Co., Ltd.), and the like.

As the singlet oxygen quencher that can be used in the present invention, any compound that can deactivate singlet oxygen by energy transfer from singlet state oxygen can be used. The anthracene compound represented by the general formula (1) of the present invention has the ability to absorb UV-A, but when an anthracene compound in an excited state that has absorbed UV-A is present in the system, It can react with oxygen to produce singlet oxygen, which can decompose anthracene compounds and / or other additives. For the purpose of preventing the reaction, the UV-A absorber containing the anthracene compound represented by the general formula (1) of the present invention preferably contains a singlet oxygen quencher.

Examples of the singlet oxygen quencher include ethylenic compounds such as tetramethylethylene, cyclopentene, cyclohexene, 2,5-dimethyl-2,4-hexadiene, 1,3-cyclopentadiene, α-terpinene; diethylamine, triethylamine, 1,4-diazabicyclooctane (DABCO), N-ethylimidazole, N, N′-diphenyl-N, N′-di (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine Amines such as N-isopropylcarbazole and N-phenylcarbazole; naphthalene, dimethylnaphthalene, pyrene, chrysene, perylene, coronene, tetracene, pentacene, rubrene, 3,4-benzofluoranthrene, 2,3-benzofluorene, 1,12-benzoperylene, 3,4- Condensed polycyclic aromatic compounds such as nzopyrene, 4,5-benzopyrene, and alkyl-substituted products thereof; 1,3-diphenylisobenzofuran, 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, penta And aromatic compounds such as phenylcyclopentadiene.

Furthermore, examples of the singlet oxygen quencher include metal complexes having a sulfur atom-containing compound as a ligand. Examples of such a singlet oxygen quencher include transitions of nickel complexes, cobalt complexes, copper complexes, manganese complexes, platinum complexes, etc. having bisdithio-α-diketone, bisphenyldithiol, and thiobisphenol as ligands. Mention may be made of metal chelate compounds. Specific examples of the transition metal chelate compound include, for example, bis (dithiobenzyl) nickel, bis (4-dimethylaminodithiobenzyl) nickel, bis (dithiobiacetyl) nickel, bis (dibutyldithiocarbamate) nickel, and bis (octylphenyl). ) Sulfide nickel, bis (1,2-dithiophenolate) nickel tetrabutylammonium salt, bis (thiocatechol) nickel tetrabutylammonium salt, bis (4,4′-di-tert-butyl-dithiobenzyl) nickel, bis (4,4′-diisopropyldithiobenzyl) nickel, 4-N, N-diethylsulfamoyl-1,2-benzenedithiolnickel and its derivatives. The same compound can be mentioned about cobalt, copper, manganese, and a platinum complex.

In the present invention, the antioxidant and / or singlet oxygen quencher can be used alone or in admixture of two or more. It can also be used in combination with a light stabilizer.

Although content of antioxidant and / or singlet oxygen quencher can be set arbitrarily, it is represented by UV-A absorber or general formula (1) which is an anthracene compound represented by general formula (1) of the present invention. It is preferable to use it by the ratio of 1: 0.1 to 1: 5 by mass ratio with respect to the ultraviolet absorber composition containing the UV-A absorber which is an anthracene compound.

<Preparation of UV-A cut film>
The UV-A absorber which is an anthracene compound represented by the general formula (1) of the present invention or the ultraviolet absorber composition containing the anthracene compound represented by the general formula (1) of the present invention is used as it is with other compounds. It can be used as a paste or mixed with a solvent or mixed with a solvent. For example, UV-A absorber which is an anthracene compound represented by the general formula (1) of the present invention or an anthracene compound represented by the general formula (1) of the present invention to a resin such as PMMA or ABS It can be used as a plate, sheet, film or the like having a UV-A cut effect by kneading the absorbent composition or adding it by dissolving or dispersing it in a solvent together with a resin. Furthermore, the UV-A absorber which is an anthracene compound represented by the general formula (1) of the present invention or the anthracene compound represented by the general formula (1) of the present invention in the polymerizable compound. After blending the composition, the polymerizable compound may be heat or photopolymerized to obtain a cured product containing the UV-A absorber, particularly a film.

In the case of a film, photopolymerization and curing are preferable because of simplicity and transparency. That is, the UV-A absorber which is an anthracene compound represented by the general formula (1) of the invention or the ultraviolet absorber composition containing the anthracene compound represented by the general formula (1) of the present invention, and if necessary. In this method, a photopolymerization initiator is added to a photopolymerizable compound to prepare a photopolymerizable composition, and the photopolymerizable composition is polymerized and cured by irradiation with light energy.

<Photopolymerizable composition>
The photopolymerizable composition may be a photocationic polymerizable composition or a photoradical polymerizable composition.

<Photopolymerization initiator>
The photoinitiator used for the photopolymerizable composition of this invention is demonstrated. Photopolymerization initiators include onium salts, benzylmethyl ketal photopolymerization initiators, α-hydroxyalkylphenone photopolymerization initiators, α-aminophenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oximes. Examples thereof include ester photopolymerization initiators and biimidazole photopolymerization initiators.

First, as the onium salt, a sulfonium salt or an iodonium salt is usually used. As the sulfonium salt, arylsulfonium salts are preferable, and S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexafluorophosphate, diphenyl-4- Examples thereof include phenylthiophenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate. For example, product name: CPI-100P, manufactured by BSF Corporation, product name: Irgacure 270 (Irgacure is B・ Registered trademark of ASF Corporation). On the other hand, as the iodonium salt, aryl iodonium salt is preferable, 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, 4-isopropylphenyl-4′-methylphenyl Examples thereof include iodonium tetrakispentafluorophenylborate. For example, trade name: Irgacure 250, or Solvay Japan, trade name: PHOTOINITIATOR 2074, manufactured by BSFS, Inc. can be used.

Examples of the benzylmethyl ketal-based radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” manufactured by BAS Corporation). As the α-hydroxyalkylphenone-based radical polymerization initiator, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Irgacure 1173” manufactured by BSF Corporation), 1-hydroxy Cyclohexyl phenyl ketone (trade name “Irgacure 184” manufactured by BSF Corporation), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- ON (trade name “Irgacure 2959” manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methyl -1-one (trade name “Irgacure 127” manufactured by BSF Corporation) is exemplified.

Further, acetophenone radical polymerization initiators such as acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, 2 -Isobutoxy-2-phenylacetophenone, benzyl radical polymerization initiator benzyl, 4,4'-dimethoxybenzyl, anthraquinone radical polymerization initiator 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-phenoxyanthraquinone 2- (phenylthio) anthraquinone, 2- (hydroxyethylthio) anthraquinone, and the like can also be used.

<Polymerizable compound>
Next, the polymerizable compound will be described. As the polymerizable compound, either a cationic polymerizable compound or a radical polymerizable compound can be used. First, the case of a cationically polymerizable compound will be described.

Examples of the photocationically polymerizable compound that can be used in the present invention include epoxy compounds and vinyl ether compounds. Common epoxy compounds are alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl compounds. As the alicyclic epoxy compound, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Delcel's Celoxide 2021P, Celoxide is a registered trademark of Daicel Corporation), 1,2-epoxy-4- Examples include vinylcyclohexane (Celoxide 2000 manufactured by Daicel Corporation), bis (3,4-epoxycyclohexyl) adipate, among which 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is particularly used. Is preferred. Examples of the aromatic glycidyl compound include 2,2'-bis (4-glycidyloxyphenyl) propane. Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like. As the epoxy-modified silicone, UV-9300 manufactured by Momentive Performance Materials Japan GK can be used.

Next, the case where the polymerizable compound is a radical polymerizable compound will be described.

As the photoradical polymerizable compound, for example, an organic compound having a double bond such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, and methacrylic acid ester can be used. . Of these radically polymerizable compounds, acrylic acid esters and methacrylic acid esters (hereinafter referred to as “(meth) acrylic acid esters” together) are preferable from the viewpoint of film forming ability and the like. (Meth) acrylic acid esters include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, tetra Examples include ethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, and imide acrylate. . These radical photopolymerizable compounds may be a single compound or a mixture of two or more.

Although it is possible to separately add the anthracene compound represented by the general formula (1) and the photopolymerization initiator to the polymerizable compound, the UV- which is the anthracene compound represented by the general formula (1) of the present invention. It is also possible to add to the polymerizable compound after pre-mixing the ultraviolet absorber composition containing the UV-A absorber, which is an A-absorber or an anthracene compound represented by the general formula (1), and a photopolymerization initiator. It is.

The amount of the anthracene compound represented by the general formula (1) in the photocationically polymerizable composition or the radically polymerizable composition of the present invention is 0.001 part by weight or more and 5 parts by weight with respect to 100 parts of the polymerizable compound. The range is less than 1 part, preferably 0.01 parts by weight or more and less than 3 parts by weight. If it is less than 0.001 part by weight, the UV-A blocking effect is poor, whereas if it is more than 5 parts by weight, the physical properties of the polymer obtained by photopolymerization are deteriorated, which is not preferable.

The amount of the photopolymerization initiator used in the photocationic polymerizable composition or the photoradical polymerizable composition of the present invention is in the range of 0.005 parts by weight or more and less than 10 parts by weight, preferably 100 parts by weight of the polymerizable compound. 0.01 parts by weight or more and less than 5 parts by weight. If it is less than 0.005 parts by weight, it takes time to photopolymerize the photopolymerizable composition. On the other hand, if it is more than 10 parts by weight, the hardness of the polymer obtained by photopolymerization decreases, and the physical properties of the polymer are reduced. This is not preferable because of worsening

<Solvent>
Since the photopolymerizable composition of the present invention is generally used by being thinly coated on a substrate, it may further contain a solvent from the viewpoint of improving the coatability. Of course, there is no problem even without solvent. A solvent will not be specifically limited if it can melt | dissolve each component mentioned above. For example, ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone; alcohols such as propylene glycol monomethyl ether (PGME) and isopropyl alcohol (IPA); cycloalkanes such as cyclohexane; toluene, xylene, Aromatic hydrocarbon compounds such as benzyl alcohol can be mentioned. Of these, methyl ethyl ketone, cyclohexanone, and MIBK are preferred from the viewpoint of excellent solubility, drying properties, and paintability. A solvent can be used individually or in combination of 2 types or more, respectively.

In the present invention, the content in the case of using a solvent is preferably 0.1 to 85% by mass in the total amount of the photopolymerizable composition from the viewpoint of coatability.

<Leveling agent>
When the composition of the present invention contains a solvent, it preferably further contains a leveling agent. Of course, there is no problem even if it is not added. Examples of the leveling agent include silicone leveling agents, acrylic leveling agents, vinyl leveling agents, and fluorine leveling agents. Among these, it is preferable to use an acrylic leveling agent because the uniformity of the polymer film is improved and as a result, the transparency of the polymer film is improved.

In this invention, it is preferable that content of arbitrary leveling agents is 0.01-3 mass% in the whole quantity of a photopolymerizable composition from a viewpoint of coating property.

<Preparation of film>
The UV-A cut film of this invention can be manufactured by apply | coating the said photopolymerizable composition on a base material, polymerizing and hardening by irradiating light, and forming a polymer film.

<Base material>
It does not specifically limit as a base material, As a constituent material, plastics, rubber | gum, glass, a metal, a ceramic etc. are mentioned, for example. Here, the plastic may be either a thermopolymerizable resin or a thermoplastic resin. Specific examples thereof include polyethylene terephthalate (PET), cycloolefin polymer (homopolymer, copolymer, hydrogenated). For example, COP and COC), polymethyl methacrylate resin (PMMA resin), polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin, etc. Is mentioned. The base material may be subjected to a surface treatment such as a corona treatment. The form of the substrate is not particularly limited, but is preferably a film. Among these, it is preferable to use a glass substrate, a metal substrate, or an oxygen barrier film as a substrate. By using these oxygen-impermeable substrates and further covering with an oxygen barrier fill, the photopolymerizable composition containing the UV-A absorber of the present invention can be stably formed into a film.

The photopolymerizable composition prepared by the above-described method is applied onto a substrate and cured to form a polymerizable film on the substrate.

The thickness of the substrate and the polymer film is not particularly limited, but the thickness of the substrate is preferably about 50 to 300 μm, and the thickness of the polymer film is preferably about 0.1 to 100 μm.

For example, the method which has the process of apply | coating the photopolymerizable composition of this invention on a film-form base material, drying, and irradiating an ultraviolet-ray is mentioned. Here, the method for coating the photopolymerizable composition of the present invention on the substrate is not particularly limited. For example, a known coating method such as brush coating, flow coating, dip coating, spray coating, spin coating or the like is used. Can be adopted. Moreover, it is preferable that the temperature dried after coating is 20-110 degreeC.

Moreover, as an irradiation amount (integrated light quantity) of the ultraviolet rays used when polymerizing the photopolymerizable composition of the present invention, 10 to 1000 mJ / cm ² is preferable from the viewpoint of fast polymerization and workability. The apparatus used for irradiating ultraviolet rays is not particularly limited. For example, the following conventionally known ones can be mentioned. A photopolymer can be obtained by irradiating the thus prepared film with ultraviolet light having a wavelength range of 250 to 500 nm at an intensity of about 1 to 1000 mW / cm ² . Examples of the light source used include a metal halide lamp, a xenon lamp, a 405 nm UV-LED, a 395 nm UV-LED, a 385 nm UV-LED, a 365 nm UV-LED, a blue LED, a white LED, a D bulb and a V bulb manufactured by Fusion. Photopolymerization with sunlight is also possible. Moreover, you may use a heating together in making it superpose | polymerize. Among these, 405 nm UV-LED and 395 nm UV-LED are particularly preferable.

In the photopolymerizable composition containing the UV-A absorber which is an anthracene compound represented by the general formula (1) of the present invention, the anthracene compound represented by the general formula (1) of the present invention absorbs ultraviolet rays. Nevertheless, photopolymerization using ultraviolet rays is not hindered and it is excellent in that it is rapidly polymerized and cured.

When photopolymerizing the photopolymerizable composition of the present invention, an oxygen barrier film is placed on the photopolymerizable composition that has been coated and dried on a substrate, and then polymerized and cured by irradiation with light. preferable. If oxygen is present at the time of light irradiation, active oxygen is generated during the photopolymerization reaction, and a reaction for decomposing the UV-A absorbent of the present invention may partially proceed. Therefore, the decomposition reaction can be prevented by covering the applied photopolymerizable composition with an oxygen barrier film.

The oxygen barrier film to be placed on the photopolymerizable composition preferably has an oxygen permeability of 100 cm ³ / (m ² · day · atm) or less under dry conditions at 20 ° C.

The oxygen permeability varies depending on the material of the film, but is also affected by the thickness of the film. Therefore, as a film having an oxygen permeability of 100 cm ³ / (m ² · day · atm) or less, for example, an ethylene-vinyl alcohol copolymer having an ethylene content of 56% can be used having a thickness of about 1 μm. . Polyethylene terephthalate is 10 μm or more, and nylon 6 is a film having a thickness of 20 μm or more.

<UV-A cut film>
The UV-A cut film containing the UV-A absorber of the present invention may have a reduced UV-A cut ability with the passage of time depending on use conditions. This decrease in the UV-A cut ability is considered to be caused by the active oxygen excited by light coming into contact with the UV-A absorber and partial decomposition of the UV-A absorber by an oxidation reaction or the like.

Therefore, in order to increase the long-term stability of the UV-A film of the present invention, it is preferable to cover the UV-A film with a high oxygen barrier film having high light transmittance and excellent oxygen barrier properties.

As one of the methods, a laminated structure in which the UV-A cut film of the present invention is sandwiched between two highly oxygen barrier film layers is preferable.

As another method, it is preferable that one of the UV-A cut films of the present invention is a glass substrate and the other is a highly oxygen barrier film layer, and a laminated structure sandwiched between the two is used.

By adopting such a laminated structure, the UV-A absorbent of the present invention can be prevented from coming into contact with oxygen under ultraviolet irradiation, and the UV-A cutting ability can be stably maintained for a long time. Become.

The high oxygen barrier film used preferably has an oxygen permeability of 10 cm ³ / (m ² · day · atm) or less. More preferably, it is 1 cm ³ / (m ² · day · atm) or less, and more preferably 0.1 cm ³ / (m ² · day · atm) or less. The lower the oxygen permeability, the better, and the higher the total light transmittance in the visible light region, the better.

As such an advanced oxygen barrier film, a thin film made of an inorganic oxide is formed on the surface of a polymer film by a vacuum process such as a vacuum deposition method or a plasma chemical vapor deposition (CVD) method, and a barrier layer is provided. Is common. Film glass can also be used. For example, what provided the vapor deposition layer, such as an alumina and a silicon oxide, on a polyethylene terephthalate film or a nylon film, etc. are mentioned.

UV absorber composition containing UV-A absorber which is an anthracene compound represented by general formula (1) of the present invention or UV-A absorber which is an anthracene compound represented by general formula (1) of the present invention In the polymerizable composition containing the product, as long as the object of the present invention is not impaired, for example, a filler, an anti-aging agent, an antistatic agent, a flame retardant, an adhesion imparting agent, an anti-blocking agent, a dispersant, an oxidation agent. An additive such as an inhibitor, an antifoaming agent, a matting agent, a surfactant, an antifoaming agent, a thickener, a lubricant, a plasticizer, a water repellent, a dye, and a pigment can be further contained.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Measurement of UV spectrum>
The measurement sample solution was prepared by adding the measurement sample to acetonitrile (Wako Pure Chemical Industries) to a concentration of 10 ppm and completely dissolving it. The sample solution was put in a quartz cell having an optical path length of 1 cm to a height of about the eighth minute so as not to generate bubbles, set in UV2600 (manufactured by Shimadzu Corporation), and UV spectrum was measured.

(Examples 1-8)
A measurement sample solution was prepared using the UV-A absorber shown in Table 1 as a measurement sample, the respective UV spectra were measured, and the absorbance at 390 nm and 400 nm was shown in Table 1.

(Comparative Examples 1 and 2)
As a comparative example, UV spectra were measured for known UV absorbers Tinuvin P and Tinuvin 326 in the same manner as in the Examples, and the absorbance at 390 nm and 400 nm is shown in Table 2.

As is clear by comparing Examples 1 to 9 with Comparative Examples 1 and 2 and Tables 1 and 2, the UV-A absorber which is an anthracene compound represented by the general formula (1) of the present invention is: It can be seen that the absorbance at 390 nm is large and the light around 390 nm is well absorbed. On the other hand, the absorbance at 400 nm is small, indicating that there is almost no absorption in the visible light region. This point is also apparent from the UV spectra of the compounds of Example 1 and Example 4 in FIGS. On the other hand, it can be seen that the conventionally used ultraviolet absorbers Tinuvin P and Tinuvin 326 have a low absorbance at 390 nm and cannot sufficiently cut light from 380 nm to 400 nm.

Example 9
<Preparation of cationic cured film>
As UV-A absorber, 1 part of 9,10-bis (octanoyloxy) anthracene (OcA), 2 parts of Irgacure 250 as photopolymerization initiator, 100 parts of Celoxide 2021P as polymerizable compound, and methyl ethyl ketone as solvent 30 parts and 0.1 part of an acrylic leveling agent (BYK361N, manufactured by Big Chemie Japan) as a leveling agent were mixed with stirring to prepare a photocationically polymerizable composition.

Each photopolymerizable composition obtained as described above was applied onto a TAC film (thickness 100 μm) using a bar coater so that the film thickness after drying was 18 μm, and 395 nm LED- manufactured by Thunder Co., Ltd. was applied thereto. Irradiation was performed using UV (irradiation conditions: irradiation intensity 3, 6 mW / cm ² ) to polymerize the photopolymerizable composition, thereby preparing a laminate.

(Evaluation)
The following evaluation was performed using the manufactured film. The results are shown in Table 3.

<Cutting ratio of 395 nm UV-LED light of film>
The film manufactured as described above is irradiated with a 395 nm UV-LED manufactured by Thunder as an apparatus, and the illuminance after transmission through the film of 395 nm is UV illuminance meter UNI-METER UIT-101 manufactured by USHIO INC., And the receiver is UVD-405PD. The transmittance (%) at 395 nm was measured. The measurement result was applied to the following formula to calculate the cut rate of light having a wavelength of 395 nm of the laminate.

(Example 10 and Comparative Example 3)
A UV-A absorber, a photopolymerization initiator, and a polymerizable compound were used as the respective components shown in Table 3 below, and the compositions (parts by mass) shown in Table 3 were mixed using a stirrer in the same manner as in Example 9 to produce light. A polymerizable composition was prepared. Then, the photopolymerizable composition obtained in the same manner as in Example 9 was polymerized to prepare a laminate, and the cut rate of 395 nm light of the polymer film was measured in the same manner as in Example 9, and the results are shown in Table 3. Described.

(Example 11)
<Preparation of radical cured film>
As UV-A absorber, 1 part 9,10-bis (octanoyloxy) anthracene (OcA), 5 parts Irgacure 1173 as photopolymerization initiator, 100 parts biscoat 400 as polymerizable compound, and methyl ethyl ketone as solvent 30 parts, 0.1 part of an acrylic leveling agent (BYK361N, manufactured by Big Chemie Japan Co., Ltd.) as a leveling agent was mixed with stirring to prepare a photoradical polymerizable composition, and UV-A was prepared in the same manner as in Example 9. Cut films were produced and evaluated in the same manner as in Example 9, and the results are shown in Table 4.

(Example 12 and Comparative Example 4)
A UV-A absorber, a photopolymerization initiator, and a polymerizable compound were used as the components shown in Table 4 below, and the compositions (parts by mass) shown in Table 4 were mixed using a stirrer in the same manner as in Example 10 to produce light. A polymerizable composition was prepared. And the photopolymerizable composition obtained by carrying out similarly to Example 10 was polymerized, a laminated body was created, the cut rate of 395 nm UV-LED light of a polymeric film was measured similarly to Example 10, and the result was shown in Table 4 It was described in.

As is apparent from the results shown in Examples 9 to 12 and Comparative Examples 3 and 4 and Tables 3 and 4, the cut rate at 395 nm of the film containing the anthracene compound represented by the general formula (1) of the present invention is general. Compared with a film prepared by blending tinuvin P, which is a novel UV absorber, the cut rate at 395 nm is very high, and the UV-A cut function of the film containing the UV-A absorber of the present invention, particularly the wavelength of 395 nm It can be seen that the cutting function is excellent.

[Example 13]
<Stabilization of UV-A absorber>
The UV-A absorber is decomposed by the coexistence of singlet oxygen, but the UV-A absorber can be stabilized by removing the oxygen that generates singlet oxygen so that the singlet oxygen does not coexist. it can.

As a UV-A absorber, 1 wt% of 9,10-bis (octanoyloxy) anthracene (OcA) was dissolved in 1-methyl-2-pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.), and this solution was put in a stainless steel cup. This stainless steel cup is put into a glove box with an oxygen concentration of 0.1 ppm or less, and the solution in the stainless steel cup is bubbled with the atmospheric gas in the glove box at a rate of 20 mL / min. Kicked out. This stainless steel cup can be covered with PET film and quartz glass and placed in an oxygen-impermeable bag (High Barrier Bijin, manufactured by Krillon Kasei Co., Ltd.) to remove trace acids entering the bag. Thus, Secure (manufactured by Nisso Fine, Secur is a registered trademark of Nisso Fine) was used as an oxygen absorbent. The bag was completely sealed with heat sealing and taken out of the glove box (left side of FIG. 3).

This was put into a light resistance tester (Atlas Suntest CPS +, manufactured by Toyo Seiki Co., Ltd.) and irradiated with light for 4 hours. Thereafter, the amount of 9,10-bis (octanoyloxy) anthracene (OcA) before and after light irradiation was quantified by high performance liquid chromatography, and the residual ratio of 9,10-bis (octanoyloxy) anthracene (OcA) was calculated. . The results are shown in Table 5.

[Comparative Example 5]
1,10-bis (octanoyloxy) anthracene (OcA) was dissolved in 1 wt% in 1-methyl-2-pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.), and this solution was put in a stainless steel cup. In the air, this stainless steel cup is covered with PET film and quartz glass, put into an oxygen-impermeable bag (High Barrier Bijin, manufactured by Krillon Kasei Co., Ltd.), and the bag is completely sealed with heat sealing ( Figure 3 right). Otherwise, the same operation as in Example 13 was performed. The results are shown in Table 5.

  As can be seen from Table 5, in Example 13, singlet oxygen is not generated because oxygen is removed from the system. Therefore, it shows that the UV-A absorber is not decomposed by monopolymerized oxygen. On the other hand, in Comparative Example 5, since oxygen is present in the system, it is found that oxygen is excited and the UV-A absorber is decomposed by the singlet oxygen generated thereby. Therefore, it is shown that the UV-A absorber can exist stably by removing oxygen or singlet acid and can absorb UV-A.

(Example 14)
1 wt% of 9,10-bis (octanoyloxy) anthracene (OcA) as a UV-A absorber was added to 1-methyl-2-pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.), and IRGANOX 1010 (pentaerythritol tetrakis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF, IRGANOX is a registered trademark of BASF) was added at 5 wt%. This solution was put in a stainless steel cup and covered with a PET film and quartz glass. This was put into a light resistance tester (Atlas Suntest CPS +, manufactured by Toyo Seiki Co., Ltd.) and irradiated with light for 4 hours. Thereafter, the amount of 9,10-bis (octanoyloxy) anthracene (OcA) before and after light irradiation was quantified by high performance liquid chromatography, and the residual ratio of 9,10-bis (octanoyloxy) anthracene (OcA) was calculated. . The results are shown in Table 6.

(Example 15)
In Example 14, instead of IRGANOX 1010, ADK STAB AO-80 (3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethyl Ethoxy] -2,4,8,10-terolaoxaspiro [5.5] undecane, manufactured by ADEKA, Adeka Stub is a registered trademark of ADEKA), and the same operation was performed. The results are shown in Table 6.

[Comparative Example 6]
The same operation was performed except that IRGANOX 1010 was not added in Example 14. The results are shown in Table 6.

As can be seen from Table 6, in Examples 14 and 15, oxygen is trapped by the antioxidant, which indicates that the UV-A absorber is not decomposed by singlet oxygen. On the other hand, in Comparative Example 6, since the antioxidant is not added, it is shown that the UV-A absorber is decomposed by the generated singlet oxygen. Therefore, it is shown that the UV-A absorber can be stably present by using an antioxidant that does not generate singlet oxygen.

Claims (16)

The UV-A absorber which contains the anthracene compound represented by following General formula (1) as an active ingredient.
(In General Formula (1), R ¹ and R ² may be the same or different, and are an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 13 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. A group or an aryloxy group having 6 to 13 carbon atoms, X and Y may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms.) In the general formula (1), R ¹ and R ² are an alkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 13 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or an aryloxy group having 6 to 13 carbon atoms. The UV-A absorber according to claim 1, characterized in that it is. The ultraviolet absorber composition characterized by containing the UV-A absorber and UV-B absorber which are anthracene compounds represented by following General formula (1).
(In General Formula (1), R ¹ and R ² may be the same or different, and are an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 13 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. A group or an aryloxy group having 6 to 13 carbon atoms, X and Y may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms.) It contains a UV-A absorber that is an anthracene compound represented by the following general formula (1) and a UV-A absorber other than the anthracene compound represented by the following general formula (1), Ultraviolet absorber composition.
(In General Formula (1), R ¹ and R ² may be the same or different, and are an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 13 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. A group or an aryloxy group having 6 to 13 carbon atoms, X and Y may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms.) In the general formula (1), R ¹ and R ² are an alkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 13 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or an aryloxy group having 6 to 13 carbon atoms. The ultraviolet absorbent composition according to claim 3, wherein the ultraviolet absorbent composition is provided. A UV-A absorber according to claim 1 or 2, further comprising a hindered amine stabilizer. 6. An ultraviolet absorbent composition, further comprising a hindered amine stabilizer in the ultraviolet absorbent composition according to any one of claims 3 to 5. The UV-A absorber according to claim 1 or 2, further comprising an antioxidant and / or a singlet oxygen quencher. The ultraviolet absorbent composition according to any one of claims 3 to 7, further comprising an antioxidant and / or a singlet oxygen quencher. The UV-A cut film which contains the UV-A absorber of Claim 1 or Claim 2 as an active ingredient. The UV-A cut film which contains the ultraviolet absorber composition as described in any one of Claims 3 thru | or 9 as an active ingredient. The UV-A absorber according to claim 1 or 2 or the ultraviolet absorber composition according to any one of claims 3 to 9 is contained on a glass substrate, a metal substrate or an oxygen barrier film. A UV-A cut film, which is a polymerized film obtained by applying a photopolymerizable composition and further covering an oxygen barrier film on the coating film and then polymerizing and curing the film by irradiation with light. The UV-A cut film according to claim 12, wherein the oxygen permeability of the oxygen barrier film is 100 cm ³ / (m ² · day · atm) or less at 20 ° C. under dry conditions. It is a laminated body containing a UV-A cut film, Comprising: This laminated body has two high oxygen barrier film layers, Between the high oxygen barrier film layers, UV of any one of Claims 10 thru | or 13 A UV-A cut film laminate comprising an A cut film. It is a laminated body containing a UV-A cut film, Comprising: This laminated body has a glass substrate and a high oxygen barrier film layer, Between the glass substrate and a high oxygen barrier film layer, any one of Claims 10 thru | or 13 The UV-A cut film laminated body characterized by including the UV-A cut film of Claim 1. 16. The UV-A cut film laminate according to claim 14, wherein the oxygen permeability of the advanced oxygen barrier film is 10 cm ³ / (m ² · day · atm) or less at 20 ° C. under dry conditions.