JP2010095661A - Ultraviolet absorber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet absorber which does not cause deposition of the ultraviolet absorber and bleed-out caused by long-term use, is excellent in the long-wavelength ultraviolet absorption performance and the light fastness while maintaining the absorption performance for a long period of time. <P>SOLUTION: The ultraviolet absorber is represented by general formula (1), wherein, A represents an ultraviolet absorbing residue; B represents a photostable residue; L represents a linking group containing at least one nitrogen atom; and x, y and z each independently represents an integer of ≥1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an ultraviolet absorber. More specifically, the present invention does not cause precipitation of an ultraviolet absorber or bleed-out due to long-term use, and is excellent in long-wave ultraviolet absorbing ability and maintains this absorbing ability for a long period of time. The present invention relates to an ultraviolet absorber having excellent light resistance.

Conventionally, ultraviolet absorbers (also referred to as ultraviolet stabilizers) are commonly used with various resins to impart ultraviolet absorptivity. An inorganic ultraviolet absorber and an organic ultraviolet absorber may be used as the ultraviolet absorber. Inorganic ultraviolet absorbers (see, for example, Patent Documents 1 to 3) are excellent in durability such as weather resistance and heat resistance, but are selected because the absorption wavelength is determined by the band gap of the compound. There are few degrees of freedom, and there is nothing which can absorb to 320-400 nm long wave ultraviolet-ray (UV-A) area | region, and what absorbs long wave ultraviolet-ray will have coloring in order to have absorption to a visible region. Among them, by coating a specific titanic acid surface having a property of shielding a short-wave ultraviolet (UV-B) region of 280 to 320 nm with a cerium oxide-based ultraviolet shielding agent for shielding the UV-A region, and combining them. It is known that a wide ultraviolet region can be shielded (see, for example, Patent Document 4).
On the other hand, since the organic ultraviolet absorber has a high degree of freedom in the structural design of the absorbent, it is possible to obtain various absorption wavelengths by devising the structure of the absorbent.

  In the past, systems using various organic ultraviolet absorbers have been studied. When absorbing up to the long wave ultraviolet region, use one with a maximum absorption wavelength in the long wave ultraviolet region or increase the concentration. There are two possible ways. However, those having the maximum absorption wavelength described in Patent Documents 5 and 6 in the long-wave ultraviolet region have poor light resistance, and the absorption ability decreases with time.

  In contrast, benzophenone-based and benzotriazole-based UV absorbers have relatively good light resistance, and can be cut relatively clearly up to a long wavelength region by increasing the concentration and film thickness (see, for example, Patent Documents 7 and 8). .) However, when these ultraviolet absorbers are usually mixed and applied in a resin or the like, the film thickness is limited to about several tens of μm. When cutting to a long wavelength region with this film thickness, it is necessary to add an ultraviolet absorber at a considerably high concentration. However, there has been a problem that simply adding to a high concentration causes precipitation of ultraviolet absorbers and bleeding out due to long-term use. Further, even when the maximum absorption wavelength is in the long wave ultraviolet region, when an ultraviolet absorber having absorption at 400 nm or more is used, yellowish coloring occurs, and the hue of a color image to be observed through transmission is deteriorated. . This becomes a significant problem when added to a high concentration. Therefore, there has been a demand for an ultraviolet absorber that effectively and effectively shields the ultraviolet region and does not absorb in the visible region.

In addition, it is known to increase the molecular weight of an ultraviolet absorber by bonding a polymerizable group to the ultraviolet absorber (see, for example, Patent Document 9). This suppresses the volatilization and elution of the UV absorber, but when combining multiple UV absorbers, it is necessary to use high molecular weight materials. If they are not mixed uniformly, the UV shielding ability is uniform. There was a problem that did not become. Further, when a polymerizable monomer having no UV-absorbing residue is used in combination for adjusting the polymerizability and the performance of the resulting polymer, there is a problem that the UV-absorbing effect per mass is lowered.
JP-A-5-339033 JP-A-5-345639 JP-A-6-56466 JP 2006-316107 A JP-A-6-145387 JP 2003-177235 A JP 2005-517787 A JP-A-7-285927 JP 2001-19711 A

  An object of the present invention is to solve the above-mentioned problems, without causing precipitation of ultraviolet absorbers and bleeding out due to long-term use, and having excellent long-wave ultraviolet absorption ability and maintaining this absorption ability for a long period of time. The object is to provide an ultraviolet absorber excellent in light resistance.

  As a result of intensive studies, the present inventors have found that the ultraviolet absorber represented by the general formula (2) described later is excellent in long-wave ultraviolet absorbing ability, and further mixes the ultraviolet absorber with a resin or the like as a composition. It was found that when used, precipitation of the ultraviolet absorber and bleeding out due to long-term use do not occur. As a result of repeated studies in more detail about the structure of the ultraviolet absorber, the present inventors have found that even when the ultraviolet absorbent does not last for a long time when used alone, It has been found that the performance can be maintained for a long time by adopting a structure in which the compounds are connected and used.

  In addition, in the known method in which the polymerizable group is bonded to increase the molecular weight of the ultraviolet absorber, ultraviolet absorption per mass is caused by the presence of a monomer having no ultraviolet absorbing residue used for performance adjustment of the polymer. The effect will be reduced. In order to obtain the same UV absorption effect, the UV absorption effect per mass as the UV absorber is reduced by directly binding the compound used in combination as a light stabilizer to increase the molecular weight. It has been found that the total mass of the ultraviolet absorber and the light stabilizer necessary for the above can be reduced as compared with the case where the ultraviolet absorber and the light stabilizer are polymerized and added independently. In addition, when an ultraviolet absorber and a light stabilizer are separately polymerized and added, and they are in a state where the ultraviolet absorbing residue and the light stabilizer residue do not exist in the vicinity due to phase separation or the like, Absorbers and light stabilizers work independently, and an effect greater than the total of each cannot be expected. In the ultraviolet absorbent according to the present invention, the ultraviolet absorbing residue and the photostable residue are surely present in the vicinity, so that a synergistic effect can be expected.

When the ultraviolet absorber and the light stabilizer are present in the vicinity, there is a case where electrons or energy are transferred from one to the other. Since the electron transfer and energy transfer efficiencies depend on the two distances, the higher the efficiency, the higher the efficiency. Therefore, in the case of the UV absorber of the present invention in which an UV-absorbing residue and a light-stable residue are linked, this can occur significantly. it is conceivable that. For example, the light stabilizer can be considered to have the advantage of effectively suppressing the degradation mechanism of the UV-absorbing residue, but when the UV-absorbing residue absorbs UV light and is in an excited state, it quickly enters the ground state. Since the lifetime of the excited state is extended by electron transfer to the generated holes, a demerit that a decomposition reaction from the excited state is likely to occur can be considered. When linking a UV-absorbing residue and a light stabilizer, it is necessary to consider the combination, and it has been found that there is a preferable combination that can provide a synergistic effect.
The present invention has been made based on such findings.

The object of the present invention has been achieved by the following method.
<1> An ultraviolet absorber represented by the following general formula (1).

［一般式（１）中、Ａは、紫外線吸収性残基を表す。但し、Ａのうち少なくとも１つが、下記一般式（２）で表される化合物の任意の位置から水素原子または１価の置換基を取り除いてなる紫外線吸収性残基である。
Ｂは、下記一般式（ＴＳ−Ｉ）〜（ＴＳ−Ｖ）のいずれかで表される化合物の任意の位置から水素原子または１価の置換基を取り除いてなる残基を表す。
Ｌは、少なくとも一つの窒素原子を含む連結基を表す。ｘ、ｙ及びｚは、それぞれ独立に１以上の整数を表す。］

[In General Formula (1), A represents an ultraviolet-absorbing residue. However, at least one of A is an ultraviolet-absorbing residue obtained by removing a hydrogen atom or a monovalent substituent from any position of the compound represented by the following general formula (2).
B represents a residue obtained by removing a hydrogen atom or a monovalent substituent from any position of the compound represented by any of the following general formulas (TS-I) to (TS-V).
L represents a linking group containing at least one nitrogen atom. x, y, and z each independently represent an integer of 1 or more. ]

〔一般式（２）中、Ａ₁は炭素原子以外の２価以上の非金属原子を表す。Ｒ及びＲ₁は互いに独立して水素原子または１価の置換基を表す。また、Ｒ及びＲ₁は互いに結合して環を形成していても良く、これがさらに縮環していてもよい。Ｙ₁及びＹ₂は互いに独立して１価の置換基を表す。〕

[In General Formula (2), A ₁ represents a divalent or higher nonmetallic atom other than a carbon atom. R and R ₁ each independently represent a hydrogen atom or a monovalent substituent. R and R ₁ may be bonded to each other to form a ring, which may be further condensed. Y ₁ and Y ₂ each independently represent a monovalent substituent. ]

〔一般式（ＴＳ−Ｉ）中、Ｒ₉₁は水素原子、アルキル基、アルケニル基、アリール基、ヘテロ環基、アシル基、アルキルもしくはアルケニルオキシカルボニル基、アリールオキシカルボニル基、アルキルスルホニル基、アリールスルホニル基、ホスフィノトリル基、ホスフィニル基、又は−Ｓｉ(Ｒ₉₇)(Ｒ₉₈)(Ｒ₉₉)を表す。ここで、Ｒ₉₇、Ｒ₉₈、Ｒ₉₉は同一でも異なってもいてもよく、それぞれアルキル基、アルケニル基、アリール基、アルコキシ基又はアルケニルオキシ基、アリールオキシ基を表す。−Ｘ₉₁−は−Ｏ−、−Ｓ−又は−Ｎ(−Ｒ₁₀₀)−を表す。ここで、Ｒ₁₀₀はＲ₉₁と同義である。Ｒ₉₂、Ｒ₉₃、Ｒ₉₄、Ｒ₉₅、Ｒ₉₆は互いに同一でも異なってもよく、それぞれ、水素原子又は置換基を表す。Ｒ₉₁とＲ₉₂、Ｒ₁₀₀とＲ₉₆、Ｒ₉₁とＲ₁₀₀は互いに結合して５〜７員環を形成していてもよい。さらに、Ｒ₉₂とＲ₉₃、Ｒ₉₃とＲ₉₄が互いに結合して、５〜７員環又はスピロ環、ビシクロ環を形成してもよい。但し、Ｒ₉₁、Ｒ₉₂、Ｒ₉₃、Ｒ₉₄、Ｒ₉₅、Ｒ₉₆、Ｒ₁₀₀のすべてが水素原子であることはなく、総炭素数は１０以上である。
一般式（ＴＳ−ＩＩ）中、Ｒ₁₀₁、Ｒ₁₀₂、Ｒ₁₀₃、Ｒ₁₀₄は各々独立に、水素原子、アルキル基、アルケニル基を表し、Ｒ₁₀₁とＲ₁₀₂、Ｒ₁₀₃とＲ₁₀₄は結合し、５〜７員環を形成してもよい。Ｘ₁₀₁は水素原子、アルキル基、アルケニル基、アルキルオキシ基、アルケニルオキシ基、アルキルもしくはアルケニルオキシカルボニル基、アリールオキシカルボニル基、アシル基、アシルオキシ基、アルキルオキシカルボニルオキシ基、アルケニルオキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アルキルもしくはアルケニルスルホニル基、アリールスルホニル基、アルキルもしくはアルケニルスルフィニル基、アリールスルフィニル基、スルファモイル基、カルバモイル基、ヒドロキシ基又はオキシラジカル基を表す。Ｘ₁₀₂は５〜７員環を形成するのに必要な非金属原子群を表す。
一般式（ＴＳ−ＩＩＩ）中、Ｒ₁₀₅、Ｒ₁₀₆は水素原子、脂肪族基、アシル基、脂肪族オキシカルボニル基、芳香族オキシカルボニル基、脂肪族スルホニル基、芳香族スルホニル基を表し、Ｒ₁₀₇は脂肪族基、脂肪族オキシ基、芳香族オキシ基、脂肪族チオ基、芳香族チオ基、アシルオキシ基、脂肪族オキシカルボニルオキシ基、芳香族オキシカルボニルオキシ基、置換アミノ基、複素環基、ヒドロキシ基を表し、可能な場合にはＲ₁₀₅とＲ₁₀₆、Ｒ₁₀₆とＲ₁₀₇、Ｒ₁₀₅とＲ₁₀₇は互いに結合し、５〜７員環を形成してもよいが、２，２，６，６−テトラアルキルピペリジン骨格を形成する場合を除く。但し、Ｒ₁₀₅、Ｒ₁₀₆の両方が水素原子であることはなく、総炭素数は７以上である。
一般式（ＴＳ−ＩＶ）中、Ｒ₁₁₁、Ｒ₁₁₂は脂肪族基を表し、Ｒ₁₁₁とＲ₁₁₂は互いに結合し、５〜７員環を形成してもよい。ｎは０、１、２を表す。但し、Ｒ₁₁₁とＲ₁₁₂の総炭素数は１０以上である。
一般式（ＴＳ−Ｖ）中、Ｒ₁₂₁、Ｒ₁₂₂は脂肪族オキシ基、芳香族オキシ基を表し、Ｒ₁₂₃は脂肪族基、芳香族基、脂肪族オキシ基、芳香族オキシ基を表し、ｍは０又は１を表す。Ｒ₁₂₁とＲ₁₂₂、Ｒ₁₂₁とＲ₁₂₃は互いに結合し、５〜８員環を形成してもよい。但し、Ｒ₁₂₁、Ｒ₁₂₂、Ｒ₁₂₃の総炭素数は１０以上である。〕

[In general formula (TS-I), R ₉₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or alkenyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group. Represents a group, a phosphinotolyl group, a phosphinyl group, or -Si (R ₉₇ ) (R ₉₈ ) (R ₉₉ ). Here, R ₉₇ , R ₉₈ and R ₉₉ may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group or an aryloxy group. —X ₉₁ — represents —O—, —S— or —N (—R ₁₀₀ ) —. Here, R ₁₀₀ is synonymous with R ₉₁ . R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ and R ₉₆ may be the same as or different from each other, and each represents a hydrogen atom or a substituent. R ₉₁ and R ₉₂ , R ₁₀₀ and R ₉₆ , and R ₉₁ and R ₁₀₀ may be bonded to each other to form a 5- to 7-membered ring. Further, R ₉₂ and R ₉₃ , R ₉₃ and R ₉₄ may be bonded to each other to form a 5- to 7-membered ring, a spiro ring, or a bicyclo ring. However, R ₉₁ , R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ , R ₉₆ and R ₁₀₀ are not all hydrogen atoms, and the total number of carbon atoms is 10 or more.
In the general formula (TS-II), R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ each independently represents a hydrogen atom, an alkyl group or an alkenyl group, and R ₁₀₁ and R ₁₀₂ , R ₁₀₃ and R ₁₀₄ are bonded. , A 5- to 7-membered ring may be formed. X ₁₀₁ is a hydrogen atom, alkyl group, alkenyl group, alkyloxy group, alkenyloxy group, alkyl or alkenyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, alkyloxycarbonyloxy group, alkenyloxycarbonyloxy group, An aryloxycarbonyloxy group, an alkyl or alkenylsulfonyl group, an arylsulfonyl group, an alkyl or alkenylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, or an oxy radical group. X ₁₀₂ represents a non-metallic atomic group necessary for forming a 5- to 7-membered ring.
In formula (TS-III), R ₁₀₅ and R ₁₀₆ represent a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group, or an aromatic sulfonyl group, and R ₁₀₇ is an aliphatic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, acyloxy group, aliphatic oxycarbonyloxy group, aromatic oxycarbonyloxy group, substituted amino group, heterocyclic group Represents a hydroxy group, and when possible, R ₁₀₅ and R ₁₀₆ , R ₁₀₆ and R ₁₀₇ , R ₁₀₅ and R ₁₀₇ may be bonded to each other to form a 5- to 7-membered ring, Except for the case where a 6,6-tetraalkylpiperidine skeleton is formed. However, R ₁₀₅ and R ₁₀₆ are not both hydrogen atoms, and the total number of carbon atoms is 7 or more.
In formula (TS-IV), R ₁₁₁ and R ₁₁₂ may represent an aliphatic group, and R ₁₁₁ and R ₁₁₂ may be bonded to each other to form a 5- to 7-membered ring. n represents 0, 1, 2; However, the total carbon number of R ₁₁₁ and R ₁₁₂ is 10 or more.
In the general formula (TS-V), R ₁₂₁ and R ₁₂₂ represent an aliphatic oxy group and an aromatic oxy group, R ₁₂₃ represents an aliphatic group, an aromatic group, an aliphatic oxy group, and an aromatic oxy group, m represents 0 or 1; R ₁₂₁ and R ₁₂₂ , and R ₁₂₁ and R ₁₂₃ may be bonded to each other to form a 5- to 8-membered ring. However, the total carbon number of R ₁₂₁ , R ₁₂₂ and R ₁₂₃ is 10 or more. ]

（式中、Ａ₄₁及びＡ₄₂はそれぞれ独立して炭素原子以外の２価以上の非金属原子を表す。Ｙ₄₁及びＹ₄₂はそれぞれ独立して１価の置換基を表す。Ｖ₄₁、Ｖ₄₂、Ｖ₄₃及びＶ₄₄はそれぞれ独立して水素原子または１価の置換基を表す。Ｖ₄₁〜Ｖ₄₄は任意の場所で炭素原子とともに環を形成してもよく、これがさらに縮環していてもよい。）
＜３＞前記一般式（４）におけるＡ₄₁及びＡ₄₂がともに硫黄原子であることを特徴とする、＜２＞項に記載の紫外線吸収剤。
＜４＞前記一般式（４）で表される化合物が下記一般式（５）で表される化合物であることを特徴とする、＜２＞項に記載の紫外線吸収剤。

（式中、Ａ₅₁及びＡ₅₂はそれぞれ独立して炭素原子以外の２価以上の非金属原子を表す。Ｙ₅₁及びＹ₅₂はそれぞれ独立して１価の置換基を表す。Ｖ₅₁及びＶ₅₂はそれぞれ独立して水素原子または１価の置換基を表す。Ｘ₅₁及びＸ₅₂はそれぞれ独立して水素原子または１価の置換基を表す。）
＜５＞前記一般式（５）中、Ｙ₅₁及びＹ₅₂が、シアノ基、−ＣＯＲ¹、−ＣＯＯＲ²、−ＣＯＮＲ³Ｒ⁴、−ＳＯＲ⁵、−ＳＯ₂Ｒ⁶、もしくは−ＳＯ₂ＮＲ⁷Ｒ⁸を表すか（Ｒ¹〜Ｒ⁸は、水素原子または１価の置換基を表す。）、又はＹ₅₁及びＹ₅₂が互いに結合して環を形成していることを特徴とする、＜４＞項に記載の紫外線吸収剤。 <2> The ultraviolet absorber according to <1>, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (4).

(In the formula, A ₄₁ and A ₄₂ each independently represent a divalent or higher-valent non-metal atom other than a carbon atom. Y ₄₁ and Y ₄₂ each independently represent a monovalent substituent. V ₄₁ , V ₄₂ , V ₄₃ and V ₄₄ each independently represents a hydrogen atom or a monovalent substituent, and V _{41 to} V ₄₄ may form a ring together with the carbon atom at an arbitrary position, which is further condensed. May be.)
<3> The ultraviolet absorber according to <2>, wherein A ₄₁ and A ₄₂ in the general formula (4) are both sulfur atoms.
<4> The ultraviolet absorber according to <2>, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5).

(In the formula, A ₅₁ and A ₅₂ each independently represent a divalent or higher non-metallic atom other than a carbon atom. Y ₅₁ and Y ₅₂ each independently represent a monovalent substituent. V ₅₁ and V ₅₂ represents each independently a hydrogen atom or a monovalent substituent, and X ₅₁ and X ₅₂ each independently represent a hydrogen atom or a monovalent substituent.)
<5> In the general formula (5), Y ₅₁ and Y ₅₂ are each a cyano group, —COR ¹ , —COOR ² , —CONR ³ R ⁴ , —SOR ⁵ , —SO ₂ R ⁶ , or —SO ₂ NR. ⁷ represents R ⁸ (R ^{1 to} R ⁸ represent a hydrogen atom or a monovalent substituent), or Y ₅₁ and Y ₅₂ are bonded to each other to form a ring, The ultraviolet absorber as described in <4> term.

（式中、Ｘ₁₀₁は、水素原子、アルキル基、アルケニル基、アルキルオキシ基、アルケニルオキシ基、アルキルもしくはアルケニルオキシカルボニル基、アリールオキシカルボニル基、アシル基、アシルオキシ基、アルキルオキシカルボニルオキシ基、アルケニルオキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アルキルもしくはアルケニルスルホニル基、アリールスルホニル基、アルキルもしくはアルケニルスルフィニル基、アリールスルフィニル基、スルファモイル基、カルバモイル基、ヒドロキシ基又はオキシラジカル基を表す。Ｒ₂₀₀は１価の置換基を表す。）
＜９＞前記一般式（ＴＳ−ＩＩａ）中、Ｒ₂₀₀が−ＮＨＣＯＲ¹⁰基である（Ｒ¹⁰は、水素原子または１価の置換基を表す。）ことを特徴とする、＜８＞項に記載の紫外線吸収剤。
＜１０＞＜１＞〜＜９＞のいずれか１項に記載の紫外線吸収剤を含むことを特徴とする紫外線吸収剤組成物。
＜１１＞＜１＞〜＜９＞のいずれか１項に記載の紫外線吸収剤を含むことを特徴とする紫外線吸収剤溶液。
＜１２＞＜１＞〜＜９＞のいずれか１項に記載の紫外線吸収剤を含むことを特徴とする高分子材料。 <6> From the group consisting of L, —NH—, aminoalkylene, diaminoalkylene, aminoarylene, diaminoarylene, aminoalkenylene, diaminoalkenylene, aminoalkynylene, and diaminoalkynylene. The ultraviolet absorber according to any one of <1> to <5>, which is a linking group selected.
<7> At least one of the B is a residue obtained by removing a hydrogen atom or a monovalent substituent from any position of the compound represented by the general formula (TS-II). <1>-<6> The ultraviolet absorber according to any one of <6>.
<8> The ultraviolet absorber according to <7>, wherein the compound represented by the general formula (TS-II) is a compound represented by the following general formula (TS-IIa).

_Wherein X ₁₀₁ is a hydrogen atom, an alkyl group, an alkenyl group, an alkyloxy group, an alkenyloxy group, an alkyl or alkenyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, an alkyloxycarbonyloxy group, an alkenyl Oxycarbonyloxy group, aryloxycarbonyloxy group, alkyl or alkenylsulfonyl group, arylsulfonyl group, alkyl or alkenylsulfinyl group, arylsulfinyl group, sulfamoyl group, carbamoyl group, hydroxy group or oxy radical group R ₂₀₀ represents 1 Represents a valent substituent.)
<9> In the general formula (TS-IIa), R ₂₀₀ is a —NHCOR ¹⁰ group (R ¹⁰ represents a hydrogen atom or a monovalent substituent). The ultraviolet absorber as described.
<10> An ultraviolet absorbent composition comprising the ultraviolet absorbent according to any one of <1> to <9>.
<11> An ultraviolet absorbent solution comprising the ultraviolet absorbent according to any one of <1> to <9>.
<12> A polymer material comprising the ultraviolet absorber according to any one of <1> to <9>.

  The ultraviolet absorbent according to the present invention does not cause precipitation of the ultraviolet absorbent or bleed-out due to long-term use, and has an excellent effect of being excellent in ultraviolet absorbing ability over a long period of time and having no absorption in the visible region.

Hereinafter, the present invention will be described in detail.
The ultraviolet absorbent according to the present invention is an ultraviolet absorbent represented by the general formula (1), wherein a hydrogen atom or at least one position of the at least one ultraviolet absorbent represented by the general formula (2) An ultraviolet-absorbing residue A obtained by removing a monovalent substituent and a hydrogen atom or a monovalent from at least one compound represented by any one of the general formulas (TS-I) to (TS-V) It is characterized in that the residue B formed by removing a substituent is bonded via a linking group L containing at least one nitrogen atom.
The compound represented by any one of the general formulas (TS-I) to (TS-V) functions as a light stabilizer that prevents the resin from being decomposed by sharing it with various resins. In the ultraviolet absorbent of the present invention formed by bonding such a compound together with the ultraviolet absorbing residue, the ultraviolet absorbing ability of the ultraviolet absorbing residue can be maintained for a long period of time.

  The ultraviolet absorbing residue in the present invention represents a group of compounds that absorb ultraviolet rays of 200 to 400 nm, re-radiate the energy mainly as harmless thermal energy, and do not alter themselves. The ultraviolet absorbing residue may have any structure. As an example of an ultraviolet absorbing structure formed by combining an ultraviolet absorbing residue with a monovalent substituent, “Characteristics and Applications of Ultraviolet Shielding (UV Cut) Materials” (published by Technical Information Association, 1997), pages 54, 112 , “New Development of Functional Additives for Polymers” (published by Toray Research Center, 1999), pages 101-120, Fine Chemical, May 2004, pages 30-32, etc. -19768, JP 57-157236, JP 51-56620, JP 6-207159, JP 7-62325, JP 7-252235, JP 8-20585, JP JP 8-259708, JP 10-77220, JP 10-158248, JP 10-182622, JP 11-255613, JP 11-263778, JP 2000-44452, JP 2000 JP-A-143608, JP-A-2000-178266, JP-A-2001-64142, JP-T 2004-513162, JP-B-6-3682, JP-A-7-11231, JP-A-7- Examples thereof include structures described in publications such as 252235, JP-A-7-324283, JP-A-2002-80788 and JP-T-2005-504047.

  The A group in the general formula (1) will be described. Group A is a UV-absorbing residue. The ultraviolet absorbing residue A is an ultraviolet absorbing residue formed by removing a hydrogen atom or a monovalent substituent from an arbitrary position of the ultraviolet absorbing compound represented by the general formula (2).

  Next, the ultraviolet absorbing compound represented by the following general formula (2) will be described.

(In the general formula (2), A ₁ represents a represents .R and R ₁ are each independently hydrogen or a monovalent substituent divalent or more nonmetal atoms other than carbon atoms. Also, R ₁ and R may be bonded to each other to form a ring, which may be further condensed, and Y ₁ and Y ₂ each independently represent a monovalent substituent.

In the general formula (2), R and R ₁ represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (eg, methyl, ethyl), aryl group (eg, phenyl, naphthyl), cyano group, carboxyl group, Alkoxycarbonyl group (eg methoxycarbonyl), aryloxycarbonyl group (eg phenoxycarbonyl), substituted or unsubstituted carbamoyl group (eg carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl group (eg acetyl) An arylcarbonyl group (eg benzoyl), a nitro group, a substituted or unsubstituted amino group (eg amino, dimethylamino, anilino), an acylamino group (eg acetamido, ethoxycarbonylamino), a sulfonamide group (eg Tansulfonamide), imide groups (eg succinimide, phthalimide), imino groups (eg benzylideneamino), hydroxy groups, alkoxy groups (eg methoxy), aryloxy groups (eg phenoxy), acyloxy groups (eg acetoxy), alkylsulfonyloxy A group (eg methanesulfonyloxy), an arylsulfonyloxy group (eg benzenesulfonyloxy), a sulfo group, a substituted or unsubstituted sulfamoyl group (eg sulfamoyl, N-phenylsulfamoyl), an alkylthio group (eg methylthio), an arylthio group (For example, phenylthio), alkylsulfonyl group (for example, methanesulfonyl), arylsulfonyl group (for example, benzenesulfonyl), heterocyclic group (for example, pyridyl, morpholino), etc. It can be mentioned. The substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. Moreover, you may combine with substituents and may form a ring.
R ₁ and R may be bonded to each other to form a ring, which may be further condensed.

A ₁ represents a divalent or higher-valent nonmetallic atom other than a carbon atom. Specifically, boron, nitrogen, oxygen, silicon, phosphorus, sulfur, selenium atom and the like are represented. Of these, boron, nitrogen, oxygen, silicon, phosphorus and sulfur atoms are preferred, nitrogen, oxygen and sulfur atoms are more preferred, and sulfur atoms are particularly preferred.

Y ₁ and Y ₂ each independently represent a monovalent substituent. Examples of the monovalent substituent include the examples of the monovalent substituent described above.
Examples of Y ₁ and Y ₂ include a cyano group, a carboxyl group (eg, —COOH), an alkoxycarbonyl group (eg, —COOMe), an aryloxycarbonyl group (eg, —COOPh), a carbamoyl group (eg, —CONH). ₂ ), an alkylcarbonyl group (eg, —COMe), an arylcarbonyl group (eg, —COPh), an alkylsulfonyl group (eg, —SO ₂ Me), or an arylsulfonyl group (eg, —SO ₂ Ph) It is done. Y ₁ and Y ₂ are preferably —COR ¹ , —COOR ² , —CONR ³ R ⁴ , —SOR ⁵ , —SO ₂ R ⁶ or —SO ₂ NR ⁷ R ⁸ . Here, R ^{1 to} R ⁸ represent a hydrogen atom or a monovalent substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, and the number of carbon atoms. 7 to 15 aralkyl group, 1 to 10 carbon heterocyclic group, 1 to 20 alkoxy group, 6 to 14 aryloxy group, 1 to 20 alkylsulfenyl group , Arylsulfenyl group having 6 to 14 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, arylsulfonyl group having 6 to 14 carbon atoms, acyl group having 2 to 21 carbon atoms, 1 to carbon atoms 25 carbamoyl groups, sulfamoyl groups having 0 to 32 carbon atoms, alkoxycarbonyl groups having 1 to 20 carbon atoms, aryloxycarbonyl groups having 7 to 15 carbon atoms, and aryls having 2 to 21 carbon atoms. Examples include a ruamino group, a sulfonylamino group having 1 to 20 carbon atoms, an amino group having 0 to 32 carbon atoms, a cyano group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, and a halogen atom. Is an alkyl group having 3 to 16 carbon atoms or an aryl group having 6 to 10 carbon atoms.
Y ₁ and Y ₂ may be bonded to each other to form a ring.

  The ultraviolet absorbing compound represented by the general formula (2) is preferably represented by the following general formula (2-2).

In General Formula (2-2), A ₂₁ and A ₂₂ have the same meanings as A ₁ in General Formula (2), and the same applies when preferred. Y ₂₁ and Y ₂₂ have the same meanings as Y ₁ and Y ₂ in the general formula (2), and the same applies when preferred. (B) represents a nonmetallic atom group in which A ₂₁ and A ₂₂ and a carbon atom together form a ring. As the ring to be formed, a nitrogen-containing 5- or 6-membered ring is preferable. Examples include a pyrimidine ring, an imidazolidine ring, an imidazoline ring, an oxazoline ring, a thiazoline ring, and the like. These rings may have a monovalent substituent, and examples of the monovalent substituent described above can be given. In addition, a condensed ring structure may be formed together with an aromatic ring. Among these, the ring formed by (B) is preferably a thiazoline ring, an oxazoline ring, a dithiol ring, an imidazoline ring, or a benzo condensed ring thereof, more preferably a benzodithiol ring, a benzoxazoline ring, or a benzothiazoline ring. , A benzimidazoline ring, particularly preferably a benzodithiol ring.

  The ultraviolet absorbing compound represented by the general formula (2-2) is more preferably an ultraviolet absorbing compound represented by the following general formula (3).

In the general formula (3), A ₃₁ and A ₃₂ have the same meaning as A ₁ in the general formula (2), and the same applies when preferred. Y ₃₁ and Y ₃₂ have the same meanings as Y ₁ and Y ₂ in the general formula (2), and the same applies when preferred. (D) represents a nonmetallic atom group forming a ring containing a carbon atom. The ring formed by (D) may further have a monovalent substituent and may be further condensed. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Specific examples of the ring formed by (D) include, for example, cycloalkanes such as cyclohexane and cyclopentane, aryls such as a benzene ring, pyridine ring, pyrrole ring, thiophene ring, thiazole ring, oxazole ring, pyrazole ring, or Examples of these heterocycles such as benzo-condensed ring are benzene rings.

  The ultraviolet absorbing compound represented by the general formula (3) is more preferably an ultraviolet absorbing compound represented by the following general formula (4).

In the general formula (4), A ₄₁ and A ₄₂ have the same meaning as A ₁ in the general formula (2), and the same applies when preferred. Y ₄₁ and Y ₄₂ have the same meanings as Y ₁ and Y ₂ in the general formula (2), and the same applies when preferred. V _{41 to} V ₄₄ each represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the examples of the monovalent substituent described above. V _{41 to} V ₄₄ may form a ring at any position with a carbon atom, and this may be further condensed.
In the general formula (4), both A ₄₁ and A ₄₂ are preferably sulfur atoms.

  The ultraviolet absorbing compound represented by the general formula (4) is particularly preferably an ultraviolet absorbing compound represented by the following general formula (5).

In the general formula (5), A ₅₁ and A ₅₂ have the same meanings as A ₁ in the general formula (2), and the same applies when preferred. Y ₅₁ and Y ₅₂ have the same meanings as Y ₁ and Y ₂ in the general formula (2), and the same applies when preferred. In particular, Y ₅₁ and Y ₅₂ represent a cyano group, —COR ¹ , —COOR ² , —CONR ³ R ⁴ , —SOR ⁵ , —SO ₂ R ⁶ , or —SO ₂ NR ⁷ R ⁸ (R ¹ -R ⁸ represents a hydrogen atom or a monovalent substituent.), Or Y ₅₁ and Y ₅₂ are preferably bonded to each other to form a ring. V ₅₁ and V ₅₂ have the same meanings as V ₄₁ and V ₄₂ in the general formula (4), and the same applies when preferred. X ₅₁ and X ₅₂ each represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the above-described examples of the monovalent substituent. More preferably, the monovalent substituent has a substituent having 2 or more carbon atoms (for example, an acetyl group, an ethyl group, 2- Ethylhexyloxycarbonyl group, 2-ethylhexyl group), particularly preferably a substituent having 6 or more carbon atoms (for example, 2-ethylhexyl group, 2-ethylhexyloxy group, 2-ethylhexylcarbonyl group) It is.

  Specific examples of the compound represented by any one of the general formulas (2), (2-2), (3), (4) or (5) used in the present invention are shown below. The invention is not limited to this.

  The ultraviolet-absorbing compound represented by any one of the general formulas (2), (2-2), and (3) to (5) in the present invention is a Journal of Chemical Crystallography, 27, 1997. , 516 page, right line 3 to page 520, right line 15 line, Liebigs Annalen der Chemie, 726, page 106, line 15 to page 109, line 37, JP-A 49-1115 Gazette 3rd page, left 7th line to 5th page, left 8th line, Bioorganic & Medicinal Chemistry Letters, 7, 1997, page 652, 9th to 19th line, Journal of Organic Chemistry ( Journal of Organic Chemistry), 43, 1978, 2153, left column, lines 2 to 12. JP-A-4-338759, page 4, left column 2 to page 5, left column 2, line 2, JP-A-3-54566 PR page 7, left column 6, line 8 to page 8, left column 10, Synthesis, 1986, 968, left column, lines 1 to 22, etc., can be synthesized by citation or similar synthesis methods.

  The compound represented by any one of the general formulas (2), (2-2), and (3) to (5) used in the present invention can take a tautomer depending on the structure and the environment in which the compound is placed. . Although it is described in one of the representative forms in the present specification, tautomers different from those described in the present specification are also included in the compounds used in the present invention.

The compound represented by any one of the general formulas (2), (2-2), and (3) to (5) used in the present invention is an isotope (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O, etc.) may be contained.

  In the ultraviolet absorber represented by the general formula (1) of the present invention, the ultraviolet absorbing compound represented by any one of the general formulas (2), (2-2), and (3) to (5) It is preferable that the ultraviolet-absorbing residue A obtained by removing a hydrogen atom or a monovalent substituent from the position is simultaneously represented by the following general formula (6).

In the general formula (6), R, R ₁ , A ₁ , Y ₁ and Y ₂ have the same meanings as those shown in the general formula (2). However, Y ₁ or Y ₂ is represented by the following general formula (7).

In the general formula (7), * represents binding to the general formula (6) at this position, and ** represents binding to the linking group L at this position.
That is, in the ultraviolet absorbent represented by the general formula (1) of the present invention, the ultraviolet absorbing residue A is at the position of Y ₁ or Y ₂ in the ultraviolet absorbing compound represented by the general formula (2). It is preferable to bind to the linking group L.

  In the present invention, two or more kinds of ultraviolet absorbing residues represented by the general formula (2) having different structures may be included together, or the ultraviolet absorbing residue represented by the general formula (2). And one or more ultraviolet-absorbing residues having other structures may be included. When two types (preferably three types) of UV-absorbing residues are contained together, UV in a wide wavelength region can be absorbed. Any ultraviolet absorbing residue having a structure other than the general formula (2) can be used. Examples of the structure of the ultraviolet absorber include triazine, benzotriazole, benzophenone, merocyanine, cyanine, dibenzoylmethane, cinnamic acid, cyanoacrylate, and benzoate. For example, Fine Chemical, May 2004 issue, pages 28-38, published by Toray Research Center, Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999), pages 96-140, Junichi Okachi Examples include the ultraviolet absorber structure described in the supervised “Development of Polymer Additives and Environmental Countermeasures” (CMC Publishing Co., Ltd., 2003), pages 54-64.

  The ultraviolet absorbing residue having a structure other than the general formula (2) is preferably benzotriazole, benzophenone, salicylic acid, cyanoacrylate, or triazine. More preferred are benzotriazole, benzophenone, and triazine. Particularly preferred are benzotriazole and triazine compounds.

Then, B group in the said General formula (1) is demonstrated. The B group is a light obtained by removing a hydrogen atom or a monovalent substituent from any position of the compound (photostable compound) represented by any one of the general formulas (TS-I) to (TS-V). It is a stable residue.
Hereinafter, compounds represented by the following general formulas (TS-I) to (TS-V) used in the present invention will be described.

In the general formula (TS-I), R ₉₁ represents a hydrogen atom, an alkyl group (including a cyclic alkyl group such as a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (a cycloalkenyl group, a bicycloalkenyl group). Cyclic alkenyl groups such as tricycloalkenyl groups), aryl groups, heterocyclic groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups (cycloalkylsulfonyl groups, bicycloalkylsulfonyl groups, tricyclo A cyclic alkylsulfonyl group such as an alkylsulfonyl group), an arylsulfonyl group, a phosphino group, a phosphinyl group, or —Si (R ₉₇ ) (R ₉₈ ) (R ₉₉ ). Here, R ₉₇ , R ₉₈ and R ₉₉ may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group or an aryloxy group. —X ₉₁ — represents —O—, —S— or —N (—R ₁₀₀ ) —. Here, R ₁₀₀ is synonymous with R ₉₁ . R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ and R ₉₆ may be the same as or different from each other, and each represents a hydrogen atom or a substituent. R ₉₁ and R ₉₂ , R ₁₀₀ and R ₉₆ , and R ₉₁ and R ₁₀₀ may be bonded to each other to form a 5- to 7-membered ring. Further, R ₉₂ and R ₉₃ , R ₉₃ and R ₉₄ may be bonded to each other to form a 5- to 7-membered ring, a spiro ring, or a bicyclo ring. However, R ₉₁ , R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ , R ₉₆ and R ₁₀₀ are not all hydrogen atoms, and the total number of carbon atoms is 10 or more.

  When a group herein contains an aliphatic moiety, the aliphatic moiety may be linear, branched or cyclic and saturated or unsaturated, such as alkyl, alkenyl, cycloalkyl, Represents cycloalkenyl, and these may be unsubstituted or may have a substituent. When an aryl moiety is included, the aryl moiety may be a single ring or a condensed ring, and may be unsubstituted or have a substituent. In addition, when a heterocyclic moiety is included, the heterocyclic moiety has a heteroatom (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) in the ring. Even if it is a saturated ring, it is an unsaturated ring. It may be a single ring or a condensed ring, may be unsubstituted or may have a substituent, and may be bonded with a cyclic hetero atom or bonded with a carbon atom. May be.

  The substituent in the present invention may be any group that can be substituted, for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a heterocyclic oxy Group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyl Oxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, Heterocyclic oxycarbonylamino group, aliphatic Rufinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom , Sulfamoylcarbamoyl group, carbamoylsulfamoyl group, phosphinyl group, phosphoryl group and the like.

The general formula (TS-I) will be described in more detail.
R ₉₁ includes a hydrogen atom, an alkyl group (including a cyclic alkyl group such as a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group, such as a methyl group, an i-propyl group, an s-butyl group, a dodecyl group). Group, methoxyethoxy group, benzyl group), alkenyl group (including cycloalkenyl group, bicycloalkenyl group, for example, allyl group), aryl group (for example, phenyl group, p-methoxyphenyl group) heterocyclic group (for example, 2- Tetrahydrfuryl group, pyranyl group), acyl group (for example, acetyl group, pivaloyl group, benzoyl group, acryloyl group), alkyl or alkenyloxycarbonyl group (for example, mexycarbonyl group, hexadecyloxycarbonyl group), aryloxycarbonyl group ( For example, phenoxycarbonyl group, p-methoxy Phenoxycarbonyl group), alkylsulfonyl group (for example, methanesulfonyl group, butanesulfonyl group), arylsulfonyl group (for example, benzenesulfonyl group, p-toluenesulfonyl group), phosphinotolyl group (for example, dimethoxyphosphino group, diphenoxyphosphino group) , Phosphinyl group (for example, diethylphosphinyl group, diphenylphosphinyl group), or -Si ( _R97 ) ( _R98 ) ( _R99 ). Here, R ₉₇ , R ₉₈ and R ₉₉ may be the same or different, and are each an alkyl group (for example, methyl group, ethyl group, t-butyl group, benzyl group), alkenyl group (for example, allyl group), aryl A group (for example, phenyl group), an alkoxy group (for example, methoxy group, butoxy group), an alkenyloxy group (for example, allyloxy group), or an aryloxy group (for example, phenoxy group) is represented.

—X ₉₁ — represents —O—, —S— or —N (—R ₁₀₀ ) —. Here, R ₁₀₀ has the same meaning as R ₉₁ , and the preferred range is also the same. R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ , and R ₉₆ may be the same or different and each represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an alkyl group (a cycloalkyl group, a bicycloalkyl group). A cyclic alkyl group such as a tricycloalkyl group), an alkenyl group (including a cyclic alkenyl group such as a cycloalkenyl group, a bicycloalkenyl group, and a tricycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic group. , Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (anilino group) An acylamino group, an aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, Alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl Examples are the groups.

Among them, preferred substituents are alkyl groups (for example, methyl group, t-butyl group, t-hexyl group, benzyl group), alkenyl groups (aryl group), aryl groups (for example, phenyl group), alkoxycarbonyl groups (for example, methoxy group). Carbonyl group, dodecyloxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkyl or alkenylsulfonyl group (for example, methanesulfonyl group, butanesulfonyl group), arylsulfonyl group (for example, benzenesulfonyl group, p-hydroxybenzene) Sulfonyl group) or -X ₉₁ -R ₉₁ .
R ₉₁ and R ₉₂ , R ₁₀₀ and R ₉₆ , and R ₉₁ and R ₁₀₀ may be bonded to each other to form a 5- to 7-membered ring (for example, a chroman ring or a morpholine ring). Furthermore, R ₉₂ and R ₉₃ , R ₉₃ and R ₉₄ may be bonded to each other to form a 5- to 7-membered ring (for example, a chroman ring or an indane ring), a spiro ring, or a bicyclo ring. However, R ₉₁ , R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ , R ₉₆ , and R ₁₀₀ are not all hydrogen atoms, and the total number of carbons is 10 or more, preferably 16 or more. is there.

The compound represented by the general formula (TS-I) used in the present invention is represented by the general formula (I) of JP-B 63-50691 and the general formulas (IIIa) and (IIIb) of JP-B-2-37575. (IIIc), general formula of JP-A-2-50457, general formula of JP-A-5-67220, general formula (IX) of JP-A-5-70809, general formula of JP-A-6-19534, JP-A-62-2 No. 227889, general formula (I), 62-244046, general formula (I) (II), JP-A-2-66541, general formula (I) (II), and JP-A-2-139544. General formulas (II) and (III), general formula (I) of JP-A-2-194602, general formulas (B), (C) and (D) of JP-A-2-212636, and JP-A-3-200788 General formula (III), JP 3-48845 General formulas (II) and (III), general formulas (B), (C) and (D) in JP-A-3-266636, general formulas (I) in JP-A-3-969440, and JP-A-4-330440 General formula (I), general formula (I) of JP-A-5-297541, general formula of JP-A-6-130602, general formulas (1), (2), (3) of WO 91/11749 German Patent Application Publication No. 4008785A1, General Formula (I), US Pat. No. 4,931,382 General Formula (II), European Patent No. 203746B1, General Formula (a), European Patent No. 264730B1 And compounds represented by general formula (I) and the like in the specification.
Examples of the compound represented by the general formula (TS-I) include compounds represented by the following general formulas (TS-IA) to (TS-IG). In the present invention, compounds having these structures are preferable. .

In the general formulas (TS-IA) to (TS-IG), R _{91 to} R ₉₇ are the same as those defined in the general formula (TS-I), and preferred ranges are also the same. R _a1 to R _a4 each represent a hydrogen atom or an aliphatic group, X ₉₂ and X ₉₃ represents a divalent linking group. As a bivalent coupling group, an alkylene group, an oxy group, and a sulfonyl group are represented, for example. In the formula, the same symbols in the same molecule may be the same or different.

In the general formula (TS-II), R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ each independently represents a hydrogen atom, an alkyl group (a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, or the like). ), An alkenyl group (including a cyclic alkenyl group such as a cycloalkenyl group, a bicycloalkenyl group, and a tricycloalkenyl group), and R ₁₀₁ and R ₁₀₂ , R ₁₀₃ and R ₁₀₄ are bonded to each other and are 5 to 7 members. A ring may be formed.
X ₁₀₁ is a hydrogen atom, an alkyl group (including a cyclic alkyl group such as a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group), an alkenyl group (a cyclic alkenyl group such as a cycloalkenyl group, a bicycloalkenyl group, or a tricycloalkenyl group). A group, an alkoxy group, an alkenyloxy group, an alkyl or alkenyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, an alkyloxycarbonyloxy group, an alkenyloxycarbonyloxy group, an aryloxycarbonyloxy group, Represents an alkyl or alkenylsulfonyl group, an arylsulfonyl group, an alkyl or alkenylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group or an oxy radical group .
X ₁₀₂ represents a non-metallic atomic group necessary for forming a 5- to 7-membered ring.

The general formula (TS-II) will be described in more detail.
In the formula, R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ are a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group), or an alkenyl group (for example, an allyl group), and preferably an alkyl group.
X ₁₀₁ represents a hydrogen atom, an alkyl group (for example, methyl group, ethyl group), an alkenyl group (for example, allyl group), an alkyloxy group (for example, methoxy group, octyloxy group, cyclohexyloxy group), an alkenyloxy group (for example, allyloxy group). Group), alkyloxycarbonyl group (for example, methoxycarbonyl group, hexadecyloxycarbonyl group), alkenyloxycarbonyl group (for example, allyloxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group, p-chlorophenoxycarbonyl group) An acyl group (eg acetyl group, pivaloyl group, methacryloyl group), an acyloxy group (eg acetoxy group, benzoyloxy group), an alkyloxycarbonyloxy group (eg methoxycarbonyloxy group, octylo group) Xycarbonyloxy group), alkenyloxycarbonyloxy group (for example, allyloxycarbonyloxy group), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy group), alkylsulfonyl group (for example, methanesulfonyl group, butanesulfonyl group), alkenylsulfonyl Group (for example, allylsulfonyl group), arylsulfonyl group (for example, benzenesulfonyl group, p-toluenesulfonyl group), alkylsulfinyl group (for example, methanesulfinyl group, octanesulphinyl group), alkenylsulfinyl group (for example, allylsulfinyl group), An arylsulfinyl group (for example, benzenesulfinyl group, p-toluenesulfinyl group), a sulfamoyl group (for example, dimethylsulfamoyl group), a carbamoyl group ( Example, if dimethylcarbamoyl group, diethylcarbamoyl group), a hydroxy group or an oxy radical group.
X ₁₀₂ represents a non-metallic atomic group necessary for forming a 5- to 7-membered ring (e.g. a piperidine ring, piperazine ring).

In the general formula (TS-II), more preferably, R ₁₀₃ , R ₁₀₄ , R ₁₀₅ and R ₁₀₆ are all alkyl groups having 1 to 3 carbon atoms, X ₁₀₁ is an oxy radical, and 1 to 12 carbon atoms. An alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an acyl group having 2 to 14 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and X ₁₀₂ represents a cyclohexane ring. To form.
The general formula (TS-II) is particularly preferably represented by the following general formula (TS-IIa).

In the formula, X ₁₀₁ has the same meaning as X ₁₀₁ in formula (TS-II), and the preferred range is also the same. R ₂₀₀ represents a monovalent substituent. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Examples of the monovalent substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (eg, methyl, ethyl), aryl group (eg, phenyl, naphthyl), cyano group, carboxyl group, Alkoxycarbonyl group (eg methoxycarbonyl), aryloxycarbonyl group (eg phenoxycarbonyl), substituted or unsubstituted carbamoyl group (eg carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl group (eg acetyl) An arylcarbonyl group (eg benzoyl), a nitro group, a substituted or unsubstituted amino group (eg amino, dimethylamino, anilino), an acylamino group (eg acetamido, ethoxycarbonylamino), a sulfonamide group (eg Tansulfonamide), imide groups (eg succinimide, phthalimide), imino groups (eg benzylideneamino), hydroxy groups, alkoxy groups (eg methoxy), aryloxy groups (eg phenoxy), acyloxy groups (eg acetoxy), alkylsulfonyloxy A group (eg methanesulfonyloxy), an arylsulfonyloxy group (eg benzenesulfonyloxy), a sulfo group, a substituted or unsubstituted sulfamoyl group (eg sulfamoyl, N-phenylsulfamoyl), an alkylthio group (eg methylthio), an arylthio group (For example, phenylthio), alkylsulfonyl group (for example, methanesulfonyl), arylsulfonyl group (for example, benzenesulfonyl), heterocyclic group (for example, pyridyl, morpholino), etc. It can be mentioned. The substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. Moreover, you may combine with substituents and may form a ring. R ₂₀₀ is preferably an acylamino group (—NHCOR ¹⁰ group (R ¹⁰ represents a hydrogen atom or a monovalent substituent)).

  The compounds represented by the above general formula (TS-II) used in the present invention are represented by the general formula (I) of JP-B-2-32298, the general formula (I) of 3-39296, and the 3- No. 40373, general formula (I) of JP-A-2-49762, general formula (II) of JP-A-2-208653, general formula (III) of JP-A-2-217845, US Pat. The compounds represented by the general formula (B) of 4906555, the general formula of European Patent Application No. 309400A2, the general formula of 309401A1, the general formula of 309402A1, etc. Include.

In the general formula (TS-III), R ₁₀₅ and R ₁₀₆ represent a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, _R107 is an aliphatic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, acyloxy group, aliphatic oxycarbonyloxy group, aromatic oxycarbonyloxy group, substituted amino group, heterocyclic ring Represents a hydroxy group, and when possible, R ₁₀₅ and R ₁₀₆ , R ₁₀₆ and R ₁₀₇ , R ₁₀₅ and R ₁₀₇ may be bonded to each other to form a 5- to 7-membered ring; , 6,6-tetraalkylpiperidine skeleton is excluded. However, R ₁₀₅ and R ₁₀₆ are not both hydrogen atoms, and the total number of carbon atoms is 7 or more.

The general formula (TS-III) will be described in more detail.
In the formula, R ₁₀₅ and R ₁₀₆ are a hydrogen atom, an aliphatic group (for example, methyl group, ethyl group, t-butyl group, octyl group, methoxyethoxy group), acyl group (for example, acetyl group, pivaloyl group, methacryloyl group), Aliphatic oxycarbonyl group (for example, methoxycarbonyl group, hexadecyloxycarbonyl group), aromatic oxycarbonyl group (for example, phenoxycarbonyl group), aliphatic sulfonyl group (for example, methanesulfonyl group, butanesulfonyl group), aromatic sulfonyl group ( For example, it represents a phenylsulfonyl group), and R ₁₀₇ represents an aliphatic group (for example, a methyl group, an ethyl group, a t-butyl group, an octyl group, a methoxyethoxy group), an aliphatic oxy group (for example, a methoxy group, an octyloxy group), Aromatic oxy group (eg phenoxy group, p-methoxyphenoxy group), aliphatic thio Group (for example, methylthio group, octylthio group), aromatic thio group (for example, phenylthio group, p-methoxyphenylthio group), acyloxy group (for example, acetoxy group, pivaloyloxy group), aliphatic oxycarbonyloxy group (for example, methoxycarbonyloxy group) , Octyloxycarbonyloxy group), aromatic oxycarbonyloxy group (for example, phenoxycarbonyloxy group), substituted amino group (substituent may be substituted, for example, aliphatic group, aromatic group, acyl group, aliphatic group) A substituted amino group such as a sulfonyl group and an aromatic sulfonyl group), a heterocyclic group (for example, a piperidine ring, a thiomorpholine ring), a hydroxy group, and when possible, R ₁₀₅ and R ₁₀₆ , R ₁₀₆ and R ₁₀₇ , R ₁₀₅ and R ₁₀₇ are bonded to each other, a 5- to 7-membered ring (e.g. a piperidine ring, Pirazoriji Ring) may be formed. However, R ₁₀₅ and R ₁₀₆ are not both hydrogen atoms, and the total number of carbon atoms is 7 or more.

The compound represented by the general formula (TS-III) used in the present invention is represented by the general formula (I) of JP-B-6-97332, the general formula (I) of JP-B-6-97334, General formula (I) of JP-A-2-148037, general formula (I) of JP-A-2-150841, general formula (I) of JP-A-2-181145, general formula (I) of JP-A-2-266636 And compounds represented by general formula (IV) of JP-A-4-350854, general formula (I) of JP-A-5-61166, and the like.
Examples of the compound represented by the general formula (TS-III) include compounds represented by the following general formulas (TS-IIIA) to (TS-IIID). In the present invention, compounds having these structures are preferable. .

In the general formulas (TS-IIIA) to (TS-IIID), R _{105 to} R ₁₀₆ are the same as those defined in the general formula (TS-III), and preferred ranges are also the same. R _b1 to R _b3 are the same meaning as R _105, preferred ranges are also the same. R _b4 , R _b5 and R _b6 each represents an aliphatic group. X ₁₀₃ represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring.

In the general formula (TS-IV), R ₁₁₁ and R ₁₁₂ may represent an aliphatic group, and R ₁₁₁ and R ₁₁₂ may be bonded to each other to form a 5- to 7-membered ring. n represents 0, 1, 2; However, the total carbon number of R ₁₁₁ and R ₁₁₂ is 10 or more.

The general formula (TS-IV) will be described in more detail.
In the general formula (TS-IV), R ₁₁₁ and R _{112 each} represents an aliphatic group (for example, methyl group, methoxycarbonylethyl group, dodecyloxycarbonylethyl group), R ₁₁₁ and R ₁₁₂ are bonded to each other, A 7-membered ring (for example, a tetrahydrothiophene ring or a thiomorpholine ring) may be formed. n represents 0, 1, 2; However, the total carbon number of R ₁₁₁ and R ₁₁₂ is 10 or more.
The compound represented by the general formula (TS-IV) used in the present invention is represented by the general formula (I) of JP-B-2-44052, the general formula (T) of JP-A-3-48242, and 3- Of general formula (A) of US Pat. No. 2,668,36, general formula (I) (II) (III) of US Pat. No. 5,323,545, general formula (I) of US Pat. No. 4,933,271, The compound represented by general formula (I) etc. is included.

In the general formula (TS-V), R ₁₂₁ and R ₁₂₂ represent an aliphatic oxy group and an aromatic oxy group, and R ₁₂₃ represents an aliphatic group, an aromatic group, an aliphatic oxy group, and an aromatic oxy group. , M represents 0 or 1. R ₁₂₁ and R ₁₂₂ , and R ₁₂₁ and R ₁₂₃ may be bonded to each other to form a 5- to 8-membered ring. However, the total carbon number of R ₁₂₁ , R ₁₂₂ and R ₁₂₃ is 10 or more.

The general formula (TS-V) will be described in more detail.
In the general formula (TS-V), R ₁₂₁ and R ₁₂₂ are aliphatic oxy groups (for example, methoxy group, t-octyloxy group), aromatic oxy groups (for example, phenoxy group, 2,4-di-t-butyl). R ₁₂₃ represents an aliphatic group (for example, methyl group, ethyl group, t-octyl group), aromatic group (for example, phenyl group, 4-t-butylphenyl group), aliphatic oxy group (for example, methoxy group). Group, t-octyloxy group) and an aromatic oxy group (for example, phenoxy group, 4-t-butylphenoxy group), and m represents 0 or 1. R ₁₂₁ and R ₁₂₂ , and R ₁₂₁ and R ₁₂₃ may be bonded to each other to form a 5- to 8-membered ring. However, the total carbon number of R ₁₂₁ , R ₁₂₂ and R ₁₂₃ is 10 or more.
The compound represented by the above general formula (TS-V) used in the present invention is represented by the general formula (I) of JP-A-3-25437, the general formula (I) of JP-A-3-142444, US Pat. It includes compounds represented by the general formula of No. 4794645, the general formula of No. 4980275, and the like.

  The compound represented by any one of the general formulas (TS-I) to (TS-V) is represented by any one of the general formulas (TS-I), (TS-II), or (TS-V). Are preferably selected from the compounds represented by the general formula (TS-I) or (TS-II), more preferably the general formula (TS-II). It is further more preferable that it is a compound represented by these. As the compound represented by the general formula (TS-II), a compound having a 2,2,6,6-tetraalkylpiperidine skeleton is particularly preferable.

  Specific examples of the compound represented by any one of the general formulas (TS-I) to (TS-V) are shown below, but the present invention is not limited thereto. In addition, TI-1 to 57 is a compound corresponding to the general formula (TS-I), and TII-1 to 36 is a compound corresponding to the general formula (TS-II). For compounds corresponding to TS-III), TIII-1 to 13 correspond to the general formula (TS-IV), and for compounds corresponding to the general formula (TS-IV), TIV-1 to 6 correspond to the general formula (TS-V). TV-1 to 8 are assigned as reference numbers to the compounds.

  When two or more compounds represented by any one of the general formulas (TS-I) to (TS-V) are included, two or more compounds from the same group may be used in combination (for example, the general formula ( TS-II) may be used in combination over two or more groups (for example, the compound represented by the general formula (TS-I) and the general compound). A case where one compound each represented by formula (TS-II) is used). Preferably, two or more types are used in combination over a plurality of groups.

Next, L, x, y and z in the general formula (1) will be described.
In the general formula (1), x and z represent an integer of 1 or more. Preferably it is 1 or more and 10 or less, More preferably, it is 1 or more and 5 or less, More preferably, it is 1 or more and 3 or less, Most preferably, it is 1.
When x is 2 or more, the plurality of ultraviolet absorbing residues A may be the same or different. The number corresponding to the ultraviolet-absorbing residue A is preferably two or less, and particularly preferably only one.
When z is 2 or more, the plurality of residues B may be the same or different. The number corresponding to the residue B is preferably 3 or less, more preferably 2 types, and particularly preferably 1 type.

  In the general formula (1), L represents a linking group containing at least one nitrogen atom. This linking group is composed of an aliphatic hydrocarbon group or an aromatic hydrocarbon group, an atom selected from hetero atoms such as a nitrogen atom, a sulfur atom, and an oxygen atom or an atomic group containing the same, and at least one nitrogen atom Including. For example, preferred examples of the divalent linking group include at least one of -NH- group or -N (R)-group (R is the above-described monovalent substituent) and an alkylene group (for example, methylene, ethylene, Propylene, butylene, pentylene), arylene groups (eg, phenylene, naphthylene), alkenylene groups (eg, ethenylene, propenylene), alkynylene groups (eg, ethynylene, propynylene), amide groups, ester groups, sulfoamide groups, sulfonic acid ester groups Ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, amino group, or heterocyclic divalent group (eg, 6-chloro-1,3,5-triazine-2,4-diyl group, One or more groups among pyrimidine-2,4-diyl group and quinoxaline-2,3-diyl group) Include linking groups 20 or less carbon number of 1 or more configured by combining. These substituents may contain a ring (aromatic or non-aromatic hydrocarbon ring or hetero ring).

L is preferably a —NH— group, an aminoalkylene group (eg, aminomethylene, aminoethylene, aminopropylene, aminobutylene, aminopentylene), a diaminoalkylene group (eg, diaminomethylene, diaminoethylene, diaminopropylene, diaminobutylene). , Diaminopentylene), aminoarylene groups (eg, aminophenylene, aminonaphthylene), diaminoarylene groups (eg, diaminophenylene, diaminonaphthylene), aminoalkenylene groups (eg, aminoethenylene, aminopropenylene), diamino Alkenylene groups (eg, diaminoethenylene, diaminopropenylene), aminoalkynylene groups (eg, aminoethynylene, aminopropynylene), diaminoalkynylene groups (eg, diaminium) Ethynylene, a diaminopropionic Opini Ren). The above linking group may further have an example of the aforementioned monovalent substituent R.
L may be linked to UV-absorbing residue A and residue B at any position.

  In the general formula (1), y represents an integer of 1 or more. Preferably it is 1 or more and 10 or less, More preferably, it is 1 or more and 5 or less, More preferably, it is 1. When y is 2 or more, the plurality of L may be the same or different.

  Although the specific example of the ultraviolet absorber represented by the said General formula (1) of this invention is shown below, this invention is not limited to this.

  The ultraviolet absorbent represented by the general formula (1) of the present invention can be efficiently prepared by utilizing various bond forming reactions well known in organic synthetic chemistry. For example, amide bond forming reaction, ester bond forming reaction, carbon-carbon bond forming reaction, ether bond forming reaction and the like can be mentioned. Examples of the method for preparing the ultraviolet absorber represented by the general formula (1) include a method of linking the ultraviolet absorbing residue A part and the residue B part last, and synthesis of the ultraviolet absorbing residue A part. Method of constructing UV-absorbing residue A after connecting linking group L and residue B moiety to raw material and intermediate, linking group L and UV-absorbing residue A to synthesis raw material and intermediate of residue B part Any method, such as a method of constructing the residue B part after linking the parts, may be selected and prepared as appropriate. Synthetic reactions for these preparations are described, for example, by RC Larock, “Comprehensive Organic Transformation-A Guide to Functional Group Preparatory. Comprehensive Organic Transformations -A Guide to Functional Group Preparations- (VCH Publishers, New York, 1989) be able to.

For example, Exemplified Compound 1-4 is prepared by synthesizing a benzodithiolane moiety by the method described in “Journal of Chemical Crystallography” (1997), 27 (9), Japanese Patent Application Laid-Open No. 2008-107767, etc., and US Pat. No. 5,017,702. By synthesizing an aminoethyl form of the HALS compound (compound represented by any one of the general formulas (TS-I) to (TS-V)) according to the method described in Examples 1 and 2 of Can do. Exemplified compound 1-5 was synthesized from commercially available 4-amino-2,2,6,6-tetramethylpiperidine in Example 1 of US Pat. No. 5,017,702 after synthesizing a bis-form of benzodithiolane by a similar method. It can be synthesized by synthesizing cyanoacetamide amides according to the method and reacting them.
Exemplary compounds 1-14 are described by FM Harmer, “Heterocyclic Compounds-Cyanine Dyes and Related Compounds”, John Willie &・ John Willey & Sons, New York, London, 1994, DMSturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Special Topics In Heterocyclic Chemistry), Chapter 18, 14: 482-515, John Willey & Sons, New York, London, 1977, “Rods Chemistry of Carbon. "Rodd's Chemistry of Carbon Compounds", 2nd Edi , Vol.4, Part B, Chapter 15: 369-422, Elsevier Science Publishing Company Inc., New York, 1977, British Patent No. 1077611, etc. It can be synthesized by the method described.

  The ultraviolet absorber of the present invention may be in any form. For example, a liquid dispersion, a solution, a polymer material, and the like can be given. In addition to the ultraviolet absorbent according to the present invention, an arbitrary compound can be appropriately contained as another component depending on the purpose.

The ultraviolet absorbent of the present invention is preferably in the state of a dispersion dispersed in a dispersion medium. Hereinafter, the ultraviolet absorbent dispersion of the present invention will be described.
Any medium may be used for dispersing the ultraviolet absorbent according to the present invention. For example, water, an organic solvent, a resin, a resin solution, and the like can be given. These may be used alone or in combination.

  Examples of the organic solvent for the dispersion medium used in the present invention include hydrocarbons such as pentane, hexane and octane, aromatics such as benzene, toluene and xylene, ethers such as diethyl ether and methyl t-butyl ether, Alcohols such as methanol, ethanol and isopropanol, esters such as acetone, ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethyl Amides such as acetamide and N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, amines such as triethylamine and tributylamine, carboxylic acids such as acetic acid and propionic acid, halogens such as methylene chloride and chloroform Tetrahydrofuran, heterocyclic ring system, such as pyridine, and the like. These can be used in combination at any ratio.

  Examples of the resin for the dispersion medium used in the present invention include thermoplastic resins and thermosetting resins conventionally used in the production of various conventionally known molded articles, sheets, films and the like. Examples of thermoplastic resins include polyethylene resins, polypropylene resins, poly (meth) acrylic ester resins, polystyrene resins, styrene-acrylonitrile resins, acrylonitrile-butadiene-styrene resins, polyvinyl chloride resins, Polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol resin, polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), liquid crystal polyester Resin (LCP), polyacetal resin (POM), polyamide resin (PA), polycarbonate resin, polyurethane resin, polyphenylene sulfide resin (PPS), and the like. It is used as a polymer blend or polymer alloy. These resins are also used as thermoplastic molding materials in which natural resins contain fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulosic fibers, glass beads, flame retardants, and the like. Moreover, conventionally used additives for resins, for example, polyolefin resin fine powder, polyolefin wax, ethylene bisamide wax, metal soap, etc. can be used alone or in combination as required.

  Examples of the thermosetting resin include epoxy resins, melamine resins, unsaturated polyester resins, and the like. These include natural resins, glass fibers, carbon fibers, semi-carbonized fibers, cellulosic fibers, glass beads, and the like. It can also be used as a thermosetting molding material containing a flame retardant.

  In the ultraviolet absorbent dispersion of the present invention, a dispersant, an antifoaming agent, a preservative, an antifreezing agent, a surfactant and the like can be used in combination. In addition, any compound may be included. Examples include dyes, pigments, ultraviolet absorbers, infrared absorbers, light stabilizers, fragrances, polymerizable compounds, polymers, inorganic substances, metals, and the like.

  As an apparatus for obtaining the ultraviolet absorbent dispersion of the present invention, a high-speed stirring type disperser having a large shearing force, a disperser that gives high-intensity ultrasonic energy, and the like can be used. Specifically, there are a colloid mill, a homogenizer, a capillary emulsifying device, a liquid siren, an electromagnetic distortion ultrasonic generator, an emulsifying device having a Paulman whistle, and the like. A high-speed stirring type disperser preferable for use in the present invention is a high-speed rotation (500 to 15,000 rpm) in a liquid in which a main part that performs a dispersing action, such as a dissolver, polytron, homomixer, homoblender, caddy mill, jet agitator. Preferably, it is a disperser of the type of 2,000 to 4,000 rpm. The high-speed agitation type disperser used in the present invention is also called a dissolver or a high-speed impeller disperser. As described in Japanese Patent Application Laid-Open No. 55-129136, a saw-tooth plate is attached to a shaft that rotates at high speed. A preferred example is one in which impellers that are alternately bent in the vertical direction are mounted.

  In preparing an emulsified dispersion comprising a hydrophobic compound, various processes can be followed. For example, when a hydrophobic compound is dissolved in an organic solvent, one kind arbitrarily selected from a high-boiling organic substance, a water-immiscible low-boiling organic solvent, or a water-miscible organic solvent, or two or more kinds of arbitrary substances Dissolve in the multi-component mixture and then disperse in water or aqueous hydrophilic colloid in the presence of a surface active compound. The mixing method of the water-insoluble phase containing the hydrophobic compound and the aqueous phase may be a so-called forward mixing method in which the water-insoluble phase is added to the aqueous phase with stirring or a reverse mixing method.

  The content of the ultraviolet absorbent in the ultraviolet absorbent dispersion of the present invention varies depending on the purpose of use and the form of use and cannot be uniquely determined, but may be any concentration depending on the purpose of use. Preferably it is 0.001-50 mass% with respect to the whole quantity of a ultraviolet absorber dispersion, More preferably, it is 0.01-20 mass%.

The ultraviolet absorbent of the present invention is preferably in the form of a solution dissolved in a liquid medium. Hereinafter, the ultraviolet absorbent solution of the present invention will be described.
Any liquid may be used for dissolving the ultraviolet absorbent according to the present invention. For example, water, an organic solvent, a resin, a resin solution, and the like can be given. Examples of the organic solvent, the resin, and the resin solution include those described as the above dispersion medium. These may be used alone or in combination.

  The solution of the ultraviolet absorber of the present invention may contain any other compound in addition. Examples include dyes, pigments, ultraviolet absorbers, infrared absorbers, light stabilizers, fragrances, polymerizable compounds, polymers, inorganic substances, metals, and the like. Except for the ultraviolet absorbent according to the present invention, it may not necessarily be dissolved.

  The content of the ultraviolet absorbent in the ultraviolet absorbent solution of the present invention varies depending on the purpose of use and the form of use and cannot be uniquely determined, but may be any concentration depending on the purpose of use. Preferably it is 0.001-30 mass% with respect to the whole quantity of a solution, More preferably, it is 0.01-10 mass%. It is also possible to prepare a solution at a high concentration in advance and dilute it when desired. The dilution solvent can be arbitrarily selected from the above-mentioned solvents.

The polymer composition is used for the preparation of the polymer material of the present invention. The polymer composition used in the present invention is obtained by adding the ultraviolet absorber of the present invention to a polymer material described later.
The ultraviolet absorber of the present invention can be contained in the polymer substance by various methods. When the ultraviolet absorbent of the present invention is compatible with the polymer substance, the ultraviolet absorbent of the present invention can be directly added to the polymer substance. The ultraviolet absorber of the present invention may be dissolved in an auxiliary solvent having compatibility with the polymer material, and the solution may be added to the polymer material. The ultraviolet absorbent of the present invention may be dispersed in a high-boiling organic solvent or polymer, and the dispersion may be added to the polymer substance.

The boiling point of the high-boiling organic solvent is preferably 180 ° C. or higher, and more preferably 200 ° C. or higher. The melting point of the high-boiling organic solvent is preferably 150 ° C. or lower, and more preferably 100 ° C. or lower. Examples of the high-boiling organic solvent include phosphate ester, phosphonate ester, benzoate ester, phthalate ester, fatty acid ester, carbonate ester, amide, ether, halogenated hydrocarbon, alcohol and paraffin. Phosphate esters, phosphonate esters, phthalate esters, benzoate esters and fatty acid esters are preferred.
As for the method of adding the ultraviolet absorber of the present invention, JP-A-58-209735, JP-A-63-264748, JP-A-4-191185, JP-A-8-272058, and British Patent No. 2011017A. Can be helpful.

  The content of the ultraviolet absorbent in the ultraviolet absorbent solution of the present invention varies depending on the purpose of use and the form of use and cannot be uniquely determined, but may be any concentration depending on the purpose of use. Preferably it is 0.001-10 mass% in a polymeric material, More preferably, it is 0.01-5 mass%.

Moreover, the ultraviolet absorber of the present invention is preferably used for a polymer material. Hereinafter, the polymer material of the present invention will be described.
The polymer substance used in the present invention will be described. The polymeric material is a natural or synthetic polymer or copolymer. Examples include the following.
<1> Monoolefin and diolefin polymers such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, and cycloolefins such as cyclopentene or norbornene. Polymers, polyethylene (which can be optionally cross-linked) such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE) Low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, ie the polymers of monoolefins exemplified in the previous paragraph, preferably polyethylene and polypropylene, can be prepared by different methods and especially by the following methods:
a) Radical polymerization (usually under high pressure and at elevated temperature).
b) Catalytic polymerization using a catalyst that normally contains one or more of the metals of groups IVb, Vb, VIb or VIII of the periodic table. These metals are usually one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls that can be π- or σ-coordinated. Have These metal complexes can be in free form or fixed to a substrate, typically activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalyst can be used as such in the polymerization or is another activator, typically a metal alkyl, metal hydride, metal alkyl halide, metal alkyl oxide or metal alkyl oxane, wherein the metal is Ia of the periodic table. , IIa and / or IIIa group elements can be used. The activator can be conveniently modified with other ester, ether, amine or silyl ether groups. These catalyst systems are usually named Philips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

<2> A mixture of the polymers mentioned in the section <1>, such as polypropylene and polyisobutylene, a mixture of polypropylene and polyethylene (for example, PP / HDPE, PP / LDPE), and a mixture of different types of polyethylene (for example, LDPE). / HDPE).

<3> Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / propylene Te-1-ene copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / vinylcyclohexane copolymer, Ethylene / cycloolefin copolymers (e.g., ethylene / norbornene such as COC (Cyclo-Olefin Copolymer)), ethylene / 1-olefin copolymers in which 1-olefin is produced in situ, propylene / Butadiene copolymer, isobutylene / isoprene copolymer, ethylene / vinylcyclohexene copolymer, ethylene / alkyl acrylate copolymer, ethylene / alkyl methacrylate copolymer, ethylene / vinyl acetate copolymer or ethylene / acrylic acid copolymer and their salts (ionomers), and ethylene and propylene And terpolymers with dienes such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with each other and with polymers mentioned above under 1), for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene -Vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLD E / EAA and alternating or random polyalkylene / carbon monoxide copolymers and their other polymers, for example mixtures of polyamide.

<4> A hydrocarbon resin (for example, having 5 to 9 carbon atoms) containing a hydrogenated product (for example, a tackifier) and a mixture of polyalkylene and starch.

  The <1> to <4> homopolymers and copolymers may have any steric structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereo block polymers are also included.

<5> Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

<6> All isomers of styrene, α-methylstyrene, vinyltoluene, in particular, all isomers of p-vinyltoluene, ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene, and vinylanthracene, and mixtures thereof. Aromatic homopolymers and copolymers derived from aromatic vinyl monomers containing. Homopolymers and copolymers can have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; atactic polymers are preferred. Stereo block polymers are also included.

<6a> Copolymers comprising the above-mentioned aromatic vinyl monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example Styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (copolymer), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; High impact resistant mixtures of styrene copolymers and other polymers such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; and styrene / butadiene On / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene block copolymers such as styrene.

<6b> A polyaromatic polymer prepared by hydrogenating a hydrogenated aromatic polymer, especially atactic polystyrene, derived from the hydrogenation of the polymer referred to in <6> above, often referred to as polyvinylcyclohexane (PVCH) Includes cyclohexylethylene (PCHE).

<6c> A hydrogenated aromatic polymer derived from hydrogenation of the polymer mentioned in the section <6a>.

  Homopolymers and copolymers can have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; atactic polymers are preferred. Stereo block polymers are also included.

<7> Graft copolymer of aromatic vinyl monomer such as styrene or α-methylstyrene, for example, styrene to polybutadiene, styrene to polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; styrene and acrylonitrile (or methacrylonitrile) to polybutadiene; Styrene, acrylonitrile and methyl methacrylate; polybutadiene with styrene and maleic anhydride; polybutadiene with styrene, acrylonitrile and maleic anhydride or maleimide; polybutadiene with styrene and maleimide; polybutadiene with styrene and alkyl acrylate or methacrylate; ethylene / propylene / dienter Styrene and acrylonitrile as polymer; polyalkyl acrylate Known as styrene and acrylonitrile to styrene or acrylonitrile; styrene / acrylonitrile to acrylate / butadiene copolymers, and mixtures thereof with the copolymers listed in <6> above, eg ABS, SAN, MBS, ASA or AES polymers A copolymer mixture.

<8> polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, In particular, polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and their copolymers such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers Halogen-containing polymers such as

<9> Polymers derived from α, β-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates; polymethylmethacrylates, polyacrylamides and polyacrylonitriles impact-modified with butylacrylate.

<10> Copolymers of the monomers mentioned in the above <9> with each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylonitrile / vinyl halide copolymers or Acrylonitrile / alkyl methacrylate / butadiene terpolymer.

<11> Polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine As well as the olefins and copolymers thereof mentioned in <1> above.

<12> Homopolymers and copolymers of cyclic ethers such as polyalkylene glycol, polyethylene oxide, polypropylene oxide or bisglycidyl ether and copolymers thereof.

<13> Polyacetals such as polyoxymethylene and polyoxymethylene containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethane, acrylate or MBS.

<14> Polyphenylene oxide and sulfide, and a mixture of polyphenylene oxide and styrene polymer or polyamide.

<15> Polyurethanes derived from hydroxyl-terminated polyethers, polyesters and polybutadienes, and the other from aliphatic or aromatic polyisocyanates, and precursors thereof.

<16> Polyamides and copolyamides derived from diamis and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylenediamine and adipic acid; from hexamethylenediamine and isophthalic acid and / or terephthalic acid and using elastomers as modifiers Polyamides prepared with or without, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide: and the above-mentioned polyamides and polyolefins, olefin copolymers, ionomers or chemically bonded Or Block copolymers with rafted elastomers; or block copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides or copolyamides modified with EPDM or ABS; and condensation during processing Polyamide (RIM polyamide system).

<17> Polyurea, polyimide, polyamido-imide, polyetherimide, polyesterimide, polyhydantoin, and polybenzimidazole.

<18> Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) Block copolyetheresters derived from polyhydroxybenzoates and hydroxyl-terminated polyethers; and also polyesters modified with polycarbonate or MBS. Polyesters and polyester copolymers as defined in US Pat. No. 5,807,932 (column 2, line 53) are incorporated herein by reference.

<19> Polycarbonate and polyester carbonate.

<20> Polyketone.

<21> Polysulfone, polyethersulfone and polyetherketone.

<22> Crosslinked polymers derived from aldehyde as one component and phenol, urea and melamine as other components, such as phenol / formaldehyde resin, urea / formaldehyde resin and melamine / formaldehyde resin.

<23> Dry and non-dry alkyd resins.

<24> Unsaturated polyester resins derived from saturated and unsaturated dicarboxylic acids, polyhydric alcohols, and vinyl compounds as crosslinking agents, and further halogen-containing modified products thereof having low flame retardancy.

<25> Crosslinkable acrylic resins derived from substituted acrylates such as epoxy acrylates, urethane acrylates or polyester acrylates.

<26> Alkyd resins, polyester resins, and acrylate resins crosslinked using melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates, or epoxy resins.

<27> Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, eg, with conventional curing agents such as anhydrides or amines, with or without accelerators Crosslinked glycidyl ether products of bisphenol A and bisphenol F.

<28> Natural polymers such as cellulose, gum, gelatin and chemically modified derivatives of their homologous series such as cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers such as methylcellulose; and rosin and them Derivatives of

<29> Blends (polyblends) of the above polymers, such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and copolymers, PA / HDPE, PA / PP PA / PPO, PBT / PC / ABS or PBT / PET / PC.

<30> based on pure monomeric compounds or natural and synthetic organic materials which are mixtures of said compounds, for example mineral oils, animal and vegetable fats, oils and waxes, or synthetic esters (for example phthalates, adipates, phosphates or trimellitates) Mixtures of oils, fats and waxes and any mass ratio of synthetic esters and mineral oils, typically mixtures used as fiber spinning compositions, and aqueous emulsions of said materials.

<31> An aqueous emulsion of natural or synthetic rubber, such as natural latex or latex of carboxylated styrene / butadiene copolymer.

<32> Polysiloxanes such as soft and hydrophilic polysiloxanes described in US Pat. No. 4,259,467 and hard polyorganosiloxanes described in US Pat. No. 4,355,147.

<33> A polyketimine in combination with an unsaturated acrylic polyacetoacetate resin or an unsaturated acrylic resin. The unsaturated acrylic resin includes urethane acrylate, polyester acrylate, vinyl or acrylic copolymer having pendant unsaturated groups, and acrylated melamine. The polyketimine is produced from a polyamine and a ketone in the presence of an acid catalyst.

<34> A radiation curable composition comprising an ethylenically unsaturated monomer or oligomer and a polyunsaturated aliphatic oligomer.

<35> An epoxy melamine resin such as a light-stabilized epoxy resin crosslinked with an epoxy-functional co-etherified high solids melamine resin such as LSE-4103 (manufactured by Monsanto).

The polymer substance used in the present invention is preferably a synthetic polymer, more preferably a polyolefin, an acrylic polymer, polyester, polycarbonate, or cellulose ester. Among these, polyethylene, polypropylene, poly (4-methylpentene), polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and triacetyl cellulose are particularly preferable.
The polymer substance used in the present invention is preferably a thermoplastic resin.

  The polymer material of the present invention may contain any additive such as an antioxidant, a light stabilizer, a processing stabilizer, an anti-aging agent, a compatibilizing agent, etc., if necessary, in addition to the above-described polymer substance and ultraviolet light inhibitor. May be contained as appropriate.

The polymer material of the present invention comprises the above polymer substance. The polymer material of the present invention may be formed only from the polymer substance, or may be formed by dissolving the polymer substance in an arbitrary solvent.
The polymer material containing the ultraviolet absorbent according to the present invention can be used for all applications in which a synthetic resin is used, but can be particularly suitably used for applications that may be exposed to sunlight or light including ultraviolet rays. . Specific examples include, for example, glass substitutes and surface coating materials thereof, housing, facilities, window glass for transportation equipment, coating materials for daylighting glass and light source protection glass, housing, facilities, window films for transportation equipment, housing, Inner and outer materials for facilities, transportation equipment and the like and coatings for inner and outer coatings and coatings formed by the coatings, alkyd resin lacquer coatings and coatings formed by the coatings, acrylic lacquer coatings and coatings formed by the coatings, Components for light sources that emit ultraviolet rays such as fluorescent lamps and mercury lamps, precision machinery, components for electronic and electrical equipment, materials for shielding electromagnetic waves generated from various displays, containers or packaging materials for food, chemicals, chemicals, bottles, boxes, Blister, cup, special packaging, compact disc coat, agricultural or industrial sheet or film material, printed matter, dyed matter Anti-fading agents such as dyes and pigments, protective films for polymer supports (for example, plastic parts such as machinery and automobile parts), printed overcoats, inkjet media coatings, laminated matte, optical light films, safety glass / Windshield intermediate layer, electrochromic / photochromic use, overlaminate film, solar heat control film, sunscreen cream, shampoo, rinse, hairdressing cosmetics, sportswear, stockings, hats and other clothing textiles and fibers, curtains, Car interior items such as carpets and wallpaper, plastic lenses, contact lenses, artificial instruments such as artificial eyes, optical filters, backlight display films, prisms, mirrors, optical materials such as photographic materials, mold films, transfer stickers, Graffiti prevention film, tape, b Click like stationery, signs, marking plate, and a marking device such as a surface coating material or the like.

  The shape of the polymer material of the present invention may be any of a flat film shape, a powder shape, a spherical particle, a crushed particle, a massive continuous body, a fiber shape, a tubular shape, a hollow fiber shape, a granular shape, a plate shape, a porous shape, and the like. There may be.

  In the present invention, a sufficient ultraviolet shielding effect can be obtained practically only with the ultraviolet absorber of the present invention, but when more strictness is required, a white pigment having a strong hiding power, such as titanium oxide, is used in combination. Also good. In addition, when the appearance and color tone become problems, or a small amount (0.05% by mass or less) of a colorant can be used in combination depending on the preference. For applications where transparency or white color is important, a fluorescent brightening agent may be used in combination. Examples of the fluorescent whitening agent include commercially available products, general formula [1] described in JP-A-2002-53824, and specific compound examples 1 to 35.

  Since the polymer material of the present invention contains the ultraviolet absorbent of the present invention, it has excellent light resistance (fastness to ultraviolet light), and precipitation of the ultraviolet absorbent and bleeding out due to long-term use occur. There is nothing. In addition, since the polymer material of the present invention has an excellent long-wave ultraviolet absorbing ability, it can be used as an ultraviolet absorbing filter or a container, and can protect compounds that are sensitive to ultraviolet rays. For example, a molded product (such as a container) made of the polymer material of the present invention can be obtained by molding the polymer substance by any method such as extrusion molding or injection molding. In addition, a molded article coated with the ultraviolet absorbing film made of the polymer material of the present invention can be obtained by applying and drying the polymer substance solution to a separately produced molded article.

  When the polymer material of the present invention is used as an ultraviolet absorption filter or an ultraviolet absorption film, the polymer material is preferably transparent. Examples of transparent polymer materials include cellulose esters (eg, diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, Polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic) Polystyrene), polyolefin (eg, polyethylene, polypropylene, polymethylpentene), polymethyl methacrylate, syndiotactic polystyrene Emissions, polysulfone, polyether sulfone, polyether ketone, polyether imide and polyoxyethylene. Preferred are cellulose ester, polycarbonate, polyester, polyolefin, and acrylic resin. The polymer material of the present invention can also be used as a transparent support, and the transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more.

  The packaging material containing the ultraviolet absorbent according to the present invention will be described. The packaging material containing the ultraviolet absorbent according to the present invention may be a packaging material made of any kind of polymer as long as it contains the ultraviolet absorbent represented by the general formula (1). For example, the thermoplastic resin described in JP-A-8-208765, the polyvinyl alcohol described in JP-A-8-15155, the polyvinyl chloride described in JP-A-8-245849, and JP-A-10-168292 , Polyester described in JP-A-2004-285189, heat-shrinkable polyester described in JP-A-2001-323082, styrene resin described in JP-A-10-298397, JP-A-11-315175, Examples thereof include polyolefins described in JP-A-2001-26081 and JP-A-2005-305745, ROMP described in JP-T-2003-524019, and the like. For example, a resin having an inorganic vapor-deposited thin film layer described in JP-A-2004-50460 and JP-A-2004-243674 may be used. For example, it may be paper coated with a resin containing an ultraviolet absorber described in JP-A-2006-240734.

  The packaging material containing the ultraviolet absorbent according to the present invention may be used for packaging foods, beverages, drugs, cosmetics, personal care products, and the like. For example, food packaging described in JP-A-11-34261, JP-A-2003-237825, colored liquid packaging described in JP-A-8-80928, liquid formulation described in JP-A-2004-51174 Packaging, pharmaceutical container packaging described in JP-A-8-301363, JP-A-11-276550, sterilization packaging for medical products described in JP-A-66-27171, publication described in JP-A-7-287353 Photosensitive material packaging, photographic film packaging described in JP-A-2000-56433, UV-curable ink packaging described in JP-A-2005-178832, JP-A-2003-200966, JP-A-2006-323339 The shrink label etc. which are described in the gazette are mentioned.

  The packaging material containing the ultraviolet absorber of the present invention may be, for example, a transparent package described in JP-A-2004-51174, or a light-shielding package described in JP-A-2006-224317, for example. May be.

  The packaging material containing the ultraviolet absorber of the present invention has not only ultraviolet shielding properties as described in, for example, JP-A-2001-26081 and JP-A-2005-305745, but also has other performances. May be. For example, those having gas barrier properties described in JP-A-2002-160321, those containing an oxygen indicator described in JP-A-2005-156220, for example, described in JP-A-2005-146278 And a combination of an ultraviolet absorber and an optical brightener.

  You may manufacture the packaging material containing the ultraviolet absorber of this invention using any method. For example, a method of forming an ink layer described in JP-A-2006-130807, for example, a method of melt-extruding and laminating a resin containing an ultraviolet absorber described in JP-A-2001-323082 and JP-A-2005-305745 For example, a method of coating on a substrate film described in JP-A-9-145539, for example, a method of dispersing an ultraviolet absorber in an adhesive described in JP-A-9-57626, and the like can be mentioned.

  The container containing the ultraviolet absorber of the present invention will be described. The container containing the ultraviolet absorbent according to the present invention may be a container made of any kind of polymer as long as it contains the ultraviolet absorbent represented by the general formula (1). For example, a thermoplastic resin container described in JP-A-8-324572, a polyester container described in JP-A-2001-48153, JP-A 2005-105004, JP-A 2006-1568, JP-A 2000 Polyethylene naphthalate container described in JP-A-238857, polyethylene container described in JP-A-2001-88815, cyclic olefin resin composition container described in JP-A-7-216152, JP-A-2001- Examples thereof include a plastic container described in Japanese Patent No. 270531 and a transparent polyamide container described in Japanese Patent Application Laid-Open No. 2004-83858. For example, it may be a paper container containing a resin described in JP-A-2001-114262 and JP-A-2001-213427. For example, a glass container having an ultraviolet absorbing layer described in JP-A-7-242444, JP-A-8-133787, and JP-A-2005-320408 may be used.

  The container containing the ultraviolet absorbent according to the present invention may be used for food, beverages, drugs, cosmetics, personal care products, shampoos and the like. For example, a liquid fuel storage container described in JP-A-5-139434, a golf ball container described in JP-A-7-289665, a food container described in JP-A-9-295664, and JP-A-2003-237825 Container, sake container described in JP-A-9-58687, drug-filled container described in JP-A-8-15507, beverage container described in JP-A-8-324572, JP-A-2006-298456 , A container for oily food described in JP-A-9-86570, a solution container for analytical reagent described in JP-A-9-113494, an instant noodle container described in JP-A-9-239910, and JP-A-11- No. 180474, JP-A 2002-68322, JP-A 2005-278678, light-resistant cosmetic container described in JP-A-11-276550, pharmaceutical container described in JP-A-11-290420 Containers for high-purity chemical liquids, containers for liquid agents described in JP-A-2001-106218, containers for ultraviolet curable inks described in JP-A-2005-178832, containers for WO04 / 93775 For example, the plastic ampules described on the frets.

  The container containing the ultraviolet absorber of the present invention has not only ultraviolet blocking properties as described in, for example, JP-A-5-305975 and JP-A-7-40954, but also has other performances in combination. Also good. For example, the antibacterial container described in JP-A-10-237312, the flexible container described in JP-A-2000-152974, the dispenser container described in JP-A-2002-264979, for example, JP-A-2005-255736 Examples include biodegradable containers described in the publication.

  You may manufacture the container containing the ultraviolet absorber of this invention using any method. For example, a method by two-layer stretch blow molding described in JP-A-2002-370723, a multi-layer coextrusion blow molding method described in JP-A-2001-88815, and an outer side of a container described in JP-A-9-241407 Method for forming ultraviolet absorbing layer, JP-A-8-91385, JP-A-9-48935, JP-T11-514387, JP-A-2000-66603, JP-A-2001-323082, JP Examples thereof include a method using a shrinkable film described in JP-A-2005-105032 and a pamphlet of WO99 / 29490, a method using a supercritical fluid described in JP-A-11-255925, and the like.

  The paint and coating film containing the ultraviolet absorber of the present invention will be described. The coating material containing the ultraviolet absorber of the present invention may be a coating material composed of any component as long as it contains the ultraviolet absorber represented by the general formula (1). For example, an acrylic resin system, a urethane resin system, an amino alkyd resin system, an epoxy resin system, a silicone resin system, a fluororesin system, etc. are mentioned. These resins can be arbitrarily mixed with a main agent, a curing agent, a diluent, a leveling agent, a repellant and the like.

  For example, when acrylic urethane resin or silicon acrylic resin is selected as the transparent resin component, polyisocyanate is used as the curing agent, hydrocarbon solvents such as toluene and xylene are used as the diluent, isobutyl acetate, butyl acetate, amyl acetate, etc. Alcohol solvents such as ester solvents, isopropyl alcohol, and butyl alcohol can be used. Here, the acrylic urethane resin refers to an acrylic urethane resin obtained by reacting a methacrylic ester (typically methyl), a hydroxyethyl methacrylate copolymer and a polyisocyanate. The polyisocyanate in this case includes tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and the like. Other examples of the transparent resin component include polymethyl methacrylate, polymethyl methacrylate styrene copolymer, polyvinyl chloride, and polyvinyl acetate. Further, in addition to these components, a leveling agent such as an acrylic resin or a silicone resin, an anti-fogging agent such as a silicone or acrylic resin, and the like can be blended as necessary.

  The use purpose of the paint containing the ultraviolet absorber of the present invention may be any use. For example, the ultraviolet shielding paint described in JP-A-7-26177, JP-A-9699950, JP-A-9-221631, JP2002-80788, UV described in JP-A-10-88039 Near-infrared shielding paint, electromagnetic wave shielding paint described in JP-A-2001-55541, clear paint described in JP-A-8-81643, metallic paint composition described in JP-A-2000-186234, Cationic electrodeposition paint described in Kaihei 7-166112, antibacterial and lead-free cationic electrodeposition paint described in JP-A-2002-294165, JP-A 2000-273362, JP-A-2001-279189, Powder paint described in JP-A-2002-271227, water-borne intermediate coating, water-based metallic paint described in JP-A-2001-9357, water-based clear paint, automobile and architecture described in JP-A-2001-316630 Paints for top coating used in products and civil engineering products, curable paints described in JP-A No. 2002-356655, JP-A No. 2004-937 Coating film-forming composition used for plastic materials such as automobile bumpers described in the report, paint for metal plates described in JP-A-2004-2700, cured gradient coating film described in JP-A-2004-169182, The coating material for electric wires described in JP-A-2004-107700, the automobile repair paint described in JP-A-6-49368, the anion electrodeposition described in JP-A-2002-38084 and JP-A-2005-307161 Paint, JP-A-5-78606, JP-A-5-85031, JP-A-10-140089, JP2000-509082, JP2004-520284, WO2006 / 097201 pamphlet Paints for automobiles, paints for coated steel sheets described in JP-A-6-945, stainless steel paints described in JP-A-6-313148, insect repellent paints for lamps described in JP-A-7-3189, UV-curable coatings described in JP-A-7-82454, antibacterial coatings described in JP-A-7-118576, and eyestrain described in JP-A-2004-217727 Work prevention paint, anti-fogging paint described in JP-A-2005-314495, super-weather resistant paint described in JP-A-10-298493, gradient paint described in JP-A-9-241534, JP-A 2002 -235028 photocatalyst paint, JP-A 2000-345109 peelable paint, JP-A 6-346022 concrete peeling paint, JP-A 2002-167545 anti-corrosion Paint, protective paint described in JP-A-8-324576, water-repellent protective paint described in JP-A-9-12924, paint for preventing sheet glass scattering described in JP-A-9-57581, JP-A-9- No. 59539, alkali-soluble protective coating, JP-A-2001-181558, water-based temporary protective coating composition, JP-A-10-183057, floor coating, JP-A-2001-115080 Emulsion paint described in Japanese Patent Laid-Open No. 2001-262056, two-component water-based paint described in Japanese Patent Laid-Open No. 2001-262056, one-component paint described in Japanese Patent Laid-Open No. 9-263729, UV curable paint described in JP 2001-288410 A, electron beam curable coating composition described in JP 2002-69331 A, thermosetting paint composition described in JP 2002-80781 A, special table Water-based paint for baking lacquer described in 2003-525325, powder paint and slurry paint described in Japanese Patent Application Laid-Open No. 2004-162021, paint for repair described in Japanese Patent Application Laid-Open No. 2006-233010, 11- An aqueous dispersion of powder coating material described in Japanese Patent No. 514689, a coating material for plastics described in Japanese Patent Application Laid-Open No. 2001-59068, Japanese Patent Application Laid-Open No. 2006-160847, and an electron beam curable coating material described in Japanese Patent Application Laid-Open No. 2002-69331 Etc.

  The paint containing the ultraviolet absorbent according to the present invention is generally composed of a paint (including a transparent resin component as a main component) and an ultraviolet absorbent, but preferably a composition of 0 to 20% by weight of the ultraviolet absorbent based on the resin. It is. The thickness at the time of application is preferably 2 to 1000 μm, more preferably 5 to 200 μm. The method of applying these paints is arbitrary, but there are a spray method, a dipping method, a roller coat method, a flow coater method, a flow coating method and the like. Although drying after application varies depending on the paint components, it is preferably performed at room temperature to 120 ° C. for about 10 to 90 minutes.

  The coating film containing the ultraviolet absorber of the present invention is a coating film containing an ultraviolet absorber composed of the ultraviolet absorber represented by the general formula (1), and the above-described coating material containing the ultraviolet absorber of the present invention is used. It is the coating film formed in this way.

  The ink containing the ultraviolet absorbent according to the present invention will be described. The ink containing the ultraviolet absorbent according to the present invention may be any form of ink as long as it contains the ultraviolet absorbent represented by the general formula (1). Examples thereof include dye ink, pigment ink, water-based ink, and oil-based ink. Moreover, you may use for any use. For example, screen printing inks described in JP-A-8-3502, flexographic printing inks described in JP-T-2006-521941, gravure printing inks described in JP-T-2005-533915, JP-A-11-504954 Lithographic offset printing ink described in Japanese Patent Publication No. JP-A-2005-533915, letterpress printing ink described in Japanese Patent Publication No. 2005-533915, UV ink described in Japanese Patent Laid-Open No. 5-254277, EB ink described in Japanese Patent Laid-Open No. 2006-30596, etc. Is mentioned. Further, for example, described in JP-A-11-199808, WO99 / 67337 pamphlet, JP-A-2005-325150, JP-A-2005-350559, JP-A-2006-8811, JP-T-2006-514130 Ink-jet inks, photochromic inks described in JP-A-2006-257165, thermal transfer inks described in JP-A-8-108650, masking inks described in JP-A-2005-23111, JP-A-2004-75888 And the fluorescent ink described in JP-A-7-164729, the DNA ink described in JP-A-2006-22300, and the like.

  Any form obtained by using the ink containing the ultraviolet absorbent of the present invention is also included in the present invention. For example, the printed matter described in JP-A-2006-70190, a laminate obtained by laminating the printed matter, a packaging material or container using the laminate, and an ink receiving layer described in JP-A-2002-127596 may be mentioned. .

  The fiber containing the ultraviolet absorbent according to the present invention will be described. The fiber containing the ultraviolet absorbent according to the present invention may be a fiber made of any kind of polymer as long as it contains the ultraviolet absorbent represented by the general formula (1). For example, Japanese Patent Laid-Open No. 5-117508, Japanese Patent Laid-Open No. 7-119036, Japanese Patent Laid-Open No. 7-196631, Japanese Patent Laid-Open No. 8-188921, Japanese Patent Laid-Open No. 10-237760, Japanese Patent Laid-Open No. 2000-54287, Polyester fibers described in JP-A-2006-299428, JP-A-2006-299438, polyphenylene sulfide fibers described in JP-A-2002-322360, JP-A-2006-265770, JP-A-7-76580 Polyamide fibers described in JP-A-2001-348785, JP-A-2003-41434, JP-A-2003-239136, epoxy fibers described in pamphlet of WO03 / 2661, described in JP-A-10-251981 Aramid fibers, polyurethane fibers described in JP-A-62-228816, cellulose fibers described in JP-A-2005-517822, and the like.

  You may manufacture the fiber containing the ultraviolet absorber of this invention by any method. For example, as described in JP-A-62-281818, a polymer containing the ultraviolet absorber represented by the general formula (1) in advance may be processed into a fiber, for example, JP-A-5-9870. A solution containing an ultraviolet absorber represented by the general formula (1) is used for a fiber processed as described in JP-A-8-188921 and JP-A-10-1587. May be processed. As described in JP 2002-212884 A and JP 2006-16710 A, treatment may be performed using a supercritical fluid.

  The fiber containing the ultraviolet absorber of the present invention can be used for various applications. For example, apparel described in JP-A-5-148703, lining described in JP-A-2004-285516, underwear described in JP-A-2004-285517, blanket described in JP-A-2003-339503, Socks described in JP-A-2004-11062, artificial leather described in JP-A-11-302982, insect-proof mesh sheet described in JP-A-7-289097, construction described in JP-A-10-1868 Mesh sheet, carpet described in JP-A-5-255644, moisture-permeable and waterproof sheet described in JP-A-5-93037, nonwoven fabric described in JP-A-6-14991, and JP-A-11-247028 Extra fine fiber described in JP-A No. 2000-144583, sheet-like material comprising fibers described in JP-A No. 2000-144583, refreshing clothing described in JP-A No. 5-148703, moisture permeability described in JP-A No. 5-93037 Waterproof sheet, flame retardant artificial suede-like structure described in JP-A-7-18854, resin tarpaulin described in JP-A-8-41785, Film agent, exterior wall material, agricultural house described in Kaihei 8-193136, net for building material described in JP-A-8-269850, mesh, filter base material described in JP-A-8-284063 An antifouling film agent described in JP-A-9-57889, a mesh fabric described in JP-A-9-13335, a land net, an underwater net described in JP-A-10-165045, and JP-A-11-247027 No. 1, JP-A-11-247028, extra fine fibers, JP-A-7-310283, JP 2003-528974, anti-woven fibers, JP-A 2001-30861, airbags For example, ultraviolet absorbent fiber products described in JP-A-7-324283, JP-A-8-20579, and JP-A-2003-147617.

  The building material containing the ultraviolet absorber of the present invention will be described. The building material containing the ultraviolet absorbent according to the present invention may be a building material made of any kind of polymer as long as it contains the ultraviolet absorbent represented by the general formula (1). For example, the vinyl chloride system described in JP-A-10-6451, the olefin system described in JP-A-10-16152, the polyester system described in JP-A-2002-161158, and JP-A 2003-49065 Examples thereof include polyphenylene ethers described above, polycarbonates described in JP-A-2003-160724, and the like.

  The building material containing the ultraviolet absorber of the present invention may be produced by any method. For example, as described in JP-A-8-269850, it may be formed into a desired shape using a material containing an ultraviolet absorber represented by the general formula (1). For example, JP-A-10-205056 A material containing an ultraviolet absorber represented by the general formula (1) may be laminated as described in the gazette, or the general formula (e.g. A coating layer using the ultraviolet absorber represented by 1) may be formed, and contains, for example, the ultraviolet absorber represented by the general formula (1) as described in JP-A-2001-172531 It may be formed by painting a paint.

  The building material containing the ultraviolet absorber of the present invention can be used for various applications. For example, exterior building materials described in JP-A-7-3955, JP-A-8-151457, and JP-A-2006-266042, wooden structures for building materials described in JP-A-89-197511, The roofing material for building materials described in JP-A-9-183159, the antibacterial building material described in JP-A-11-236734, the building material substrate described in JP-A-10-205056, and JP-A-11-300880 The antifouling building material described in the above, the flame retardant material described in JP 2001-9811 A, the ceramic building material described in JP 2001-172531, the decorative building material described in JP 2003-328523, Coated articles for building materials described in JP-A No. 2002-226764, cosmetic materials described in JP-A No. 10-6451, JP-A No. 10-16152, JP-A No. 2006-306020, JP-A No. 8-269850 The building material net described in the gazette, the moisture permeable waterproof sheet for building material described in JP-A-9-277414, the mesh sheet for building work described in JP-A-10-1868, and JP-A-7-269016 Film for building material described in the above, cover film described in JP 2003-211538 A, coating material for building material described in JP 9-239921 A, JP 9-254345 A, JP 10-44352 A An adhesive composition for building materials described in JP-A-8-73825, a civil engineering building structure described in JP-A-8-207218, a coating material for walking paths described in JP-A-2003-82608, JP-A-2001-139700, sheet-like photocurable resin, JP-A-5-2553559, wood protective coating, JP-A-2005-2941780, pushbutton switch cover, JP-A-9- 183159, a bonding sheet agent described in JP 10-44352 A, a building material base material described in JP 10-44352 A, a wallpaper described in JP 2000-226778 A, a cover polyester described in JP 2003-211538 A Film, polyester film for covering a molded member described in JP2003-211606, flooring described in JP2004-3191, and the like It is.

  A recording medium containing the ultraviolet absorber of the present invention will be described. The recording medium containing the ultraviolet absorbent according to the present invention may be any recording medium containing the ultraviolet absorbent represented by the general formula (1). For example, JP-A-9-309260, JP-A-2002-178625, JP-A-2002-212237, JP-A-2003-266926, JP-A-2003-266927, JP-A-2004-181813 Inkjet recording media described in Japanese Patent Application Laid-Open No. 8-108650 Image transfer medium for thermal transfer ink, Sublimation transfer image-receiving sheet described in JP-A-10-203033, Image recording medium described in JP-A-2001-249430, The thermal recording medium described in JP-A-8-258415, the reversible thermosensitive recording medium described in JP-A-9-95055, JP-A 2003-145949, JP-A-2006-167996, JP-A-2002-367227 Examples thereof include an optical information recording medium described in the publication.

  An image display device containing the ultraviolet absorber of the present invention will be described. The image display device containing the ultraviolet absorbent according to the present invention may be any one as long as it contains the ultraviolet absorbent represented by the general formula (1). For example, an image display device using an electrochromic element described in JP-A-2006-301268, an image display device called so-called electronic paper described in JP-A-2006-293155, and described in JP-A-9-306344 And an image display device using an organic EL element described in JP-A-2000-223271. The ultraviolet absorber of the present invention may be one in which an ultraviolet absorbing layer is formed in a laminated structure described in, for example, JP-A-2000-223271, or a circularly polarizing plate described in, for example, JP-A-2005-189645 is necessary. A member containing an ultraviolet absorber may be used.

  The cover for solar cells containing the ultraviolet absorber of this invention is demonstrated. The solar cell applied in the present invention may be a solar cell comprising any type of element such as a crystalline silicon solar cell, an amorphous silicon solar cell, and a dye-sensitized solar cell. In crystalline silicon solar cells and amorphous silicon solar cells, a cover material is used as a protective member for imparting antifouling, impact resistance and durability as described in JP-A-2000-174296. Also, in dye-sensitized solar cells, as described in JP-A-2006-282970, a metal oxide semiconductor that becomes active when excited by light (particularly ultraviolet rays) is used as an electrode material, so that it is adsorbed as a photosensitizer. There is a problem that the dyes that have been deteriorated and the photovoltaic power generation efficiency gradually decreases, and it has been proposed to provide an ultraviolet absorbing layer.

  The solar cell cover containing the ultraviolet absorber of the present invention may be made of any kind of polymer. For example, polyester described in JP-A-2006-310461, thermosetting transparent resin described in JP-A-2006-257144, α-olefin polymer described in JP-A-2006-210906, JP-A-2003-168814 Polypropylene described in the publication, polyethersulfone described in JP-A-2005-129713, acrylic resin described in JP-A-2004-227843, transparent fluororesin described in JP-A-2004-168057, etc. Can be mentioned.

  You may manufacture the cover for solar cells containing the ultraviolet absorber of this invention by any method. For example, an ultraviolet absorbing layer described in JP-A-11-40833 may be formed, or layers containing respective ultraviolet absorbers described in JP-A-2005-129926 may be laminated, or JP2000-2000A may be laminated. May be contained in the resin of the filler layer described in JP-A-91611, or a film may be formed from a polymer containing an ultraviolet absorber described in JP-A-2005-346999.

  The solar cell cover including the ultraviolet absorbent according to the present invention may have any shape. Films and sheets described in JP-A-2000-91610, JP-A-11-261085, for example, laminated films described in JP-A-11-40833, cover glass structure described in JP-A-11-214736, etc. Is mentioned. The sealing material described in JP-A-2001-261904 may contain an ultraviolet absorber.

  Other examples of use include a light source cover for an illuminating device described in JP-A-8-102296, JP-A-2000-67629, JP-A-2005-353554, JP-A-5-272076, JP-A-2003. Artificial leather described in JP-A-239181, sports goggles described in JP-A-2006-63162, deflection lenses described in JP-A-2007-93649, JP-A-2001-214121, JP-A-2001-214122 Hard coats for various plastic products described in JP-A-2001-315263, JP-A-2003-206422, JP-A-2003-25478, JP-A-2004-137457, and JP-A-2005-132999 , A hard coat for pasting a window described in JP-A-2002-36441, a window covering film described in JP-A-10-250004, and a high-definition anti-glare hard coat described in JP-A-2002-36452 Film, antistatic hard coat film described in JP-A-2003-39607, transmission described in JP-A-2004-114355 Hard coat film, anti-counterfeiting book described in JP-A-2002-113937, turf purpura inhibitor described in JP-A-2002-293706, resin film sheet bonding described in JP-A-2006-274179 Sealing agent, light guide described in JP-A-2005-326761, rubber coating agent described in JP-A-2006-335855, JP-A-10-34841, JP-A-2002-114879 Agricultural coating materials, dyeing candles described in JP-T-2004-532306, JP-T 2004-530024, fabric rinsing compositions described in JP-T 2004-525273, JP-A-10-194796 Laminated glass, prism sheet described in JP-A-10-287804, protective layer transfer sheet described in JP-A-2000-71626, photocurable resin product described in JP-A-2001-139700, The floor sheet described in Japanese Patent Application Laid-Open No. 2001-159228, the water droplet adhesion prevention property and the heat ray shielding property described in Japanese Patent Application Laid-Open No. 2002-127310. A glass plate having a light-shielding printing label described in JP-A-2002-189415, an oiling cup described in JP-A-2002-130591, an article coated with a hard coating film described in JP-A-2002-307619, Intermediate transfer recording medium described in JP-A-2002-307845, artificial hair described in JP-A-2006-316395, low-temperature heat-shrinkable film for labels described in WO99 / 29490 pamphlet, JP-A-2004-352847 Fishing gear described in JP 2000-224942, microbeads described in JP-A-8-208976, pre-coated metal plate described in JP-A-8-318592, described in JP-A-2005-504735 Thin film, heat shrinkable film described in JP-A-2005-105032, label for in-mold molding described in JP-A-2005-37642, projection screen described in JP-A-2005-55615, 9-300537, JP 2000-25180, JP 2003-19776, 2005-74735 Decorative sheet, hot melt adhesive described in JP-A-2001-207144, JP-T 2002-543265, JP-T 2002-543266, U.S. Pat. Electrodeposition coat and base coat described in JP 2004-352783 A, wood surface protection described in JP 7-268253 A, JP 2003-253265 A, JP 2005-105131 A, JP 2005-300962 , A light control material described in Japanese Patent No. 3915339, a light control film, a light control glass, a flashlight described in JP-A-2005-304340, a touch panel described in JP-A-2005-44154, Sealing agent for resin film sheet bonding described in Kaikai 2006-274197, polycarbonate film coating described in JP-A-2006-89697, optical fiber tape described in JP-A-2000-231044, special table 2002-527559 The solid wax described in the publication No. is mentioned.

Next, a method for evaluating the light resistance of the polymer material will be described. As a method for evaluating the light resistance of polymer materials, “Polymer Light Stabilization Technology” (CMC Co., Ltd., 2000), pages 85 to 107, “Basic and Physical Properties of High-Functional Paints” (CMC Co., Ltd.) , 2003) 314-359, "Durability of polymer materials and composite products" (CMC Corporation, 2005), "Extension of polymer materials and environmental measures" (CMC Corporation, 2000), H.Zweifel, “Plastics Additives Handbook 5th Edition” (Hanser Publishers), pages 238-244, Tadahiko Katsurara, “Basic Science 2: Science of Plastic Packaging Containers” (Japan Packaging Society, 2003), Chapter 8 You can refer to the description.
The evaluation for each application can be achieved by the following known evaluation method.
Degradation due to light of polymer materials is JIS-K7105: 1981, JIS-K7101: 1981, JIS-K7102: 1981, JIS-K7219: 1998, JIS-K7350-1: 1995, JIS-K7350-2: 1995, JIS -K7350-3: 1996, JIS-K7350-4: 1996, and a method based on this method can be used for evaluation.

The light resistance when used as a packaging / container application can be evaluated by the method of JIS-K7105 and a method referring to this. Specific examples thereof include light transmittance and transparency evaluation of a bottle body described in JP-A-2006-298456, sensory test evaluation of bottle contents after UV exposure using a xenon light source, JP-A-2000-238857 Haze value evaluation after xenon lamp irradiation described in JP-A-2006-224317, haze value evaluation as a halogen lamp light source described in JP-A-2006-224317, blue wool scale after exposure to mercury lamp described in JP-A-2006-240734 Yellow degree evaluation, haze value evaluation using a sunshine weather meter described in JP-A-2005-105004, JP-A-2006-1568, visual evaluation of colorability, JP-A-7-40954, JP-A-8 -151455, JP-A-10-168292, JP-A-2001-323082, JP-A-2005-146278, UV transmittance evaluation, JP-A-9-48935, JP-A-942539 JP-A-9-241407, JP-A 2004-2436 74, JP-A-2005-320408, JP-A-2005-305745, JP-A-2005-156220, light transmittance evaluation described in JP-A-2005-178832, ink in ink container described in JP-A-2005-178832 Viscosity evaluation, light transmittance evaluation described in JP-A-2005-278678, sample in container after sun exposure, color difference ΔE evaluation, UV transmittance after white fluorescent lamp irradiation described in JP-A-2004-51174 Evaluation, light transmittance evaluation, color difference evaluation, light transmittance evaluation described in JP-A-2004-285189, haze value evaluation, color tone evaluation, yellowness evaluation described in JP-A-2003-237825, JP-A 2003- Light-shielding evaluation described in Japanese Patent No. 20966, whiteness evaluation using L ^* a ^* b ^* color difference color difference formula, after exposure for each wavelength after spectrum of xenon light described in Japanese Patent Laid-Open No. 2002-68322 evaluation yellowing using the color difference ΔEa ^* b ^* in the sample, after ultraviolet exposure described in JP-a-2001-26081, UV absorbency rating, JP Evaluation of film tensile elongation after exposure using a sunshine weather meter described in JP-A-10-298397, antibacterial evaluation after exposure to a xenon weather meter described in JP-A-10-237312, JP-A-9-239910 Evaluation of fading of packaged contents after irradiation of fluorescent lamp, evaluation of peroxide value of oil after fluorescent lamp exposure to bottle filled with salad oil described in JP-A-9-86570, evaluation of color tone, JP-A-8-301363 Absorbance difference evaluation after chemical lamp irradiation described in the above, surface gloss retention after exposure using a sunshine weather meter described in JP-A-8-208765, appearance evaluation, described in JP-A-7-216152 Examples thereof include color difference after exposure using a sunshine weatherometer, evaluation of bending strength, evaluation of light shielding ratio described in JP-A-5-139434, evaluation of the amount of peroxide produced in kerosene, and the like.

Long-term durability when used for paints and coatings is JIS-K5400, JIS-K5600-7-5: 1999, JIS-K5600-7-6: 2002, JIS-K5600-7-7: 1999, JIS -K5600-7-8: 1999, JIS-K8741 method and a method based on this method can be used for evaluation. Specific examples are the color density after exposure using the xenon light resistance tester and UVCON device described in JP 2000-509082, and the color difference ΔEa ^* b ^* in the CIE L ^* a ^* b ^* color coordinates and residual gloss. Evaluation of absorbance after exposure to xenon arc light resistance tester on quartz slide film described in JP-T 2004-520284, color density after exposure to fluorescent lamp and UV lamp in wax, and CIE L ^* a ^* b ^* Evaluation using color difference ΔEa ^* b ^* in color coordinates, Hue evaluation after exposure using a metal weather resistance tester described in JP-A-2006-160847, JP-A-2005-307161 Evaluation of gloss retention after exposure test using metal hydride lamp and evaluation using color difference ΔEa ^* b ^* , evaluation of glossiness after exposure using sunshine carbon arc light source, metal described in JP-A-2002-69331 Using a weathering tester Evaluation using color difference ΔEa ^* b ^* after exposure, gloss retention, appearance evaluation, gloss retention evaluation after exposure using a sunshine weatherometer according to JP 2002-38084, JP 2001-59068 Evaluation using the color difference ΔEa ^* b ^* after exposure using the QUV weather resistance tester described in Japanese Patent Publication No. 2001-115080, JP-A-6-49368, JP 2001 Evaluation of gloss retention after exposure using a sunshine weatherometer described in JP-A-262056, JP-A-8-324576, JP-A-9-12924, JP-A9-169950, JP-A-9-241534 Appearance evaluation after exposure using a sunshine weatherometer to a coated plate described in JP-A-2001-181558, gloss after exposure using a sunshine weatherometer described in JP-A-2000-186234 Retention rate, brightness value change evaluation, duplication for coating film described in JP-A-10-298493 Appearance evaluation of coating deterioration state after cycle WOM exposure, UV transmittance evaluation of coating film described in JP-A-7-26177, coating described in JP-A-7-3189, JP-A-9-263729 Evaluation of UV blocking rate of the film, comparative evaluation of time when the gloss retention rate of the coating film is 80% using a sunshine weatherometer described in JP-A No. 6-1945, dew panel described in JP-A No. 6-313148 Evaluation of rust generation after exposure using light control weather meter, strength evaluation of concrete against pre-painted formwork described in JP-A-6-346022, outdoor exposure described in JP-A-5-85031 Evaluation using post color difference ΔEa ^* b ^* , cross-cut adhesion evaluation, surface appearance evaluation, gloss retention evaluation after outdoor exposure described in JP-A-5-78606, described in JP-A-2006-63162 Evaluation of yellowing degree (ΔYI) after exposure using carbon arc light source It is.

Light resistance when used as an ink application can be evaluated by the method of JIS-K5701-1: 2000, JIS-K7360-2, ISO105-B02 and a method referring to this. Specifically, evaluation by measuring the color density and CIE L ^* a ^* b ^* color coordinates after exposure using a fluorescent lamp for offices described in JP-T-2006-514130, a fading tester, JP 2006-514130 Electrophoretic evaluation after exposure to ultraviolet rays using a xenon arc light source described in JP 22300, density evaluation of printed matter using a xenon fade meter described in JP 2006-8811 A, 100 W described in JP 2005-23111 Evaluation of ink detachment using a chemical lamp, evaluation of dye residual ratio of image forming site by weather meter described in JP-A-2005-325150, printed matter using eye super UV tester described in JP-A-2002-127596 CIE L ^* a ^* b ^* color difference ΔEa ^* b ^* in the color coordinates of the printed matter after exposure to xenon fade meter described in JP-A-11-199808 and JP-A-8-108650. Evaluation used, JP-A-7-164729 And reflectance evaluation after exposure using a carbon arc light source described in Japanese Patent Publication No. Gazette.

  The light resistance of the solar cell module can be evaluated by the method of JIS-C8917: 1998, JIS-C8938: 1995 and a method referring to this. Specifically, IV measurement photovoltaic power generation efficiency evaluation after exposure with a light source in which a correction filter for solar simulation is mounted on a xenon lamp described in JP-A-2006-282970, JP-A-11-261085, JP-A-2000 No. -144583 publication, chromatic weather scale evaluation, color, and appearance adhesion evaluation after exposure using a sunshine weather meter and a fade meter.

The light resistance of fibers and textile products is JIS-L1096: 1999, JIS-A5905: 2003, JIS-L0842, JIS-K6730, JIS-K7107, DIN75.202, SAEJ1885, SN-ISO-105-B02, AS / NZS4399 This method can be evaluated by the method described above and a method based on this method. JP-A-10-1587, JP-A-2006-299428, JP-A-2006-299438, UV transmittance evaluation, JP-A-62-281616, JP-A-7-76580, JP-A-8 No. 188921, No. 11-247028, No. 11-247027, No. 2000-144583, No. 2002-322360, No. 2003-339503, No. 2004-11062 The xenon light source described in the Gazette No., the blue scale discoloration evaluation after exposure using a carbon arc light source, the UV cut rate evaluation described in the JP 2003-147617 A, and the UV blocking described in the JP 2003-41434 A Evaluation, post-exposure blue scale discoloration evaluation using a carbon arc light source after dry cleaning described in JP-A-11-302982, JP-A7-119036, fade described in JP-A-10-251981 lightness after exposure using Ometer, color difference Delta] E ^* Rating based on psychometric chroma coordinates, JP-9-57889 Evaluation of tensile strength after exposure using UV tester and sunshine weather meter described in JP-A-9-137335, JP-A-10-1868, JP-A-10-237760, JP-A-8-41785 UV protection described in Japanese Patent Laid-Open No. 8-193136, total transmittance evaluation, strong retention rate evaluation, Special Table 2003-528974, Special Table 2005-517822, and Japanese Patent Laid-Open No. 8-20579 Coefficient (UPF) evaluation, change after exposure using the high-temperature fade meter described in JP-A-62-281818, JP-A-7-324283, JP-A-796631, JP-A-7-18854 Amber gray scale evaluation, appearance evaluation after outdoor exposure described in JP-A-7-289097, yellowness (YI) after yellow exposure described in JP-A-7-289665, yellowing degree (ΔYI) evaluation, An example of the regulation reflectance evaluation described in JP-T-2003-528974.

The light resistance of building materials can be evaluated by the method of JIS-A1415: 1999 and a method based on this method. Specifically, surface color evaluation after exposure using a sunshine weatherometer described in JP-A-2006-266402, carbon arc light source described in JP-A-2004-3191 and JP-A-2006-306020 Appearance evaluation after exposure using CRT, Appearance evaluation after exposure using Eye Super UV tester, Absorbance evaluation after exposure, Chromaticity after exposure, Color difference evaluation, CIE L ^* after exposure using metal hydride light source Evaluation using color difference ΔEa ^* b ^* in a ^* b ^* color coordinates, evaluation of gloss retention, JP-A-10-44352, JP-A2003-211538, JP-A-9-239921, JP-A-9- Evaluation of change in haze value after exposure using a sunshine weather meter described in JP-A-254345, JP-A-2003-211606, evaluation of elongation retention using a tensile tester after exposure, JP-A-2002-161158 UV transmittance evaluation after immersion in the solvent as described in, using eye super UV tester Appearance visual evaluation after exposure, gloss rate change evaluation after QUV test described in JP-A-2002-226764, gloss retention evaluation after exposure using sunshine weatherometer described in JP-A-2001-172531 Evaluation using a color difference ΔEa ^* b ^* after exposure to ultraviolet rays using a black light blue fluorescent lamp described in JP-A-11-300880, using a cove-con accelerated tester described in JP-A-10-205056 Evaluation of adhesion retention after exposure, evaluation of UV blocking properties, appearance evaluation after outdoor exposure (JIS-A1410) described in JP-A-8-207218 and JP-A-9-183159, evaluation of total light transmittance, haze Change evaluation, tensile shear bond strength evaluation, total light transmittance evaluation after exposure using a xenon weather meter described in JP-A-8-151457, haze evaluation, yellowing degree evaluation, JP-A-7-3955 Yellowing after exposure using the sunshine weatherometer as described in Degree (ΔYI), evaluation of residual ratio of ultraviolet absorber, and the like.

The light resistance when used as a recording medium can be evaluated by the method of JIS-K7350 and a method referring to this. Specifically, the background color difference change evaluation in the printed part after the fluorescent lamp irradiation described in JP-A-2006-167996, the xenon weather meter described in JP-A-10-203033, JP-A-2004-181813 Image density residual rate evaluation by exposure used, optical reflection density change evaluation by exposure using a xenon weather meter described in JP-A-2002-207845, Suntest CPS light fading test described in JP-A-2003-266926 Evaluation of yellowing by the L ^* a ^* b ^* evaluation form after exposure using a machine, discoloration evaluation after exposure using a fade meter described in JP2003-145949, JP2002-212237A Visual evaluation of fading after exposure using the described xenon fade meter, evaluation of color density retention after exposure to indoor sunlight described in JP-A-2002-178625, color density retention after exposure using a xenon weather meter Evaluation, described in JP 2002-367227 A C / N evaluation after exposure using a fade meter, fog density evaluation after exposure to a fluorescent lamp described in JP-A-2001-249430, after exposure using a fluorescent lamp described in JP-A-9-95055 Optical reflection density evaluation, erasability evaluation, post-exposure color difference ΔE ^* evaluation using an atlas fade meter described in JP-A-9-309260, carbon arc fade meter described in JP-A-8-258415 Visual evaluation after exposure, organic EL device color conversion characteristics retention evaluation described in JP-A-2000-223271, organic EL display brightness after exposure by a xenon fading tester described in JP-A-2005-189645 Measurement evaluation etc. are mentioned.

  As other evaluation methods, it can be evaluated by the method of JIS-K7103 and ISO / DIS9050 and a method based on this method. Specifically, the appearance evaluation of the polycarbonate-coated film described in JP-A-2006-89697 after exposure with a UV tester, the blue scale evaluation after exposure to UV rays in artificial hair described in JP-A-2006-316395, Evaluation of treatment water contact angle after exposure using the accelerated weathering tester described in Kaikai 2006-335855, projection screen after exposure using the weathering tester described in JP-A-2005-55615 Visual evaluation of projected images, Sunshine weather meter described in JP-A-2005-74735, test piece surface deterioration after exposure using a metal weather meter, visual change of design properties, JP-A-2005-326761 Appearance visual evaluation after lighting exposure using the metal lamp reflector described in JP-A-2002-189415, JP-A-2004-352847 JP-A-2003-19776 Kise described in Evaluation of deterioration of polypropylene after exposure under humidity conditions using a non-weather meter, evaluation of deterioration of a hard coat film using a sunshine weatherometer described in JP 2002-36441 A, JP 2003-25478 A Evaluation of deterioration of material, hydrophilicity evaluation, scratch resistance evaluation, gray scale color difference evaluation of artificial leather after exposure using xenon lamp light source described in JP2003-239181A, described in JP2003-253265A Evaluation of liquid crystal device characteristics after exposure using a mercury lamp, Adhesion evaluation after exposure using a sunshine weatherometer described in JP-A-2002-307619, Purpura of turf described in JP-A-2002-293706 Evaluation of degree, UV transmittance evaluation after exposure using a xenon arc light source described in JP-A-2002-114879, tensile strength evaluation, evaluation of concrete adhesion speed described in JP-A-2001-139700, JP-A-2001-315263 After exposure using the carbon arc light source described in JP 2001-214121 A, JP 2001-214122 A Yellowing degree, adhesion evaluation, adhesion performance evaluation using an ultraviolet fade meter described in JP-A-2001-207144, insect fly-inhibition evaluation during lighting, disclosed in JP-A-2000-67629, Evaluation of surface appearance after performing yellowing degree (ΔYI) evaluation of laminated glass using eye super UV tester described in Kaihei 10-194796, QUV irradiation and moisture resistance test described in JP-A-8-318592 Evaluation of gloss retention, color difference with time using a dew panel light control weather meter described in JP-A-8-208976, wood after exposure using a xenon weatherometer described in JP-A-7-268253 In the substrate application state Glossiness (DI), Yellowness Index (YI) Evaluation, Special Table 2002-5443265 Publication, Special Table 2002-543266 Publication, UV Absorption Rate Evaluation after Repeated Darkness, Special Table 2004 -532306, and the dye fading color difference ΔE evaluation after exposure to ultraviolet rays.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

Example 1
(Preparation of exemplary compound (1-2))
Exemplified compound (1-2) was prepared according to the following scheme (1).

25 g of 4-amino-2,2,6,6-tetramethylpiperidine and 18.1 g of ethyl cyanoacetate were dissolved in 20 ml of ethanol and heated to reflux for 3 hours. Ethanol was distilled off under reduced pressure. To this, 50 ml of toluene and 20 ml of isopropanol were added and stirred at room temperature for 2 hours. The crystals were filtered and dried to obtain 25.3 g of compound (1-2-a). Yield 71%. m / z = 223.
13 g of compound (1-2-a) and 10 g of separately synthesized compound (1-2-b) were heated to reflux in isopropanol for 4 hours. Then, it stirred and cooled, 120 ml of water was added, and it stirred at room temperature. The obtained crystals were washed with water, isopropanol, and ethanol to obtain 18.65 g of compound (1-2-c). Yield 100%. m / z = 405.
While stirring 6.9 g of the compound (1-2-c), 70 ml of acetonitrile, and 4.5 ml of triethylamine at room temperature, 6.9 g of 2-ethylhexanoyl chloride was slowly added dropwise. After completion of the addition, the mixture was stirred at 40 ° C. for 3 hours. After completion of the reaction, 100 ml of water and 100 ml of ethyl acetate were added and stirred. After extraction with ethyl acetate, the dry solvent was distilled off, and 50 ml of isopropanol was added and stirred at room temperature for 1 hour. The crystals were collected by filtration to obtain 2.9 g of exemplary compound (1-2). Yield 26%. m / z = 657.

  2 mg of the obtained exemplary compound (1-2) was dissolved in 100 ml of ethyl acetate to prepare a sample solution.

Example 2
(Preparation of exemplary compound (1-1))
Exemplified Compound (1-1) was prepared in the same manner as Exemplified Compound (1-2), except that acetyl chloride was used instead of 2-ethylhexanoyl chloride.

  2 mg of the obtained exemplary compound (1-1) was dissolved in 100 ml of ethyl acetate to prepare a sample solution.

[Measurement of absorption spectrum]
The absorption spectrum of each sample solution was measured by the following method.
Each sample solution was irradiated with light with an xenon lamp so that the illuminance was 170,000 lux, and the remaining amount of the ultraviolet absorber after irradiation for 48 hours was measured. The residual rate was calculated according to the following formula.
Residual rate (%) = 100 × (100−transmittance after irradiation) / (100−transmittance before irradiation)
Here, the transmittance was measured at 380 nm using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation. The results are shown in Table 1.

  As is clear from the results in Table 1, it was found that all of the ultraviolet absorbers of the present invention have a high residual rate and can maintain long-wave ultraviolet absorbing ability over a long period of time.

Example 3
3 mg of each of Exemplified Compounds (1-1) and (1-2) was weighed in a cylindrical aluminum dish having a diameter of 2 mm and a height of 2 mm, heated in an oven at 280 ° C. for 30 minutes, and then allowed to cool to room temperature. . From the mass change before and after heating, the mass reduction rate by heating was investigated. The mass reduction rate was determined by the following formula.
Mass reduction rate (%) = (mass before heating−mass after heating) / (mass before heating) × 100

On the other hand, as a comparison, the ultraviolet absorbing compound A in which a hydrogen atom or an alkyl group is bonded to the ultraviolet absorbing residue A and residue B constituting the exemplary compound (1-1) or (1-2), respectively, and photostability Compound B was prepared. Next, the ultraviolet absorbing compound A and the photostable compound B are mixed at the same ratio (molar ratio) as the existing ratio of the ultraviolet absorbing residue A and the residue B in the corresponding exemplified compound (1-1) or (1-2). ) To prepare comparative mixtures (1-1-M) and (1-2-M) in which the structures of the UV-absorbing group A and the photostable group B contained are the same but are not bonded to each other. did. The compounds used and the mixing ratio are shown in Table 2 below.
Each of the prepared comparative mixtures was examined for mass reduction rate in the same manner as described above.
Each result is shown in Table 3.

  As is clear from the results in Table 3, the weight loss of the mixture of the comparative example was significant. On the other hand, the mass of the ultraviolet absorber represented by the general formula (1) of the present invention was small. From this, the ultraviolet absorber represented by the general formula (1) of the present invention comprises the ultraviolet absorbing compound A and the photostable compound B corresponding to the ultraviolet absorbing residue A and residue B constituting the same. It was found that there was less sublimation and volatilization during heating compared to the case where they were mixed and used.

Claims (12)

The ultraviolet absorber represented by the following general formula (1).

[In General Formula (1), A represents an ultraviolet-absorbing residue. However, at least one of A is an ultraviolet-absorbing residue obtained by removing a hydrogen atom or a monovalent substituent from any position of the compound represented by the following general formula (2).
B represents a residue obtained by removing a hydrogen atom or a monovalent substituent from any position of the compound represented by any of the following general formulas (TS-I) to (TS-V).
L represents a linking group containing at least one nitrogen atom. x, y, and z each independently represent an integer of 1 or more. ]

[In General Formula (2), A ₁ represents a divalent or higher nonmetallic atom other than a carbon atom. R and R ₁ each independently represent a hydrogen atom or a monovalent substituent. R and R ₁ may be bonded to each other to form a ring, which may be further condensed. Y ₁ and Y ₂ each independently represent a monovalent substituent. ]

[In general formula (TS-I), R ₉₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or alkenyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group. Represents a group, a phosphinotolyl group, a phosphinyl group, or -Si (R ₉₇ ) (R ₉₈ ) (R ₉₉ ). Here, R ₉₇ , R ₉₈ and R ₉₉ may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group or an aryloxy group. —X ₉₁ — represents —O—, —S— or —N (—R ₁₀₀ ) —. Here, R ₁₀₀ is synonymous with R ₉₁ . R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ and R ₉₆ may be the same as or different from each other, and each represents a hydrogen atom or a substituent. R ₉₁ and R ₉₂ , R ₁₀₀ and R ₉₆ , and R ₉₁ and R ₁₀₀ may be bonded to each other to form a 5- to 7-membered ring. Further, R ₉₂ and R ₉₃ , R ₉₃ and R ₉₄ may be bonded to each other to form a 5- to 7-membered ring, a spiro ring, or a bicyclo ring. However, R ₉₁ , R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ , R ₉₆ and R ₁₀₀ are not all hydrogen atoms, and the total number of carbon atoms is 10 or more.
In the general formula (TS-II), R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ each independently represents a hydrogen atom, an alkyl group or an alkenyl group, and R ₁₀₁ and R ₁₀₂ , R ₁₀₃ and R ₁₀₄ are bonded. , A 5- to 7-membered ring may be formed. X ₁₀₁ is a hydrogen atom, alkyl group, alkenyl group, alkyloxy group, alkenyloxy group, alkyl or alkenyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, alkyloxycarbonyloxy group, alkenyloxycarbonyloxy group, An aryloxycarbonyloxy group, an alkyl or alkenylsulfonyl group, an arylsulfonyl group, an alkyl or alkenylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, or an oxy radical group. X ₁₀₂ represents a non-metallic atomic group necessary for forming a 5- to 7-membered ring.
In formula (TS-III), R ₁₀₅ and R ₁₀₆ represent a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group, or an aromatic sulfonyl group, and R ₁₀₇ is an aliphatic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, acyloxy group, aliphatic oxycarbonyloxy group, aromatic oxycarbonyloxy group, substituted amino group, heterocyclic group Represents a hydroxy group, and when possible, R ₁₀₅ and R ₁₀₆ , R ₁₀₆ and R ₁₀₇ , R ₁₀₅ and R ₁₀₇ may be bonded to each other to form a 5- to 7-membered ring, Except for the case where a 6,6-tetraalkylpiperidine skeleton is formed. However, R ₁₀₅ and R ₁₀₆ are not both hydrogen atoms, and the total number of carbon atoms is 7 or more.
In formula (TS-IV), R ₁₁₁ and R ₁₁₂ may represent an aliphatic group, and R ₁₁₁ and R ₁₁₂ may be bonded to each other to form a 5- to 7-membered ring. n represents 0, 1, 2; However, the total carbon number of R ₁₁₁ and R ₁₁₂ is 10 or more.
In the general formula (TS-V), R ₁₂₁ and R ₁₂₂ represent an aliphatic oxy group and an aromatic oxy group, R ₁₂₃ represents an aliphatic group, an aromatic group, an aliphatic oxy group, and an aromatic oxy group, m represents 0 or 1; R ₁₂₁ and R ₁₂₂ , and R ₁₂₁ and R ₁₂₃ may be bonded to each other to form a 5- to 8-membered ring. However, the total carbon number of R ₁₂₁ , R ₁₂₂ and R ₁₂₃ is 10 or more. ] The ultraviolet absorber according to claim 1, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (4).

(In the formula, A ₄₁ and A ₄₂ each independently represent a divalent or higher-valent non-metal atom other than a carbon atom. Y ₄₁ and Y ₄₂ each independently represent a monovalent substituent. V ₄₁ , V ₄₂ , V ₄₃ and V ₄₄ each independently represents a hydrogen atom or a monovalent substituent, and V _{41 to} V ₄₄ may form a ring together with the carbon atom at an arbitrary position, which is further condensed. May be.) The ultraviolet absorber according to claim 2, wherein A ₄₁ and A ₄₂ in the general formula (4) are both sulfur atoms. The ultraviolet absorber according to claim 2, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5).

(In the formula, A ₅₁ and A ₅₂ each independently represent a divalent or higher non-metallic atom other than a carbon atom. Y ₅₁ and Y ₅₂ each independently represent a monovalent substituent. V ₅₁ and V ₅₂ represents each independently a hydrogen atom or a monovalent substituent, and X ₅₁ and X ₅₂ each independently represent a hydrogen atom or a monovalent substituent.) In Formula (5), Y ₅₁ and Y ₅₂ is a cyano ^{group, -COR 1, -COOR 2, -CONR} 3 R 4, -SOR 5, -SO 2 R 6 or -SO ₂ NR ⁷ R ^8, (R ^{1 to} R ⁸ represent a hydrogen atom or a monovalent substituent), or Y ₅₁ and Y ₅₂ are bonded to each other to form a ring. The ultraviolet absorber as described.   The L is selected from the group consisting of —NH— group, aminoalkylene group, diaminoalkylene group, aminoarylene group, diaminoarylene group, aminoalkenylene group, diaminoalkenylene group, aminoalkynylene group, and diaminoalkynylene group. It is a coupling group, The ultraviolet absorber of any one of Claims 1-5 characterized by the above-mentioned.   The at least one of the B is a residue obtained by removing a hydrogen atom or a monovalent substituent from any position of the compound represented by the general formula (TS-II). The ultraviolet absorber of any one of 1-6. The ultraviolet absorber according to claim 7, wherein the compound represented by the general formula (TS-II) is a compound represented by the following general formula (TS-IIa).

_Wherein X ₁₀₁ is a hydrogen atom, an alkyl group, an alkenyl group, an alkyloxy group, an alkenyloxy group, an alkyl or alkenyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, an alkyloxycarbonyloxy group, an alkenyl Oxycarbonyloxy group, aryloxycarbonyloxy group, alkyl or alkenylsulfonyl group, arylsulfonyl group, alkyl or alkenylsulfinyl group, arylsulfinyl group, sulfamoyl group, carbamoyl group, hydroxy group or oxy radical group R ₂₀₀ represents 1 Represents a valent substituent.) The ultraviolet absorber according to claim 8, wherein in the general formula (TS-IIa), R ₂₀₀ is a —NHCOR ¹⁰ group (R ¹⁰ represents a hydrogen atom or a monovalent substituent). .   The ultraviolet absorber composition characterized by including the ultraviolet absorber of any one of Claims 1-9.   The ultraviolet absorber solution characterized by including the ultraviolet absorber of any one of Claims 1-9.   A polymer material comprising the ultraviolet absorber according to claim 1.