JP5342896B2 - Heterocyclic compounds - Google Patents

Abstract

Disclosed is a compound represented by general formula (1): (In the formula, L1 represents a substituted or unsubstituted ethenylene group or ethinylene group. R1a-R1h each independently represent a hydrogen atom or monovalent substituent. X1a-X1d each independently represent a heteroatom. Y1a-Y1d each independently represent a heteroatom or carbon atom. Q1 and Q2 each independently represent an oxygen atom, sulfur atom, or NRa (Wherein Ra represents a hydrogen atom or monovalent substituent.). Z1 and Z2 each independently represent a group of atoms necessary to form a 4- to 8-membered ring with Y1a-Y1d. n1a and n1b each independently represent an integer of 1 or greater, and m1 represents an integer of 1 or greater.)

Description

  The present invention relates to a heterocyclic compound, and an ultraviolet absorber and a fluorescent brightening agent comprising the compound.

Conventionally, ultraviolet absorbers have been imparted by sharing ultraviolet absorbers with various resins. 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 free to be selected because the absorption wavelength is determined by the band gap of the compound. There is no such thing that can absorb up to 400 nm in the long wave ultraviolet (UV-A) region, and those that absorb long wave ultraviolet light have absorption up to the visible region and are colored.
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, and when absorbing up to the long wave ultraviolet region, whether the maximum absorption wavelength is in the long wave ultraviolet region or whether the concentration is increased. There are two possible ways. However, those having the maximum absorption wavelength described in Patent Documents 4 and 5 in the long-wave ultraviolet region have poor light resistance, and the absorption capacity decreases with time.

  In contrast, benzophenone and benzotriazole 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 6 and 7). .) A benzoxazinone-based ultraviolet absorber is also known (see, for example, Patent Document 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. With this film thickness, it is necessary to add an ultraviolet absorber at a considerably high concentration in order to cut to a long wavelength region. 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. In addition, some benzophenone and benzotriazole ultraviolet absorbers have skin irritation properties and accumulation properties in the living body, and careful attention is required for use.

JP-A-5-339033 JP-A-5-345639 JP-A-6-56466 JP-A-6-145387 JP 2003-177235 A JP-A-2005-517787 JP-A-7-285927 JP 62-11744 A

  The object of the present invention is to solve the above-mentioned problems, not only to improve the ultraviolet light durability of the polymer material to be shared, but also to stabilize the other by using the polymer material as an ultraviolet filter. An object of the present invention is to provide a compound that can suppress decomposition of the compound and can be used as an ultraviolet absorber that maintains long-wave ultraviolet absorption ability for a long time.

  As a result of examining the heterocyclic compounds in detail, the present inventors have found a compound having a conventionally unknown structure that has high light fastness and can absorb ultraviolet rays in a long wavelength region that could not be covered so far. The present invention has been completed.

［Ｌ¹は、置換または無置換のエテニレン基又はエチニレン基を表す。
Ｒ^1a、Ｒ^1b、Ｒ^1c、Ｒ^1d、Ｒ^1e、Ｒ^1f、Ｒ^1g及びＲ^1h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^1a、Ｒ^1b、Ｒ^1c、Ｒ^1d、Ｒ^1e、Ｒ^1f、Ｒ^1g及びＲ^1hは、互いに連結して環を形成していても良い。
Ｘ^1a、Ｘ^1b、Ｘ^1c及びＸ^1dは、互いに独立してヘテロ原子を表す。また、Ｘ^1a〜Ｘ^1dは置換基を有していても良い。
Ｙ^1a、Ｙ^1b、Ｙ^1c及びＹ^1dは、互いに独立してヘテロ原子または炭素原子を表す。また、Ｙ^1a〜Ｙ^1dは置換基を有していても良い。
Ｑ¹及びＱ²は、それぞれ独立して酸素原子、硫黄原子または、ＮＲ^aを表す（Ｒ^aは、水素原子または１価の置換基を表す。）。
Ｚ¹及びＺ²は、それぞれ独立して、Ｙ^1a及びＹ^1bまたはＹ^1c及びＹ^1dと一緒になって４〜８員環を形成するのに必要な原子群を表す。
ｎ^1a及びｎ^1bは、互いに独立して１以上の整数を表し、ｍ¹は、１以上の整数を表す。］ The object of the present invention has been achieved by the following method.
<1> A compound represented by the following general formula (1).

[L ¹ represents a substituted or unsubstituted ethenylene group or an ethynylene group.
R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1f , R ^1g and R ^1h each independently represent a hydrogen atom or a monovalent substituent. R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1f , R ^1g and R ^1h may be connected to each other to form a ring.
X ^1a , X ^1b , X ^1c and X ^1d each independently represent a hetero atom. X ^{1a to} X ^1d may have a substituent.
Y ^1a , Y ^1b , Y ^1c and Y ^1d each independently represent a hetero atom or a carbon atom. Y ^{1a to} Y ^1d may have a substituent.
Q ¹ and Q ² each independently represents an oxygen atom, a sulfur atom or NR ^a (R ^a represents ^a hydrogen atom or a monovalent substituent).
Z ¹ and Z ² each independently represents an atomic group necessary for forming a 4- to 8-membered ring together with Y ^1a and Y ^1b or Y ^1c and Y ^1d .
n ^1a and n ^1b each independently represent an integer of 1 or more, and m ¹ represents an integer of 1 or more. ]

［Ｌ²は、前記一般式（１）のＬ¹と同義である。
Ｒ^2a、Ｒ^2b、Ｒ^2c、Ｒ^2d、Ｒ^2e、Ｒ^2f、Ｒ^2g及びＲ^2hは、それぞれ前記一般式（１）のＲ^1a、Ｒ^1b、Ｒ^1c、Ｒ^1d、Ｒ^1e、Ｒ^1f、Ｒ^1g及びＲ^1hと同義である。
Ｒ²ⁱ、Ｒ^2j、Ｒ^2k、Ｒ^2p、Ｒ^2q、Ｒ^2r、Ｒ^2s及びＲ^2t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、Ｒ²ⁱ、Ｒ^2j、Ｒ^2k、Ｒ^2p、Ｒ^2q、Ｒ^2r、Ｒ^2s及びＲ^2tは、互いに連結して環を形成していても良い。
Ｘ^2a、Ｘ^2b、Ｘ^2c及びＸ^2dは、それぞれ前記一般式（１）のＸ^1a、Ｘ^1b、Ｘ^1c及びＸ^1dと同義である。
ｎ^2a及びｎ^2bは、それぞれ前記一般式（１）のｎ^1a及びｎ^1bと同義である。ｍ²は、前記一般式（１）のｍ¹と同義である。］ <2> The compound according to <1>, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

[L ² has the same meaning as L ^{1 in} formula (1).
R ^2a , R ^2b , R ^2c , R ^2d , R ^2e , R ^2f , R ^2g and R ^2h are respectively R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^{1f in the} general formula (1). , R ^1g and R ^1h .
R ²ⁱ , R ^2j , R ^2k , R ^2p , R ^2q , R ^2r , R ^2s and R ^2t each independently represent a hydrogen atom or a monovalent substituent. R ²ⁱ , R ^2j , R ^2k , R ^2p , R ^2q , R ^2r , R ^2s and R ^2t may be connected to each other to form a ring.
X ^2a , X ^2b , X ^2c and X ^2d have the same ^meanings as X ^1a , X ^1b , X ^1c and X ^{1d in the} general formula (1), respectively.
n ^2a and n ^2b have the same ^meanings as n ^1a and n ^{1b in} the general formula (1), respectively. m ² has the same meaning as m ^{1 in the} general formula (1). ]

［Ｌ³は、前記一般式（２）のＬ²と同義である。
Ｒ^3a、Ｒ^3b、Ｒ^3c、Ｒ^3d、Ｒ^3e、Ｒ^3f、Ｒ^3g、Ｒ^3h、Ｒ³ⁱ、Ｒ^3j、Ｒ^3k、Ｒ^3p、Ｒ^3q、Ｒ^3r、Ｒ^3s及びＲ^3tは、それぞれ前記一般式（２）のＲ^2a、Ｒ^2b、Ｒ^2c、Ｒ^2d、Ｒ^2e、Ｒ^2f、Ｒ^2g、Ｒ^2h、Ｒ²ⁱ、Ｒ^2j、Ｒ^2k、Ｒ^2p、Ｒ^2q、Ｒ^2r、Ｒ^2s及びＲ^2tと同義である。
ｎ^3a及びｎ^3bは、それぞれ前記一般式（２）のｎ^2a及びｎ^2bと同義である。ｍ³は、前記一般式（２）のｍ²と同義である。］ <3> The compound according to <2>, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

[L ³ has the same meaning as L ^{2 in the} general formula (2).
R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g , R ^3h , R ³ⁱ , R ^3j , R ^3k , R ^3p , R ^3q , R ^3r , R ^3s and R ^3t are respectively R ^2a , R ^2b , R ^2c , R ^2d , R ^2e , R ^2f , R ^2g , R ^2h , R ²ⁱ , R ^2j , R ^2k , R ^2p , R ^2q , R ^2r , R in the general formula (2) it is synonymous with ^2s and R ^2t.
n ^3a and n ^3b have the same ^meanings as n ^2a and n ^{2b in} the general formula (2), respectively. m ³ has the same meaning as m ^{2 in the} general formula (2). ]

［Ｌ⁴は、前記一般式（３）のＬ³と同義である。
Ｒ^4a、Ｒ^4b、Ｒ^4c、Ｒ^4d、Ｒ^4e、Ｒ^4f、Ｒ^4g、Ｒ^4h、Ｒ⁴ⁱ、Ｒ^4j、Ｒ^4k、Ｒ^4p、Ｒ^4q、Ｒ^4r、Ｒ^4s及びＲ^4tは、それぞれ前記一般式（３）のＲ^3a、Ｒ^3b、Ｒ^3c、Ｒ^3d、Ｒ^3e、Ｒ^3f、Ｒ^3g、Ｒ^3h、Ｒ³ⁱ、Ｒ^3j、Ｒ^3k、Ｒ^3p、Ｒ^3q、Ｒ^3r、Ｒ^3s及びＲ^3tと同義である。
ｍ⁴は、前記一般式（３）のｍ³と同義である。］ <4> The compound according to <3>, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (4).

[L ⁴ has the same meaning as L ^{3 in} formula (3).
R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g , R ^4h , R ⁴ⁱ , R ^4j , R ^4k , R ^4p , R ^4q , R ^4r , R ^4s and R ^4t are respectively In the general formula (3), R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g , R ^3h , R ³ⁱ , R ^3j , R ^3k , R ^3p , R ^3q , R ^3r , R Synonymous with ^3s and R ^3t .
m ⁴ has the same meaning as m ^{3 in the} general formula (3). ]

［Ｌ⁵は、置換または無置換のエテニレン基を表す。
Ｒ^5a、Ｒ^5b、Ｒ^5c、Ｒ^5d、Ｒ^5e、Ｒ^5f、Ｒ^5g、Ｒ^5h、Ｒ⁵ⁱ、Ｒ^5j、Ｒ^5k、Ｒ^5p、Ｒ^5q、Ｒ^5r、Ｒ^5s及びＲ^5tは、それぞれ前記一般式（４）のＲ^4a、Ｒ^4b、Ｒ^4c、Ｒ^4d、Ｒ^4e、Ｒ^4f、Ｒ^4g、Ｒ^4h、Ｒ⁴ⁱ、Ｒ^4j、Ｒ^4k、Ｒ^4p、Ｒ^4q、Ｒ^4r、Ｒ^4s及びＲ^4tと同義である。
ｍ⁵は、前記一般式（４）のｍ⁴と同義である。］ <5> The compound according to <4>, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5).

[L ⁵ represents a substituted or unsubstituted ethenylene group.
R ^5a , R ^5b , R ^5c , R ^5d , R ^5e , R ^5f , R ^5g , R ^5h , R ⁵ⁱ , R ^5j , R ^5k , R ^5p , R ^5q , R ^5r , R ^5s and R ^5t are respectively In the general formula (4), R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g , R ^4h , R ⁴ⁱ , R ^4j , R ^4k , R ^4p , R ^4q , R ^4r , R It is synonymous with ^4s and R ^4t .
m ⁵ has the same meaning as m ^{4 in the} general formula (4). ]

［Ｒ^6a、Ｒ^6b、Ｒ^6c、Ｒ^6d、Ｒ^6e、Ｒ^6f、Ｒ^6g、Ｒ^6h、Ｒ⁶ⁱ、Ｒ^6j、Ｒ^6k、Ｒ^6p、Ｒ^6q、Ｒ^6r、Ｒ^6s及びＲ^6tは、それぞれ前記一般式（５）のＲ^5a、Ｒ^5b、Ｒ^5c、Ｒ^5d、Ｒ^5e、Ｒ^5f、Ｒ^5g、Ｒ^5h、Ｒ⁵ⁱ、Ｒ^5j、Ｒ^5k、Ｒ^5p、Ｒ^5q、Ｒ^5r、Ｒ^5s及びＲ^5tと同義である。
Ｒ^6u及びＲ^6v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。］
＜７＞＜１＞〜＜６＞のいずれか１項に記載の化合物からなる紫外線吸収剤。
＜８＞＜１＞〜＜６＞のいずれか１項に記載の化合物からなる蛍光増白剤。 <6> The compound according to <5>, wherein the compound represented by the general formula (5) is a compound represented by the following general formula (6).

[R ^6a , R ^6b , R ^6c , R ^6d , R ^6e , R ^6f , R ^6g , R ^6h , R ⁶ⁱ , R ^6j , R ^6k , R ^6p , R ^6q , R ^6r , R ^6s and R ^6t are R ^5a , R ^5b , R ^5c , R ^5d , R ^5e , R ^5f , R ^5g , R ^5h , R ⁵ⁱ , R ^5j , R ^5k , R ^5p , R ^5q , R ^5r , respectively in the general formula (5) the same meaning as R ^5s and R ^5t.
R ^6u and R ^6v each independently represent a hydrogen atom or a monovalent substituent. ]
<7> An ultraviolet absorber comprising the compound according to any one of <1> to <6>.
<8> A fluorescent brightening agent comprising the compound according to any one of <1> to <6>.

  The compound of the present invention can be used as an ultraviolet absorber having high light fastness and a fluorescent whitening agent having high whitening property. Moreover, the light stability of a polymer molded product can be enhanced by incorporating the compound of the present invention into a polymer molded product such as plastic or fiber. Furthermore, the polymer material containing the compound of the present invention can be used as a filter or a container for protecting contents vulnerable to ultraviolet rays by utilizing the excellent ultraviolet absorbing ability.

Hereinafter, the present invention will be described in detail.
In the general formula (1), L ¹ represents a substituted or unsubstituted ethenylene group (—CH ₂ ═CH ₂ —) or an ethynylene group (—CH≡CH—).

A monovalent substituent is mentioned as a substituent. Examples of the monovalent substituent (hereinafter referred to as R) include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group having 1 to 20 carbon atoms (for example, methyl and ethyl), and a carbon number of 6 To 20 aryl groups (eg phenyl, naphthyl), cyano groups, carboxyl groups, alkoxycarbonyl groups (eg methoxycarbonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), substituted or unsubstituted carbamoyl groups (eg carbamoyl, N- Phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl group (eg acetyl), arylcarbonyl group (eg benzoyl), nitro group, substituted or unsubstituted amino group (eg amino, dimethylamino, anilino), acylamino group ( For example, acetamide, ethoxy Rubonylamino), sulfonamide group (eg methanesulfonamide), imide group (eg succinimide, phthalimide), imino group (eg benzylideneamino), hydroxy group, alkoxy group having 1 to 20 carbon atoms (eg methoxy), aryloxy group (Eg phenoxy), acyloxy groups (eg acetoxy), alkylsulfonyloxy groups (eg methanesulfonyloxy), arylsulfonyloxy groups (eg benzenesulfonyloxy), sulfo groups, substituted or unsubstituted sulfamoyl groups (eg sulfamoyl, N- Phenylsulfamoyl), alkylthio group (eg methylthio), arylthio group (eg phenylthio), alkylsulfonyl group (eg methanesulfonyl), arylsulfonyl group (eg benze) Sulfonyl), and the like Hajime Tamaki having 6 to 20 carbon atoms (e.g. pyridyl, morpholino). Further, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. In that case, the above-mentioned monovalent substituent R can be mentioned as an example of a substituent. Moreover, you may combine with substituents and may form a ring.
Preferred examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. More preferred are an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms, and particularly preferred is an alkyl group having 1 to 20 carbon atoms.

R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1f , R ^1g and R ^1h each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent include the examples of the monovalent substituent R described above. R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1f , R ^1g and R ^1h may be connected to each other to form a ring.

X ^1a , X ^1b , X ^1c and X ^1d each independently represent a hetero atom. Examples of the hetero atom include a boron atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a selenium atom, and a tellurium atom. A hetero atom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. More preferably, they are a nitrogen atom and an oxygen atom. X ^1a , X ^1b , X ^1c and X ^1d may be different from each other, but it is more preferable that X ^1a and X ^1b , and X ^1c and X ^1d each represent the same combination, particularly preferably X ^{In this case, 1a} and X ^1c represent an oxygen atom, and X ^1b and X ^1d represent a nitrogen atom. X ^{1a to} X ^1d may have a substituent. Examples of the substituent include the examples of the monovalent substituent R described above.

Y ^1a , Y ^1b , Y ^1c and Y ^1d each independently represent a hetero atom or a carbon atom. Examples of the atoms constituting Y ^{1a to} Y ^1d include a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. The atoms constituting Y ^{1a to} Y ^1d are preferably a carbon atom, a nitrogen atom, and an oxygen atom, and more preferably a carbon atom and a nitrogen atom. More preferred is a carbon atom, and particularly preferred is a case where all represent a carbon atom. Y ^{1a to} Y ^1d may have a substituent. Examples of the substituent include the examples of the monovalent substituent R described above.

Q ¹ and Q ² each independently represents an oxygen atom, a sulfur atom or ═NR ^a (R ^a represents ^a hydrogen atom or a monovalent substituent. The substituent is the above-described monovalent substituent R. The oxygen atom is preferably ═NR ^a . More preferred is an oxygen atom. Q ¹ and Q ² may be different from each other but are preferably the same. In particular, it is particularly preferable that both Q ¹ and Q ² are oxygen atoms.

Z ¹ and Z ² each independently represents an atomic group necessary for forming a 4- to 8-membered ring together with Y ^1a and Y ^1b or Y ^1c and Y ^1d . These rings may have a substituent and may further be condensed. Examples of the ring to be formed include aliphatic hydrocarbon rings such as cyclohexane and cyclopentane, aromatic hydrocarbon rings such as benzene ring and naphthalene ring, pyridine, pyrrole, pyridazine, thiophene, imidazole, furan, pyrazole, oxazole, triazole, thiazo And heterocyclic rings such as benzo-condensed compounds thereof. An aromatic hydrocarbon ring and a hetero ring are preferable. An aromatic hydrocarbon ring is more preferable, and a benzene ring is particularly preferable.

n ^1a and n ^1b each independently represent an integer of 1 or more, preferably 1 to 3 independently of each other.
m ¹ represents an integer of 1 or more, and preferably 1 to 3 independently of each other.

  The compound represented by the general formula (1) is preferably a compound represented by the general formula (2). Hereinafter, the compound represented by the general formula (2) will be described.

L ² has the same meaning as L ^{1 in the} general formula (1), and is the same when preferred.
R ^2a , R ^2b , R ^2c , R ^2d , R ^2e , R ^2f , R ^2g and R ^2h are respectively R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^{1f in the} general formula (1). , R ^1g and R ^1h, and the same ^applies to preferred cases.

R ²ⁱ , R ^2j , R ^2k , R ^2p , R ^2q , R ^2r , R ^2s and R ^2t each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent include the examples of the monovalent substituent R described above. Any two substituents of R ²ⁱ , R ^2j , R ^2k and R ^2p and any two substituents of R ^2q , R ^2r , R ^2s and R ^2t are bonded to each other to form a ring. Alternatively, it may be further condensed. R ^{2i to} R ^2t are preferably a hydrogen atom, an alkyl group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, and a hydroxy group, and more preferably a hydrogen atom and an alkoxy group having 10 or less carbon atoms. More preferred is a hydrogen atom, and particularly preferred is a case where all of R ^{2i to} R ^2t represent a hydrogen atom.

X ^2a , X ^2b , X ^2c, and X ^2d have the same ^meanings as X ^1a , X ^1b , X ^1c, and X ^{1d in the} general formula (1), respectively, and are the same when preferred.
n ^2a and n ^2b have the same ^meanings as n ^1a and n ^{1b in} the general formula (1), respectively, and the same applies when preferred.
m ² has the same meaning as m ^{1 in the} general formula (1), and is the same when preferred.

  Furthermore, the compound represented by the general formula (2) is preferably a compound represented by the general formula (3). Hereinafter, the compound represented by the general formula (3) will be described.

L ³ has the same meaning as L ^{2 in the} general formula (2), and is the same when preferred.
R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g , R ^3h , R ³ⁱ , R ^3j , R ^3k , R ^3p , R ^3q , R ^3r , R ^3s and R ^3t are respectively R ^2a , R ^2b , R ^2c , R ^2d , R ^2e , R ^2f , R ^2g , R ^2h , R ²ⁱ , R ^2j , R ^2k , R ^2p , R ^2q , R ^2r , R in the general formula (2) have the same meanings as ^2s and R ^2t, the favorable examples thereof are also the same.
n ^3a and n ^3b have the same ^meanings as n ^2a and n ^{2b in} the general formula (2), respectively, and the same applies when preferred.
m ³ has the same meaning as m ^{2 in the} general formula (2), and is the same when preferred.

  Furthermore, the compound represented by the general formula (3) is preferably a compound represented by the general formula (4). Hereinafter, the compound represented by the general formula (4) will be described.

L ⁴ has the same meaning as L ^{3 in the} general formula (3), and is the same when preferred.
R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g , R ^4h , R ⁴ⁱ , R ^4j , R ^4k , R ^4p , R ^4q , R ^4r , R ^4s and R ^4t are respectively In the general formula (3), R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g , R ^3h , R ³ⁱ , R ^3j , R ^3k , R ^3p , R ^3q , R ^3r , R have the same meanings as ^3s and R ^3t, the favorable examples thereof are also the same.
m ⁴ has the same meaning as m ^{3 in the} general formula (3), and is the same when preferred.

  Furthermore, the compound represented by the general formula (4) is preferably a compound represented by the general formula (5). Hereinafter, the compound represented by the general formula (5) will be described.

L ⁵ represents a substituted or unsubstituted ethenylene group. Examples of the substituent include the examples of the monovalent substituent R described above.
R ^5a , R ^5b , R ^5c , R ^5d , R ^5e , R ^5f , R ^5g , R ^5h , R ⁵ⁱ , R ^5j , R ^5k , R ^5p , R ^5q , R ^5r , R ^5s and R ^5t are respectively In the general formula (4), R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g , R ^4h , R ⁴ⁱ , R ^4j , R ^4k , R ^4p , R ^4q , R ^4r , R It is synonymous with ^4s and ^R4t, and the same ^applies to preferred cases.
m ⁵ has the same meaning as m ^{4 in the} general formula (4), and is the same when preferred.

  Furthermore, the compound represented by the general formula (5) is preferably a compound represented by the general formula (6). Hereinafter, the compound represented by the general formula (6) will be described.

R ^6a , R ^6b , R ^6c , R ^6d , R ^6e , R ^6f , R ^6g , R ^6h , R ⁶ⁱ , R ^6j , R ^6k , R ^6p , R ^6q , R ^6r , R ^6s and R ^6t are respectively R ^5a, R ^5b in the formula ^{(5), R 5c, R} 5d, R 5e, R 5f, R 5g, R 5h, R 5i, R 5j, R 5k, R 5p, R 5q, R 5r, R have the same meanings as ^5s and R ^5t, the favorable examples thereof are also the same.
R ^6u and R ^6v each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent include the examples of the monovalent substituent R described above.

  The compound represented by any one of the general formulas (1) to (6) can be synthesized by any method. For example, publicly known patent documents and non-patent documents, for example, an example of page 4 left 43th line to right 8th line of JP-A-2000-264879, page 4 right column 5th line 30 to 30 of JP-A-2003-155375. It can be synthesized with reference to the example of the line, “Bioorganic & Medicinal Chemistry”, 2000, 8, pp. 2095-2103, “Bioorganic & Medicinal Chemistry Letters”, 2003, Vol. 13, pp. 4077-4080. For example, exemplary compound (23) can be synthesized by reaction of 4,4'-stilbene dicarboxylic acid and 3-methylanthranilic acid. The exemplified compound (28) can be synthesized by reacting 4,4'-stilbene dicarboxylic acid with 5-hydroxyanthranilic acid. Exemplary compound (29) can be synthesized by reaction of 4,4'-stilbene dicarboxylic acid and 5-methoxyanthranilic acid. The exemplified compound (38) can be synthesized by a reaction of 4,4'-stilbene dicarboxylic acid and 3-amino-2-naphthoic acid. The exemplified compound (40) can be synthesized by reacting 4,4'-stilbene dicarboxylic acid with 2-aminonicotinic acid.

  Specific examples of the compound represented by any one of the general formulas (1) to (6) are shown below, but the present invention is not limited thereto.

  The compounds of the present invention can take tautomers depending on the structure and the environment in which they are placed. Although the present invention is described in one of the representative forms, tautomers different from those described in the present invention are also included in the compounds of the present invention.

The compound of the present invention may contain isotopes (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O and the like).

  A polymer containing the structure of the compound represented by any one of the general formulas (1) to (6) in the repeating unit can also be suitably used in the present invention. The polymer may be a homopolymer or a copolymer composed of two or more types of repeating units. Further, it may be a copolymer containing other repeating units. The polymer containing the ultraviolet absorber structure in the repeating unit is described in JP-B-1-53455, JP-A-61-189530, and European Patent 27242. The description of these patent documents can be referred to for the method of obtaining the polymer.

  The compound represented by any one of the general formulas (1) to (6) is particularly suitable for stabilizing an organic material against damage caused by light, oxygen, or heat. Among them, it can be suitably used as a light stabilizer, particularly an ultraviolet absorber. Hereinafter, the case where the compound represented by any one of the general formulas (1) to (6) is used as an ultraviolet absorber will be described.

  The compound represented by any one of the general formulas (1) to (6) can be preferably used as a long wavelength ultraviolet absorber. The maximum absorption wavelength is preferably in the range of 320 to 460 nm, more preferably in the range of 340 to 440 nm, and particularly preferably in the range of 360 to 420 nm.

What is stabilized by the ultraviolet absorber of the present invention includes dyes, pigments, foods, beverages, body care products, vitamins, pharmaceuticals, inks, oils, fats, waxes, surface coatings, cosmetics, photographic materials, textiles and the like Examples include pigments, plastic materials, rubber, paints, polymer materials, polymer additives, and the like.
Any use form of the ultraviolet absorber of the present invention may be used. For example, a liquid dispersion, a solution, a polymer material, and the like can be given.

The ultraviolet absorbent comprising the compound represented by any one of the general formulas (1) to (6) of the present invention can be used in the state of a dispersion dispersed in a dispersion medium. Hereinafter, the ultraviolet absorbent dispersion containing the ultraviolet absorbent 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 dispersion containing the ultraviolet absorbent according to 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 thereof include dyes, pigments, infrared absorbers, fragrances, polymerizable compounds, polymers, inorganic substances, metals, and the like.

  As a device for obtaining a dispersion containing the ultraviolet absorbent according to the present invention, a high-speed stirring disperser having a large shearing force, a disperser giving high-intensity ultrasonic energy, or 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.

Moreover, the ultraviolet absorber of this invention can be used in the state of the solution melt | dissolved in the liquid medium. Hereinafter, the ultraviolet absorbent solution containing the ultraviolet absorbent 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 thereof include dyes, pigments, infrared absorbers, 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 absorber in the solution containing the ultraviolet absorber 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 containing the ultraviolet absorber 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 point 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 absorber in the solution containing the ultraviolet absorber 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.
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. As the fluorescent brightening agent, in addition to the compound represented by any one of the above general formulas (1) to (6), a commercially available product, the general formula [1] described in JP-A No. 2002-53824, or a specific compound Examples 1-35 etc. are mentioned.

  Subsequently, the polymer substance used in the present invention will be described. The polymer substance may be either a natural or synthetic polymer. Polyolefins (eg, polyethylene, polypropylene, polyisobutylene, poly (1-butene), poly-4-methylpentene, polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly (α-methylstyrene), polyisoprene, polybutadiene, Polycyclopentene, polynorbornene, etc.), copolymers of vinyl monomers (eg, ethylene / propylene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / vinylcyclohexane copolymers, ethylene / cycloolefin copolymers (eg, ethylene / norbornene) Such as cycloolefin copolymer (COC), propylene / butadiene copolymer, isobutylene / isoprene copolymer, Ethylene / vinylcyclohexene copolymer, ethylene / alkyl acrylate copolymer, ethylene / alkyl methacrylate copolymer, etc.), acrylic polymer (eg, polymethacrylate, polyacrylate, polyacrylamide, polyacrylonitrile, etc.), polyvinyl chloride, polyvinylidene chloride, polyfluoride Vinyl, polyvinylidene fluoride, vinyl chloride / vinyl acetate copolymer, polyether (eg, polyalkylene glycol, polyethylene oxide, polypropylene oxide, etc.), polyacetal (eg, polyoxymethylene), polyamide, polyimide, polyurethane, polyurea, polyester ( For example, polyethylene terephthalate, polyethylene naphthalate, etc.), polycarbonate, polyketone, polyethylene Sulfone polyether ketone, phenol resin, melamine resin, cellulose ester (for example, diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polysiloxane, natural polymer (for example, cellulose) , Rubber, gelatin, etc.).

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 containing the ultraviolet absorbent according to the present invention includes 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 absorbent. Any additive may be appropriately contained.
When the ultraviolet absorbent according to the present invention is used, the mode thereof may be any method. Although the ultraviolet absorber of the present invention may be used alone or as a composition, it is preferably used as a composition. Especially, it is preferable that it is a polymeric material containing the ultraviolet absorber of this invention. Hereinafter, the polymer material containing the ultraviolet absorbent according to the present invention will be described.

The polymer material containing the ultraviolet absorbent according to the present invention uses the polymer material. The polymer material containing the ultraviolet absorbent according to 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 coating materials for interior and exterior facilities and transportation equipment, coating films formed by the coating, alkyd resin lacquer coating and coating formed by the coating, acrylic lacquer coating and coating formed by the coating, 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, dyeing Anti-fading agents such as coating materials, protective films for polymer supports (eg for plastic parts such as machinery and automotive parts), printed overcoats, inkjet media coatings, laminated matte, optical light films, safety glass / front Glass interlayers, electrochromic / photochromic applications, overlaminate films, solar thermal control films, sunscreen creams, shampoos, rinses, hairdressing cosmetics, sportswear, stockings, hats and other clothing textiles and fibers, curtains, carpets Interior products for home use such as wallpaper, plastic lenses, contact lenses, medical devices such as artificial eyes, optical filters, backlight display films, prisms, mirrors, optical materials such as photographic materials, mold films, transfer stickers, graffiti Statements such as prevention film, tape, ink Examples include a utensil, a sign plate, a sign device, and a surface coating material thereof.

  Examples of the shape of the polymer material containing the ultraviolet absorbent according to the present invention include a 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, and a porous shape. Any shape may be sufficient.

  Since the polymer material containing the ultraviolet absorber of the present invention contains the ultraviolet absorber of the present invention, it has excellent light resistance (fastness to ultraviolet light), and precipitation of the ultraviolet absorber and long-term use No bleed out occurs. 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 containing the ultraviolet absorber of the present invention is used as an ultraviolet absorption filter or an ultraviolet absorption film, the polymer substance 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 imides, polyoxyethylene, and the like. Preferred are cellulose ester, polycarbonate, polyester, polyolefin, and acrylic resin, and more preferred are polycarbonate and polyester. Further preferred is polyester, and particularly preferred is polyethylene terephthalate. The polymer material containing the ultraviolet absorber 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.

  In the present invention, two or more compounds represented by any one of the general formulas (1) to (6) having different structures may be used in combination, or any one of the general formulas (1) to (6). A compound represented by the above formula and one or more ultraviolet absorbers having other structures may be used in combination. When two types (preferably three types) of ultraviolet absorbers are used in combination, ultraviolet rays in a wide wavelength region can be absorbed. In addition, when two or more kinds of ultraviolet absorbers are used in combination, the dispersion state of the ultraviolet absorber is also stabilized. Any ultraviolet absorber having a structure other than one of the general formulas (1) to (6) 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 ultraviolet absorbers described in the supervision of “Development of polymer additives and environmental measures” (CMC Publishing Co., Ltd., 2003), pages 54 to 64.

  The ultraviolet absorber having a structure other than any one of the general formulas (1) to (6) is preferably a benzotriazole, benzophenone, salicylic acid, cyanoacrylate, or triazine compound. More preferred are benzotriazole, benzophenone and triazine compounds. Particularly preferred are benzotriazole compounds.

  The effective absorption wavelength of the benzotriazole compound is about 270 to 380 nm, and representative examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-t-butyl). Phenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t) -Butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5 '-(2- (octyloxycarbonyl) ethyl) phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′- -T-amylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di- (dimethylbenzyl) phenyl) Benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) benzotriazole, 2,2′-methylene-bis (2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole) 2 -(2'-hydroxy-3 '-(3,4,5,6-tetrahydrophthalimidylmethyl) -5'-methylbenzyl) phenyl) benzotriazole and the like.

  The effective absorption wavelength of the benzophenone compound is about 270 to 380 nm, and representative examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4- Dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxypropoxy) benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy- 4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2-hydroxy-4-diethylamino 2′-hexyloxycarbonylbenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 1 , 4-bis (4-benzyloxy-3-hydroxyphenoxy) butane and the like.

  The effective absorption wavelength of the salicylic acid compound is about 290 to 330 nm, and representative examples include phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, and the like.

  The effective absorption wavelength of the cyanoacrylate compound is about 270 to 350 nm, and representative examples include 2-ethylhexyl 2-cyano-3, 3-diphenyl acrylate, ethyl 2-cyano-3, 3-diphenyl acrylate, hexadecyl 2-cyano- 3- (4-methylphenyl) acrylate, 2-cyano-3- (4-methylphenyl) acrylate, 1,3-bis ((2′-cyano-3,3′-diphenylacryloyl) oxy) -2 , 2-bis (((2′-cyano-3,3′-diphenylacryloyl) oxy) methyl) propane and the like.

  The effective absorption wavelength of the triazine compound is about 270 to 380 nm, and representative examples include 2- (4-hexyloxy-2-hydroxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (4- Octyloxy-2-hydroxyphenyl) -4,6-di (2,5-dimethylphenyl) -1,3,5-triazine, 2- (4-butoxy-2-hydroxyphenyl) -4,6-di (4 -Butoxyphenyl) -1,3,5-triazine, 2- (4-butoxy-2-hydroxyphenyl) -4,6-di (2,4-dibutoxyphenyl) -1,3,5-triazine, 2 -(4- (3- (2-ethylhexyloxy) -2-hydroxypropoxy) -2-hydroxyphenyl) -4,6-di (2,4-dimethylphenyl) -1,3,5-triazine, 2 − ( -(3-dodecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl) -4,6-di (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-di (4-butoxy- 2-hydroxyphenyl) -6- (4-butoxyphenyl) -1,3,5-triazine, 2,4-di (4-butoxy-2-hydroxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine and the like.

  Moreover, the compound represented by any one of the general formulas (1) to (6) can be suitably used as a fluorescent brightening agent. In general, the optical brightener comprises a compound having the property of absorbing light having a wavelength of about 320 to about 410 nm and emitting light having a wavelength of about 410 to about 500 nm. In addition to the original yellow reflected light, the fabric dyed with these fluorescent whitening agents is added with blue light having a wavelength of about 410 to about 500 nm, which is newly emitted by the fluorescent whitening agent, so that the reflected light is white. And the energy of visible light is increased by the amount due to the fluorescence effect, resulting in whitening.

  Hereinafter, the fluorescent brightener comprising the compound represented by any one of the general formulas (1) to (6) will be described. Any use form of the optical brightener of the present invention may be used. For example, a liquid dispersion, a solution, a polymer material, and the like can be given.

  The optical brightener of the present invention can be used in the state of a dispersion dispersed in a dispersion medium. The dispersion medium of the dispersion containing the optical brightener of the present invention, the adjustment process, the content of the optical brightener and the dispersing apparatus are the same as those of the above-described ultraviolet absorber.

  The fluorescent brightener of the present invention can be used in the state of a solution dissolved in a liquid medium. The addition method, content, and solution of the fluorescent whitening agent in the solution containing the fluorescent whitening agent of the present invention are the same as those of the above-described ultraviolet absorber.

  Moreover, the optical brightener of the present invention is preferably used for a polymer material. The polymer material, additive, shape, and use of the polymer material containing the fluorescent brightener of the present invention are the same as those of the above-described ultraviolet absorber.

When the short wavelength region cannot be sufficiently cut with the fluorescent brightener of the present invention alone, it is preferable to use an ultraviolet absorber in combination.
Any ultraviolet absorber can be used in combination. As an example, the ultraviolet absorber represented by either of the said general formula (1)-(6) and the example of the above-mentioned ultraviolet absorber can be mentioned. These ultraviolet absorbers can be used alone or in combination of two or more.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1
(Preparation of exemplary compound (1))
14.2 g of oxalyl chloride was added dropwise to a mixture of 10.0 g of 4,4′-stilbene dicarboxylic acid in 30 ml of toluene. After adding a few drops of DMF (N, N-dimethylformamide), the mixture was stirred at room temperature for 30 minutes and at 80 ° C. for 10 minutes. This reaction solution was added to a solution of 10.2 g of anthranilic acid in 40 ml of DMAc (N, N-dimethylacetamide), and the resulting solid was filtered and washed with water to obtain 18.0 g of synthetic intermediate A (yield 95). %).

To 10.0 g of the synthetic intermediate A, 50 ml of acetic anhydride and 50 ml of toluene were added. The mixture was reacted under reflux for 10 hours. After cooling to room temperature, 8.5 g of Exemplified Compound (1) was obtained by filtration and washing with acetone (yield 91%).
MS: m / z 470 (M +)
¹ H NMR (CDCl ₃ ): δ 7.32 (2H), δ 7.52-7.55 (2H), δ 7.69-7.73 (6H), δ 7.83-7.87 (2H), δ 8. 25-8.27 (2H), δ 8.34-8.36 (4H)
λmax = 374 nm (EtOAc)

Example 2
(Preparation of exemplary compound (2))
14.2 g of oxalyl chloride was added dropwise to a mixture of 30 ml of toluene of 11.0 g of 4,4 ′-(butadiene-1,4-diyl) dibenzoic acid. After adding a few drops of DMF, the mixture was stirred at room temperature for 30 minutes and at 80 ° C. for 10 minutes. This reaction solution was added to a solution of 10.2 g of anthranilic acid in 40 ml of DMAc, and the resulting solid was filtered and washed with water to obtain 18.7 g of synthetic intermediate B (yield 94%).

  50 ml of acetic anhydride and 50 ml of toluene were added to 10.5 g of the synthetic intermediate B. The mixture was reacted under reflux for 10 hours. After cooling to room temperature, 9.1 g of Exemplified Compound (2) was obtained by filtration and washing with acetone (yield 93%).

Example 3
(Preparation of exemplary compound (5))
14.2 g of oxalyl chloride was added dropwise to a mixture of 10.0 g of 4,4 ′-(ethyne-1,2-diyl) dibenzoic acid in 30 ml of toluene. After adding a few drops of DMF, the mixture was stirred at room temperature for 30 minutes and at 80 ° C. for 10 minutes. This reaction solution was added to a solution of 10.2 g of anthranilic acid in 40 ml of DMAc, and the obtained solid was filtered and washed with water to obtain 17.1 g of synthetic intermediate C (yield 90%).

  50 ml of acetic anhydride and 50 ml of toluene were added to 10.5 g of the synthetic intermediate C. The mixture was reacted under reflux for 10 hours. After cooling to room temperature, 8.7 g of Exemplified Compound (5) was obtained by filtration and washing with acetone (yield 89%).

Example 4
(Preparation of Exemplified Compound (10))
14.2 g of oxalyl chloride was added dropwise to a mixture of 15.7 g of 4 ′, 4 ″-(ethene-1,2-diyl) dibiphenyl-4-carboxylic acid in 30 ml of toluene. After adding several drops of DMF, 30 minutes at room temperature. The reaction mixture was added to a solution of 10.2 g of anthranilic acid in 40 ml of DMAc, and the resulting solid was filtered and washed with water to obtain 23.3 g of synthetic intermediate D (yield 95). %).

  50 ml of acetic anhydride and 50 ml of toluene were added to 13.0 g of the synthetic intermediate D. The mixture was reacted under reflux for 10 hours. After cooling to room temperature, 11.8 g of Exemplified Compound (10) was obtained by filtration and washing with acetone (yield 96%).

Example 5
(Preparation of exemplary compound (18))
14.2 g of oxalyl chloride was added dropwise to a mixture of 10.0 g of 4,4′-stilbene dicarboxylic acid in 30 ml of toluene. After adding a few drops of DMF, the mixture was stirred at room temperature for 30 minutes and at 80 ° C. for 10 minutes. This reaction solution was added to a solution of 11.3 g of 6-amino-m-toluic acid in 40 ml of DMAc, and the obtained solid was filtered and washed with water to obtain 18.7 g of synthetic intermediate E (yield 94%).

  50 ml of acetic anhydride and 50 ml of toluene were added to 10.6 g of the synthetic intermediate E. The mixture was reacted under reflux for 10 hours. After cooling to room temperature, 9.0 g of Exemplified Compound (18) was obtained by filtration and washing with acetone (yield 91%).

Example 6
(Preparation of Exemplified Compound (24))
14.2 g of oxalyl chloride was added dropwise to a mixture of 10.0 g of 4,4′-stilbene dicarboxylic acid in 30 ml of toluene. After adding a few drops of DMF, the mixture was stirred at room temperature for 30 minutes and at 80 ° C. for 10 minutes. This reaction solution was added to a solution of 12.3 g of 3,5-dimethylanthranilic acid in 40 ml of DMAc, and the obtained solid was filtered and washed with water to obtain 19.9 g of synthetic intermediate F (yield 95%).

  50 ml of acetic anhydride and 50 ml of toluene were added to 11.1 g of the synthetic intermediate F. The mixture was reacted under reflux for 10 hours. After cooling to room temperature, 9.8 g of Exemplified Compound (24) was obtained by filtration and washing with acetone (yield 94%).

Example 7
(Preparation of Exemplified Compound (25))
14.2 g of oxalyl chloride was added dropwise to a mixture of 10.0 g of 4,4′-stilbene dicarboxylic acid in 30 ml of toluene. After adding a few drops of DMF, the mixture was stirred at room temperature for 30 minutes and at 80 ° C. for 10 minutes. This reaction solution was added to a solution of 12.8 g of 5-chloroanthranilic acid in 40 ml of DMAc, and the obtained solid was filtered and washed with water to obtain 19.4 g of synthetic intermediate G (yield 96%).

  50 ml of acetic anhydride and 50 ml of toluene were added to 11.4 g of the synthetic intermediate G. The mixture was reacted under reflux for 10 hours. After cooling to room temperature, 9.9 g of Exemplified Compound (25) was obtained by filtration and washing with acetone (yield 93%).

Example 8
(Preparation of Exemplified Compound (30))
14.2 g of oxalyl chloride was added dropwise to a mixture of 10.0 g of 4,4′-stilbene dicarboxylic acid in 30 ml of toluene. After adding a few drops of DMF, the mixture was stirred at room temperature for 30 minutes and at 80 ° C. for 10 minutes. This reaction solution was added to a solution of 14.7 g of 4,5-dimethoxyanthranilic acid in 40 ml of DMAc, and the obtained solid was filtered and washed with water to obtain 19.4 g of synthetic intermediate H (yield 92%).

  50 ml of acetic anhydride and 50 ml of toluene were added to 12.4 g of the synthetic intermediate H. The mixture was reacted under reflux for 10 hours. After cooling to room temperature, 11.1 g of Exemplified Compound (30) was obtained by filtration and washing with acetone (yield 95%).

Example 9
(Preparation of exemplary compound (43))
14.2 g of oxalyl chloride was added dropwise to a mixture of 10.0 g of 4,4′-stilbene dicarboxylic acid in 30 ml of toluene. After adding a few drops of DMF, the mixture was stirred at room temperature for 30 minutes and at 80 ° C. for 10 minutes. This reaction solution was added to a DMAc 40 ml solution of 2-aminobenzamide 10.2 g, and the obtained solid was filtered and washed with water to obtain 18.0 g of synthetic intermediate I (yield 95%).

  500 ml of methanol was added to 5.0 g of the synthetic intermediate I. An aqueous solution in which 8 g of cesium carbonate was dissolved in 30 ml of water was added to this mixture. The mixture was reacted at 70 ° C. for 2 hours. After cooling to room temperature, water and hydrochloric acid were added, and the resulting solid was filtered and washed with water and acetone to obtain 4.2 g of Exemplified Compound (43) (yield 90%).

<Preparation and evaluation of sample solution>
1 mg of exemplified compound (1) was dissolved in 100 ml of ethyl acetate to prepare a sample solution. Similarly, exemplary compound (2), exemplary compound (5), exemplary compound (10), exemplary compound (18), exemplary compound (24), exemplary compound (25), exemplary compound (30), exemplary compound (43 ), As well as the comparative compounds, sample solutions were prepared. The absorbance of each sample solution was measured in a 1 cm quartz cell using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation. The cell in which this sample solution was sealed was irradiated with a xenon lamp from which the UV filter had been removed so that the illuminance was 170,000 lux, and the residual amount of each compound after irradiation for 2 days was measured. The remaining amount was calculated according to the following formula.
Residual amount (%) = 100 × (100−transmittance after irradiation) / (100−transmittance before irradiation)
The transmittance is a value measured at the maximum absorption wavelength of each compound. The results are shown in Table 1.

  As is clear from the results in Table 1, the compound of the present invention has a higher residual rate in the sample solution compared to the comparative compound (existing ultraviolet absorber having absorption in the UV-A region), and is irradiated by light irradiation. It turned out to be difficult to disassemble.

Claims (8)

A compound represented by the following general formula (1).

[L ¹ represents a substituted or unsubstituted ethenylene group or an ethynylene group.
R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1f , R ^1g and R ^1h each independently represent a hydrogen atom or a monovalent substituent. R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^1f , R ^1g and R ^1h may be connected to each other to form a ring.
X ^1a , X ^1b , X ^1c and X ^1d each independently represent a hetero atom. X ^{1a to} X ^1d may have a substituent.
Y ^1a , Y ^1b , Y ^1c and Y ^1d each independently represent a hetero atom or a carbon atom. Y ^{1a to} Y ^1d may have a substituent.
Q ¹ and Q ² each independently represents an oxygen atom, a sulfur atom or NR ^a (R ^a represents ^a hydrogen atom or a monovalent substituent).
Z ¹ and Z ² each independently represents an atomic group necessary for forming a 4- to 8-membered ring together with Y ^1a and Y ^1b or Y ^1c and Y ^1d .
n ^1a and n ^1b each independently represent an integer of 1 or more, and m ¹ represents an integer of 1 or more. ] 2. The compound according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

[L ² has the same meaning as L ^{1 in} formula (1).
R ^2a , R ^2b , R ^2c , R ^2d , R ^2e , R ^2f , R ^2g and R ^2h are respectively R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ^{1f in the} general formula (1). , R ^1g and R ^1h .
R ²ⁱ , R ^2j , R ^2k , R ^2p , R ^2q , R ^2r , R ^2s and R ^2t each independently represent a hydrogen atom or a monovalent substituent. R ²ⁱ , R ^2j , R ^2k , R ^2p , R ^2q , R ^2r , R ^2s and R ^2t may be connected to each other to form a ring.
X ^2a , X ^2b , X ^2c and X ^2d have the same ^meanings as X ^1a , X ^1b , X ^1c and X ^{1d in the} general formula (1), respectively.
n ^2a and n ^2b have the same ^meanings as n ^1a and n ^{1b in} the general formula (1), respectively. m ² has the same meaning as m ^{1 in the} general formula (1). ] 3. The compound according to claim 2, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

[L ³ has the same meaning as L ^{2 in the} general formula (2).
R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g , R ^3h , R ³ⁱ , R ^3j , R ^3k , R ^3p , R ^3q , R ^3r , R ^3s and R ^3t are respectively R ^2a , R ^2b , R ^2c , R ^2d , R ^2e , R ^2f , R ^2g , R ^2h , R ²ⁱ , R ^2j , R ^2k , R ^2p , R ^2q , R ^2r , R in the general formula (2) it is synonymous with ^2s and R ^2t.
n ^3a and n ^3b have the same ^meanings as n ^2a and n ^{2b in} the general formula (2), respectively. m ³ has the same meaning as m ^{2 in the} general formula (2). ] 4. The compound according to claim 3, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (4).

[L ⁴ has the same meaning as L ^{3 in} formula (3).
R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g , R ^4h , R ⁴ⁱ , R ^4j , R ^4k , R ^4p , R ^4q , R ^4r , R ^4s and R ^4t are respectively In the general formula (3), R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g , R ^3h , R ³ⁱ , R ^3j , R ^3k , R ^3p , R ^3q , R ^3r , R Synonymous with ^3s and R ^3t .
m ⁴ has the same meaning as m ^{3 in the} general formula (3). ] 5. The compound according to claim 4, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5).

[L ⁵ represents a substituted or unsubstituted ethenylene group.
R ^5a , R ^5b , R ^5c , R ^5d , R ^5e , R ^5f , R ^5g , R ^5h , R ⁵ⁱ , R ^5j , R ^5k , R ^5p , R ^5q , R ^5r , R ^5s and R ^5t are respectively In the general formula (4), R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g , R ^4h , R ⁴ⁱ , R ^4j , R ^4k , R ^4p , R ^4q , R ^4r , R It is synonymous with ^4s and R ^4t .
m ⁵ has the same meaning as m ^{4 in the} general formula (4). ] 6. The compound according to claim 5, wherein the compound represented by the general formula (5) is a compound represented by the following general formula (6).

[R ^6a , R ^6b , R ^6c , R ^6d , R ^6e , R ^6f , R ^6g , R ^6h , R ⁶ⁱ , R ^6j , R ^6k , R ^6p , R ^6q , R ^6r , R ^6s and R ^6t are R ^5a , R ^5b , R ^5c , R ^5d , R ^5e , R ^5f , R ^5g , R ^5h , R ⁵ⁱ , R ^5j , R ^5k , R ^5p , R ^5q , R ^5r , respectively in the general formula (5) the same meaning as R ^5s and R ^5t.
R ^6u and R ^6v each independently represent a hydrogen atom or a monovalent substituent. ]   The ultraviolet absorber which consists of a compound of any one of Claims 1-6.   A fluorescent whitening agent comprising the compound according to claim 1.