WO2009123154A1

WO2009123154A1 - Ultraviolet absorbing material

Info

Publication number: WO2009123154A1
Application number: PCT/JP2009/056571
Authority: WO
Inventors: 賀彦藤江; 直幸花木; 友昭中村; 明弘金子; 慎一市川; 優高崎; 尚御子柴; 稔彦八幡
Original assignee: 富士フイルム株式会社
Priority date: 2008-03-31
Filing date: 2009-03-30
Publication date: 2009-10-08
Also published as: JP2009263617A

Abstract

Disclosed is an ultraviolet absorbing material comprising a compound represented by the following generic formula (1). (In generic formula (1), X¹ and X² each independently represents an oxygen atom, a sulfur atom, or -NR¹⁷-, and R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ each independently represents a hydrogen atom or a monohydric substituent.)

Description

UV absorbing material

The present invention relates to an ultraviolet absorbing material containing a compound having a specific structure.

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 selected because the absorption wavelength is determined by the band gap of the compound. There are few things that have a low degree of freedom and can absorb up to 320-400 nm long wave ultraviolet (UV-A) region. Moreover, since the thing which absorbs a long wave ultraviolet-ray has absorption to a visible region, it will be 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.

So far, various organic ultraviolet absorbers have been studied. In the case of absorbing up to the long wave ultraviolet region, two methods are considered, that is, using one having a maximum absorption wavelength in the long wave ultraviolet region or increasing the concentration. However, those having the maximum absorption wavelength described in Patent Documents 4 and 5 in the long wave ultraviolet region have the disadvantage that the light resistance is poor and the absorption ability decreases with time.

In contrast, benzophenone-based and benzotriazole-based UV absorbers are relatively excellent in 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). .) 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. In order to cut to a long wavelength region with this film thickness, it is necessary to add an ultraviolet absorber at a high concentration. In such a case, there has been a problem that precipitation of the ultraviolet absorber and bleeding out due to long-term use occur. Furthermore, some benzophenone-based and benzotriazole-based UV absorbers have concerns about skin irritation and in vivo accumulation. Patent Documents 8, 9, and 10 describe 5-membered ring compounds containing two sulfur atoms.

JP-A-5-339033 JP-A-5-345639 JP-A-6-56466 JP-A-6-145387 JP 2003-177235 A JP 2005-517787 A JP-A-7-285927 JP 2007-304287 A JP 60-170842 A Japanese Patent No. 25552550

An object of the present invention is to solve the above-mentioned problems, and to provide a long-wavelength ultraviolet absorbing material that is excellent in long-wavelength ultraviolet absorbing ability and excellent in light resistance that does not change for a long time. To do.

The present inventors have repeated synthesis and evaluation in detail focusing on 1,3-benzodithiolane compounds, and in particular, 1,3-benzodithiolane-2-ylidene-3,5-pyrazolidinedione compounds are particularly preferred. It has been found that it has high fastness, and further, other azoles (for example, benzothiazole) -2-ylidene-3,5-pyrazolidinedione compounds have also been found to have high fastness. In addition, the present inventors have found that benzodithiolane-2-ylidenepyrazolidinedione compounds having specific substituents are colorless UV absorbers that hardly absorb in the visible region. As a result, it has been found that the above problems can be solved by using the ultraviolet absorber, and the present invention has been completed.
According to the present invention, the following means are provided:

(1) An ultraviolet absorbing material comprising a compound represented by the following general formula (1).

(In the general formula (1), X ¹ and X ² each independently represents an oxygen atom, a sulfur atom or —NR ¹⁷ —, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ Each independently represents a hydrogen atom or a monovalent substituent.)
(2) The ultraviolet absorbing material according to item (1), wherein X ¹ and X ² in the general formula (1) are both sulfur atoms.

(3) A compound represented by the following general formula (2).

(In the general formula (2), R ²¹ and R ²² each independently represents a substituted or unsubstituted alkyl group, and R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a monovalent substituent. Represents.)
(4) R ²³ , R ²⁴ , R ²⁵ and R ²⁶ in the general formula (2) are atomic groups necessary for the sum of Hammett's substituent constant σ _p values to be 0 or more. (3 ).

(5) A compound represented by the following general formula (3).

(In the general formula (3), R ³¹ and R ³² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted or unsubstituted. Acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted Or an unsubstituted sulfamoyl group, wherein R ³³ and R ³⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted or Unsubstituted acyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted alkoxy It represents a carbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted sulfamoyl group.)
(6) R ³¹ and R ³² in the compound represented by the general formula (3) are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted acyl group, and R ³³ and R ³⁶ are , Each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted carbamoyl group.

The ultraviolet absorbing material of the present invention exhibits an excellent effect of giving high light fastness, a high molar extinction coefficient ε and sharp absorption in the long wavelength ultraviolet region, and its ultraviolet absorbing ability does not change for a long period of time. Excellent light resistance.

The above and other features and advantages of the present invention will become more apparent from the following description with reference to the accompanying drawings as appropriate.

FIG. 1 is an absorption spectrum of the sample solution 202 produced in Example 1. FIG. 2 is an absorption spectrum of the coating film 301 produced in Example 2.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Compound represented by the general formula (1)]
First, the compound represented by the general formula (1) will be described in detail.
The compound represented by the general formula (1) is a merocyanine dye having a 3,5-pyrazolidinedione skeleton as an acidic heterocycle (the acidic heterocycle here is, for example, described by James, “The “Theory of the Photographic Process”, 4th edition, Macmillan Publishers, 1977, page 197. The merocyanine dyes used here are, for example, Nobu Okawara, Ken Matsuoka, Hirashima Tsuneaki, Kojiro Kitao, “Functional dyes”, Kodansha Scientific Co., 1992, p. 52)).
The compound represented by the general formula (1) itself is known as a sensitizing dye in a photosensitive composition of a photographic material or a printing material (see, for example, Japanese Patent No. 2552550). However, the usefulness as an ultraviolet absorber has not been reported, and it has not been possible to imagine that the compound represented by the general formula (1) exhibits particularly excellent performance as an ultraviolet absorbing material.

In the general formula (1), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom or —NR ¹⁷ —. R ¹⁷ represents a hydrogen atom or a monovalent substituent.
Preferably, X ¹ and X ² are each independently a sulfur atom or —NR ¹⁷ —, and it is particularly preferable that X ¹ and X ² are both sulfur atoms.

R ¹⁷ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and more preferably a substituted or unsubstituted 1 to 20 carbon atoms. An alkyl group, particularly preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms.

In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a monovalent substituent. These substituents are not particularly limited, but typical examples include halogen atoms, aliphatic groups [saturated aliphatic groups (alkyl groups, cycloalkyl groups, bicycloalkyl groups, bridged cyclic saturated hydrocarbon groups or spiro saturated hydrocarbons. A cyclic saturated aliphatic group containing a group), an unsaturated aliphatic group (a chain unsaturated aliphatic group having a double bond or a triple bond, such as an alkenyl group or an alkenyl group, or a cycloalkenyl group, bicyclo An alkenyl group, a cyclic unsaturated aliphatic group including a bridged cyclic unsaturated hydrocarbon group or a spiro unsaturated hydrocarbon group)], an aryl group (preferably a phenyl group which may have a substituent), hetero A ring group (preferably, the ring-constituting atom is a 5- to 8-membered ring containing an oxygen atom, sulfur atom or nitrogen atom, which may be condensed with an alicyclic ring, aromatic ring or heterocyclic ring), Group, aliphatic oxy group (typically alkoxy group), aryloxy group, acyloxy group, carbamoyloxy group, aliphatic oxycarbonyloxy group (typically alkoxycarbonyloxy group), aryloxycarbonyloxy group, amino group [aliphatic An amino group (typically an alkylamino group), an anilino group and a heterocyclic amino group], an acylamino group, an aminocarbonylamino group, an aliphatic oxycarbonylamino group (typically an alkoxycarbonylamino group), an aryloxycarbonylamino group, Sulfamoylamino group, aliphatic (typically alkyl) or arylsulfonylamino group, aliphatic thio group (typically alkylthio group), arylthio group, sulfamoyl group, aliphatic (typically alkyl) or aryl Sulfinyl group, aliphatic (typically alkyl) or arylsulfonyl group, acyl group, aryloxycarbonyl group, aliphatic oxycarbonyl group (typically alkoxycarbonyl group), carbamoyl group, aryl or heterocyclic azo group, imide group, fat Group oxysulfonyl groups (typically alkoxysulfonyl groups), aryloxysulfonyl groups, hydroxyl groups, nitro groups, carboxyl groups, and sulfo groups, and each group further has a substituent (for example, the substituents mentioned here). You may have.

Hereinafter, the above ^{^{^{R 11, R 12, R 13}}} , R 14, R 15, substituents R ¹⁶ and R ^17, further ^{^{^{R 11, R 12, R 13}}} , R 14, R 15, R ¹⁶ and R ¹⁷ The substituents that may be substituted for each substituent will be described in more detail.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable.

The aliphatic group is a linear, branched, or cyclic aliphatic group. As described above, the saturated aliphatic group includes an alkyl group, a cycloalkyl group, and a bicycloalkyl group, and has a substituent. May be. These carbon numbers are preferably 1 to 30. Examples include methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, benzyl and 2-ethylhexyl. Can do. Here, the cycloalkyl group includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms. Examples include a cyclohexyl group, a cyclopentyl group, and a 4-n-dodecylcyclohexyl group. Examples of the bicycloalkyl group include substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms, that is, monovalent groups obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Examples include a bicyclo [1.2.2] heptan-2-yl group and a bicyclo [2.2.2] octan-3-yl group. Further, it includes a tricyclo structure having many ring structures.

The unsaturated aliphatic group is a linear, branched or cyclic unsaturated aliphatic group, and includes an alkenyl group, a cycloalkenyl group, a bicycloalkenyl group, and an alkynyl group. The alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. The alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms. Examples include vinyl group, allyl group, prenyl group, geranyl group, and oleyl group. The cycloalkenyl group is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms. Examples include 2-cyclopenten-1-yl group and 2-cyclohexen-1-yl group. The bicycloalkenyl group includes a substituted or unsubstituted bicycloalkenyl group. The bicycloalkenyl group is preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. Examples include a bicyclo [2.2.1] hept-2-en-1-yl group and a bicyclo [2.2.2] oct-2-en-4-yl group. The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include an ethynyl group and a propargyl group.

The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, and an o-hexadecanoylaminophenyl group. The phenyl group which may have a substituent is preferable.

The heterocyclic group is a monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and they may be further condensed. These heterocyclic groups are preferably 5- or 6-membered heterocyclic groups, and the hetero atoms of the ring structure are preferably oxygen atoms, sulfur atoms and nitrogen atoms. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. The heterocyclic ring in the heterocyclic group includes pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, quinazoline ring, cinnoline ring, phthalazine ring, quinoxaline ring, pyrrole ring, indole ring, furan ring Benzofuran ring, thiophene ring, benzothiophene ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, isothiazole ring, benzisothiazole ring, thiadiazole ring, Examples include isoxazole ring, benzisoxazole ring, pyrrolidine ring, piperidine ring, piperazine ring, imidazolidine ring and thiazoline ring.

The aliphatic oxy group (typically an alkoxy group) includes a substituted or unsubstituted aliphatic oxy group (typically an alkoxy group), and preferably has 1 to 30 carbon atoms. Examples include methoxy group, ethoxy group, isopropoxy group, n-octyloxy group, methoxyethoxy group, hydroxyethoxy group, and 3-carboxypropoxy group.

The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group and the like. Preferably, it is a phenyloxy group that may have a substituent.

The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. Examples of the acyloxy group include formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group and the like.

The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Examples of carbamoyloxy groups include N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octyl A carbamoyloxy group can be exemplified.

The aliphatic oxycarbonyloxy group (typically an alkoxycarbonyloxy group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group.

The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group, and the like. Preferable is a phenoxycarbonyloxy group which may have a substituent.

The amino group includes an amino group, an aliphatic amino group (typically an alkylamino group), an arylamino group, and a heterocyclic amino group. The amino group is preferably a substituted or unsubstituted aliphatic amino group having 1 to 30 carbon atoms (typically an alkylamino group) or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of amino groups include, for example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, hydroxyethylamino group, carboxyethylamino group, sulfoethylamino group, 3,5-Dicarboxyanilino group, 4-quinolylamino group and the like can be mentioned.

The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. Examples of the acylamino group include formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group and the like.

The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the aminocarbonylamino group include carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group and the like. The term “amino” in this group has the same meaning as “amino” in the aforementioned amino group.

The aliphatic oxycarbonylamino group (typically an alkoxycarbonylamino group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, and an N-methyl-methoxycarbonylamino group.

The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, and an mn-octyloxyphenoxycarbonylamino group. The phenyloxycarbonylamino group which may have a substituent is preferable.

The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. Examples of the sulfamoylamino group include a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, and an Nn-octylaminosulfonylamino group.

An aliphatic (typically alkyl) or arylsulfonylamino group is a substituted or unsubstituted aliphatic sulfonylamino group having 1 to 30 carbon atoms (typically an alkylsulfonylamino group), a substituted or unsubstituted group having 6 to 30 carbon atoms. An arylsulfonylamino group (preferably a phenylsulfonylamino group which may have a substituent) is preferable. Examples thereof include a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, and a p-methylphenylsulfonylamino group.

The aliphatic thio group (typically an alkylthio group) is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. Examples of the alkylthio group include a methylthio group, an ethylthio group, and an n-hexadecylthio group.

The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of the sulfamoyl group include N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfa group. A moyl group, an N- (N′-phenylcarbamoyl) sulfamoyl) group, and the like.

The aliphatic (typically alkyl) or arylsulfinyl group is a substituted or unsubstituted aliphatic sulfinyl group having 1 to 30 carbon atoms (typically an alkylsulfinyl group), a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms (preferably Is preferably a phenylsulfinyl group which may have a substituent. Examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, and a p-methylphenylsulfinyl group.

The aliphatic (typically alkyl) or arylsulfonyl group is a substituted or unsubstituted aliphatic sulfonyl group having 1 to 30 carbon atoms (typically an alkylsulfonyl group), a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms (preferably Is preferably a phenylsulfonyl group which may have a substituent. For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl group and the like can be mentioned.

The acyl group includes a formyl group, a substituted or unsubstituted aliphatic carbonyl group having 2 to 30 carbon atoms (typically an alkylcarbonyl group), a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms (preferably a substituent). An optionally substituted phenylcarbonyl group), and a heterocyclic carbonyl group bonded to the carbonyl group by a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms is preferable. Examples thereof include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl group and the like.

The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl group and the like. A phenyloxycarbonyl group which may have a substituent is preferable.

The aliphatic oxycarbonyl group (typically an alkoxycarbonyl group) preferably has 2 to 30 carbon atoms and may have a substituent. For example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl group and the like can be mentioned.

The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl group and the like.

Examples of the aryl or heterocyclic azo group include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo group and the like.

Examples of the imide group include an N-succinimide group and an N-phthalimide group.

The aliphatic oxysulfonyl group (typically an alkoxysulfonyl group) preferably has 1 to 30 carbon atoms and may have a substituent. For example, methoxysulfonyl, ethoxysulfonyl, n-butoxysulfonyl group and the like can be mentioned.

The aryloxysulfonyl group preferably has 6 to 12 carbon atoms and may have a substituent. For example, phenoxysulfonyl, 2-naphthoxyphenyl group and the like can be mentioned.

In addition to these, there are a hydroxyl group, a cyano group, a nitro group, a sulfo group, and a carboxyl group.

Each of these groups may further have a substituent, and examples of such a substituent include the above-described substituents.

R ¹¹ and R ¹² are preferably each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted carbon group having 2 to 30 carbon atoms. An alkoxycarbonyl group, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, and particularly preferred. Is an unsubstituted alkyl group having 1 to 18 carbon atoms.

R ¹³ and R ¹⁶ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number. An aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms, a hydroxyl group, and a halogen atom, more preferably a hydrogen atom, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted acyloxy group having 2 to 20 carbon atoms, and particularly preferably a substituted or unsubstituted acyloxy group having 2 to 18 carbon atoms.

R ¹⁴ and R ¹⁵ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a halogen atom, or a cyano group. More preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom.

As for the preferred combination of substituents of the compound represented by the general formula (1), a compound in which at least one of these substituents is the preferred group is preferred, and more various substituents are preferred groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

A preferred combination is that X ¹ is a sulfur atom, X ² is a sulfur atom or —NR ¹⁷ — (R ¹⁷ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms), and R ¹¹ is substituted or unsubstituted. Is an alkyl group having 1 to 30 carbon atoms, R ¹² is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R ¹³ is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms A substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms, R ¹⁴ is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, R ¹⁵ is a hydrogen atom, and R ¹⁶ Is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms or a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms.
A more preferred combination is that X ¹ is a sulfur atom, X ² is a sulfur atom, R ¹¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ¹² is a substituted or unsubstituted carbon number. An alkyl group having 1 to 20 carbon atoms, R ¹³ is a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms or a substituted or unsubstituted acyloxy group having 2 to 20 carbon atoms, and R ¹⁴ is a hydrogen atom. A combination in which R ¹⁵ is a hydrogen atom, and R ¹⁶ is a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms or a substituted or unsubstituted acyloxy group having 2 to 20 carbon atoms.
A particularly preferred combination is that X ¹ is a sulfur atom, X ² is a sulfur atom, R ¹¹ is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and R ¹² is a substituted or unsubstituted carbon number. An alkyl group having 1 to 18 carbon atoms, R ¹³ is a substituted or unsubstituted acyloxy group having 2 to 18 carbon atoms, R ¹⁴ is a hydrogen atom, R ¹⁵ is a hydrogen atom, and R ¹⁶ is a substituted or unsubstituted alkyl group. The combination is a substituted acyloxy group having 2 to 18 carbon atoms, or a compound represented by the general formula (2) or (3).

[Compound represented by formula (2)]
The compound represented by the general formula (2) is a compound having a 1,3-benzodithiolane-2-ylidene-3,5-pyrazolidinedione skeleton, and these are merocyanine dyes. Among the compounds having a pyrazolidinedione skeleton known as a sensitizing dye as an acidic heterocyclic ring, in particular, the compound represented by the general formula (2) is useful as an ultraviolet absorber. It has not been possible to imagine that it exhibits particularly excellent performance that the absorption capacity hardly changes over time.

R ²¹ and R ²² in the general formula (2) each independently represent a substituted or unsubstituted alkyl group. The substituents that may be substituted on the respective substituents of R ²¹ and R ²² are substituted on the aforementioned substituents of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ^17. And the preferred range is also the same.

R ²¹ and R ²² are each independently preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, particularly preferably. An unsubstituted alkyl group having 1 to 18 carbon atoms.

R ²³ , R ²⁴ , R ²⁵ and R ²⁶ in the general formula (2) have the same meanings as R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ in the general formula (1), respectively, and the preferred ranges are also the same. Particularly preferred is a group of atoms necessary for the sum of Hammett's substituent constants σ _p of each of R ²³ , R ²⁴ , R ²⁵ and R ²⁶ to be 0 or more.

Hammett's substituent constant σ _p value will be described. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. This is a rule of thumb advocated by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σ _p value and a σ _m value, and these values can be found in many general books. For example, J. et al. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill) and “Areas of Chemistry”, No. 122, pages 96-103, 1979 (Nankodo), Chem. Rev. 1991, 91, 165-195.
“The Hammett substituent constant σ _p of the substituent is 0 or more” indicates that the substituent is not electron donating. That is, “the sum of Hammett's substituent constants σ _p of each of R ²³ , R ²⁴ , R ^25, and R ²⁶ is 0 or more” indicates that the overall average is not electron donating. The σ _p value is preferably 0.05 or more, more preferably 0.1 or more, and particularly preferably 0.15 or more.

Examples of substituents having Hammett's substituent constant σ _p value of 0 or more include a cyano group (0.66), a carboxyl group (—COOH: 0.45), an alkoxycarbonyl group (—COOMe: 0.45), Aryloxycarbonyl group (—COOPh: 0.44), carbamoyl group (—CONH ₂ : 0.36), alkylcarbonyl group (—COMe: 0.50), arylcarbonyl group (—COPh: 0.43), alkyl Sulfonyl group (—SO ₂ Me: 0.72), arylsulfonyl group (—SO ₂ Ph: 0.68), acyloxy (—OCOMe: 0.31), alkylsulfonyloxy (—OSO ₂ Me: 0.36) Etc. In the present specification, Me represents a methyl group, and Ph represents a phenyl group. The values in parentheses are the σp values of typical substituents in Chem. Rev. 1991, Vol. 91, pp. 165-195.

As for the preferred combination of substituents of the compound represented by the general formula (2), a compound in which at least one of these substituents is the preferred group is preferred, and more various substituents are the preferred groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

A preferred combination is that R ²¹ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, R ²² is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R ²³ is substituted or unsubstituted. An alkoxy group having 1 to 30 carbon atoms or a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms, and R ²⁴ is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. , R ²⁵ is a hydrogen atom, and R ²⁶ is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms or a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms.
A more preferred combination is that R ²¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R ²² is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ²³ is substituted or unsubstituted. Is an alkoxy group having 1 to 20 carbon atoms or a substituted or unsubstituted acyloxy group having 2 to 20 carbon atoms, R ²⁴ is a hydrogen atom, R ²⁵ is a hydrogen atom, and R ²⁶ is substituted or unsubstituted. The combination is a substituted alkoxy group having 1 to 20 carbon atoms or a substituted or unsubstituted acyloxy group having 2 to 20 carbon atoms.
A particularly preferred combination is that R ²¹ is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, R ²² is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and R ²³ is substituted or unsubstituted. In which R ²⁴ is a hydrogen atom, R ²⁵ is a hydrogen atom, and R ²⁶ is a substituted or unsubstituted acyloxy group having 2 to 18 carbon atoms.

[Compound represented by formula (3)]
R ³¹ and R ³² in the general formula (3) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted group. Acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or It represents an unsubstituted sulfamoyl group. Substituents that may be substituted on the substituents of R ³¹ and R ³² are substituted on the substituents of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ^17. And the preferred range is also the same.

R ³¹ and R ³² are each independently preferably a substituted or unsubstituted alkoxycarbonyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbamoyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number of 1 An alkylsulfonyl group having 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted acyl group having 1 to 25 carbon atoms, more preferably a substituted or unsubstituted 1 carbon atom. An alkoxycarbonyl group having 20 carbon atoms, a substituted or unsubstituted carbamoyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted acyl group having 1 to 16 carbon atoms And particularly preferably, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted acyl group having 1 to 10 carbon atoms. A.

R ³³ and R ³⁶ in the general formula (3) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted or unsubstituted Acyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted Alternatively, it represents an unsubstituted sulfamoyl group. The substituents that may be substituted on the substituents of R ³³ and R ³⁶ are substituted on the substituents of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ described above. And the preferred range is also the same.

R ³³ and R ³⁶ are each independently preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted carbon. An alkylsulfonyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, a substituted or unsubstituted sulfamoyl group having 0 to 20 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms Group, a substituted or unsubstituted acyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted carbamoyl group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms. A substituted or unsubstituted acyl group having 2 to 16 carbon atoms, or a substituted or unsubstituted carbamoyl group having 1 to 16 carbon atoms. Details, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted acyl group having 2 to 10 carbon atoms or a substituted or unsubstituted carbamoyl group having 1 to 10 carbon atoms.

As for the preferred combination of substituents of the compound represented by the general formula (3), a compound in which at least one of these substituents is the preferred group is preferred, and more various substituents are the preferred groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

A preferred combination is that R ³¹ is a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted acyl group having 1 to 16 carbon atoms, and R ³² is a substituted or unsubstituted carbon group having 1 to 16 alkyl groups, or substituted or unsubstituted acyl groups having 1 to 16 carbon atoms, wherein R ³³ is a substituted or unsubstituted alkyl group having 2 to 16 carbon atoms, substituted or unsubstituted 2 to 16 carbon atoms An acyl group, a substituted or unsubstituted carbamoyl group having 1 to 16 carbon atoms, and R ³⁶ is a substituted or unsubstituted alkyl group having 2 to 16 carbon atoms, a substituted or unsubstituted acyl group having 2 to 16 carbon atoms, substituted or unsubstituted, The combination is an unsubstituted 1 to 16 carbamoyl group.
A more preferred combination is that R ³¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted acyl group having 1 to 10 carbon atoms, and R ³² is a substituted or unsubstituted carbon number of 1 An alkyl group having ˜10, or a substituted or unsubstituted acyl group having 1 to 10 carbon atoms, wherein R ³³ is a substituted or unsubstituted alkyl group having 2 to 10 carbon atoms, substituted or unsubstituted carbon number 2 to 10 A substituted or unsubstituted 1 to 10 carbamoyl group, wherein R ³⁶ is a substituted or unsubstituted alkyl group having 2 to 10 carbon atoms, a substituted or unsubstituted acyl group having 2 to 10 carbon atoms, substituted Alternatively, it is a combination that is an unsubstituted 1 to 10 carbamoyl group.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto. In this specification, Me, Et, Pr, Bu, Hex, Ph, Ts, and Ac represent a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a phenyl group, a tosyl group, and an acetyl group, respectively. In the table, Σσ _p represents the total sum of Hammett's substituent constants of R ¹³ to R ¹⁶ . Note that the value of sigma _p values n- butoxy group, such as alkoxy group having 4 or more carbon atoms is impossible sigma _p values obtained from the literature, sigma _p value of acyloxy group value of acetyloxy group and tosyl The σ _p value of the group is a value using the value of the benzenesulfonyloxy group for convenience, and is shown in parentheses. The wavy line in the table indicates the bonding site with the benzene ring and the hetero ring in the general formula (1).

Here, the exemplified compounds 1 to 35, 40 to 45, 51 to 60, 63, and 66 to 68 are also specific examples of the compound represented by the general formula (2). Exemplified compounds 20, 24 to 59 and 61 to 66 are also specific examples of the compound represented by the general formula (3).

These compounds can be synthesized in accordance with conventionally known methods for synthesizing similar compounds (for example, Journal of Chemical Crystallography, pages 27, 997, 516, right column, line 3 to page 520, right). 15th line, Liebigs Analen der Chemie, pages 726, 106, 15th line to 109th page, 37th line, JP 491-1115, 3rd line, left line, 7th to 5th line, left column 8th line, Bioorganic & Medicinal Chemistry Letters 7, 1997, 652 page 9th line- 9th line, Journal of Organic Chemistry 43, 1978, 2153, left 2nd line to 12th line, JP 4-338759, page 4 2nd left line, 2nd line to 5th left line 2 Lines, JP-A-3-54566, page 7, left line, 6th to 8th page, left line, 10th line, Synthesis 1986/968 page, left line, 1st line to 22nd line, etc. It can synthesize | combine by the synthesis method according to.

Specifically, for example, benzodithiol, benzothiazole or benzoxazole having a nitrogen leaving group, sulfur leaving group or oxygen leaving group represented by the following general formula (4) or (5) and the following general formula (6) The compound can be obtained by reacting a pyrazolidinedione compound represented by This will be specifically described in Examples.

(R ¹³ in the general formula (4), R ^14, R ¹⁵ and R ¹⁶ are respectively synonymous with R ^13, R ^14, R ¹⁵ and R ¹⁶ in the general formula (1), and preferred ranges are also the same. Z represents a counter anion, and R ³¹ and R ³² each independently represents a substituted or unsubstituted alkyl group, and R ³¹ and R ³² may be bonded to each other to form a ring.)

(X ¹ in the general formula ^{(5), X 2, R} 13, R 14, R 15 and R ^16, X ¹ in the general formula (1), ^{^{respectively, X 2, R 13, R}} 14, R 15 and R ¹⁶ Z represents a counter anion, Y represents a sulfur atom or an oxygen atom, and R ³³ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. )

(Formula (R ¹¹ in 6) and R ¹² have the same meanings as R ¹¹ and R ¹² in the general formula (1), and preferred ranges are also the same.)

The compound represented by the above general formula (4) can be synthesized according to the method described in, for example, Angewte Chemie International Edition (Angew. Chem. Int. Ed.) 42, 24, (2003) 2765. .
The compound represented by the general formula (5) is, for example, J. Prakt. Chem. 325, 5, (1983) 811, or J ) (1958) can be synthesized according to the method described on page 854.
The compound represented by the general formula (6) is, for example, Monosh. Chem. 112, (1981) page 369, or is commercially available (for example, catalog number 322-39723 manufactured by Wako Pure Chemical Industries, Ltd.).

The compound represented by any one of the general formulas (1) to (3) is preferably used as a long wavelength ultraviolet absorber, and the maximum absorption wavelength is preferably in the range of 300 to 400 nm, more preferably. Is in the range of 340 to 390 nm, particularly preferably in the range of 365 to 385 nm.

The ultraviolet absorbing material of the present invention contains a compound (ultraviolet absorber) represented by the general formula (1).
The ultraviolet absorbing material here may be in any form as long as it contains the compound represented by the general formula (1). Examples include dispersions, solutions, mixtures, and coatings.

The ultraviolet absorbing material of the present invention can be used in the state of a dispersion dispersed in a dispersion medium. Hereinafter, the dispersion containing the compound represented by the general formula (1) will be described.

Any medium for dispersing the compound represented by the general formula (1) may be used. 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 Systems, tetrahydrofuran, heterocyclic ring system, such as pyridine, and the like. These can be used in combination at any ratio.

Examples of the dispersion medium resin 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 compound represented by the general formula (1), 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, ultraviolet absorbers, infrared absorbers, fragrances, polymerizable compounds, polymers, inorganic substances, and metals.

As a device for obtaining a dispersion containing the compound represented by the general formula (1), a high-speed stirring type disperser having a large shearing force, a disperser that gives 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 such as a dissolver, polytron, homomixer, homoblender, ket mill, or jet agitator is dispersed. A dispersion machine of a type that preferably has a speed of 2,000 to 4,000 rpm. The high-speed stirring 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 containing 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 compound represented by the general formula (1) in the dispersion of the ultraviolet absorbing material of the present invention cannot be uniquely determined because it varies depending on the purpose of use and the form of use, but depends on the purpose of use. Any concentration may be used. Preferably, the content is 0.001 to 80% by mass, more preferably 0.01 to 50% by mass, based on the total amount of the dispersion.

The ultraviolet absorbing material of the present invention can be used in the state of a solution dissolved in a liquid medium. Hereinafter, the solution containing the compound represented by the general formula (1) will be described.
Any liquid may be used for dissolving the compound represented by the general formula (1). 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 absorbing material of the present invention may contain any other compound in addition. Examples thereof include dyes, pigments, ultraviolet absorbers, infrared absorbers, fragrances, polymerizable compounds, polymers, inorganic substances, and metals. The compound other than the compound represented by the general formula (1) may not necessarily be dissolved.

The content of the compound represented by the general formula (1) in the solution of the ultraviolet absorbing material of the present invention cannot be uniquely determined because it varies depending on the purpose of use and the form of use, but is arbitrary depending on the purpose of use. It may be a concentration. Preferably, the content is 0.001 to 30% by mass, and more preferably 0.01 to 10% by mass with respect to the total amount of the solution. 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.

Further, the ultraviolet absorbing material of the present invention can be used in the state of a mixture with an arbitrary compound. Hereinafter, the mixture containing the compound represented by the general formula (1) will be described.

The mixture containing the compound represented by the general formula (1) may have any shape / state. For example, liquid, solid, liquid crystal, etc. are mentioned. In the case of solid, flat film, powder, spherical particles, crushed particles, continuous lumps, fibrous, tubular, hollow fiber, granular, plate, porous Etc. Moreover, the thing comprised by the layer form and the thing whose composition is not uniform are mentioned. Among these, a polymer material containing the ultraviolet absorbing material of the present invention is preferable.

The polymer composition is used for the preparation of the polymer material. The polymer composition is obtained by adding a compound represented by the general formula (1) to a polymer material described later.
The compound represented by the general formula (1) can be contained in the polymer substance by various methods. When the compound represented by the general formula (1) is compatible with the polymer substance, the compound represented by the formula (1) can be directly added to the polymer substance. The compound represented by the general formula (1) may be dissolved in an auxiliary solvent having compatibility with the polymer material, and the solution may be added to the polymer material. The compound represented by the general formula (1) may be dispersed in a high boiling point organic solvent or polymer, and the dispersion may be added to the polymer substance. Further, the dispersion may be coated on the surface of the polymer material.

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.
With respect to the method of adding the compound represented by the general formula (1), JP-A-58-209735, JP-A-63-264748, JP-A-4-191185, JP-A-8-272058 and British Patent No. Reference can be made to the specification of 2015017A.

The polymer substance used for the polymer composition will be described. The polymeric material is a natural or synthetic polymer or copolymer. For example, the following are mentioned.
<1> Polymers of monoolefins and diolefins 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 polymers mentioned in the above <1>, for example, 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 (eg, ethylene / norbornene, such as COC (Cyclo-Olefin Copolymer)), ethylene / 1-olefin produced in situ Olefin copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and their salts (ionomers), And terpolymers of ethylene with propylene and diene 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 (EA) ), LLDPE / EVA, LLDPE / 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 homopolymers and copolymers of <1> to <4> can have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; 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, especially 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; where 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> prepared by hydrogenating a hydrogenated aromatic polymer, especially atactic polystyrene, derived from hydrogenation of the polymer referred to in <6> above, often referred to as polyvinylcyclohexane (PVCH) Includes cyclohexylethylene (PCHE).

<6c> Hydrogenated aromatic polymer derived from the 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, eg styrene to polybutadiene, styrene to polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; styrene and acrylonitrile (or methacrylonitrile) to polybutadiene; Styrene, acrylonitrile and methyl methacrylate; styrene and maleic anhydride to polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide to polybutadiene; styrene and maleimide to polybutadiene; styrene and alkyl acrylate or methacrylate to polybutadiene; ethylene / propylene / dienter Styrene and acrylonitrile as polymer; polyalkyl acrylate Known as styrene and acrylonitrile to acrylate or polyalkylmethacrylate; styrene / acrylonitrile to acrylate / butadiene copolymer, 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 with impact resistance improved with butylacrylate.

<10> Copolymers of the monomers mentioned in the above <9> with each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymer, acrylonitrile / alkyl acrylate copolymer, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymer 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 use, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide: and polyamides and polyolefins, olefin copolymers, ionomers or chemically bonded as described above 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 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 acrylate, urethane acrylate or polyester acrylate.

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

<27> Crosslinked epoxy resins derived from aliphatic, alicyclic, 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, rubber, 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, such as mineral oil, animal and vegetable fats, oils and waxes, or synthetic esters (for example phthalate, adipate, phosphate or trimellitate) 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> Polyketimine combined with unsaturated acrylic polyacetoacetate resin or 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 containing 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 solid content melamine resin such as LSE-4103 (trade name, 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.

In addition to the above-described polymer substance and the compound represented by the general formula (1), the polymer material of the ultraviolet absorbing material of the present invention includes an antioxidant, a light stabilizer, a processing stabilizer, and aging as necessary. You may contain suitably arbitrary additives, such as an inhibitor and a compatibilizing agent.

Moreover, the ultraviolet-absorbing material of the present invention may be used in combination with two or more compounds represented by the general formula (1) (ultraviolet absorbers) having different structures as necessary. You may use together the compound represented by 1), and 1 or more types of ultraviolet absorbers which have another structure. When two kinds (preferably three kinds) 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 the general formula (1) can be used. For example, supervised by Shinichi Daikatsu, “Development of Polymer Additives and Environmental Measures” (CMC Publishing, 2003) Chapter 2, edited by Toray Research Center Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999) 2.3.1, and the like. For example, triazine, benzotriazole, benzophenone, merocyanine, cyanine, dibenzoylmethane, cinnamic acid, acrylate, benzoate oxalate diamide, etc., known as UV absorber structures Compounds. For example, Fine Chemical, May 2004, 28-38 pages, published by Research Department of Toray Research Center “New Development of Functional Additives for Polymers” (Toray Research Center, 1999) 96-140 pages, Junichi Okachi Supervised by “Development of Polymer Additives and Environmental Measures” (CM Publishing, 2003), pages 54-64.

Preferred are benzotriazole, benzophenone, salicylic acid, acrylate and triazine compounds. More preferred are benzotriazole, benzophenone and triazine compounds. Particularly preferred are benzotriazole and triazine compounds.

The benzotriazole-based compound preferably has an effective absorption wavelength of about 270 to 380 nm. Representative examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) 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′-dodecyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- ( 2'-hydroxy-5 '-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) Nzotriazole, 2- (2′-hydroxy-3 ′-(3,4,5,6-tetrahydrophthalimidylmethyl) -5′-methylbenzyl) phenyl) benzotriazole, 2- (3′-sec- Butyl-5′-t-butyl-2′-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-bis- (α, α-dimethylbenzyl) -2′-hydroxyphenyl) benzotriazole, 2- ( 3′-tert-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3′-tert-butyl-5 ′-[2- ( 2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5 -(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3′-t-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3′-t-butyl-5 ′-[2- (2-ethylhexyloxy) ) Carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-t-butyl-2'-hydroxy -5 ′-(2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2′-methylene-bis [4- 1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl phenol] and the like.

The triazine compound preferably has an effective absorption wavelength of about 270 to 380 nm. Representative examples include 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-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, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- ( , 4-Dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2 , 4-Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2 -(2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl)- 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2 4-Dimethyl) -1,3,5-triazine, 2- [2-Hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl)- 1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 , 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl) -1,3,5-triazine, 2- (2-hydroxy Phenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxy- Propyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- (2-ethylhexyl) oxy) phenyl-4,6- Examples include di (4-phenyl) phenyl-1,3,5-triazine.

The benzophenone compound is preferably a compound having an effective absorption wavelength of about 270 to 380 nm. Representative examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 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'-hex Ruoxycarbonylbenzophenone, 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 can be mentioned.

The salicylic acid compound is preferably a compound having an effective absorption wavelength of about 290 to 330 nm. Representative examples include phenyl salicylate, 4-t-butylphenyl salicylate, 4-octylphenyl salicylate, dibenzoyl resorcinol, bis (4-t-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-t-butylphenyl Examples include 3,5-di-t-butyl-4-hydroxysalicylate, hexadecyl, 3,5-di-t-butyl-4-hydroxysalicylate, and the like.

The acrylate compound is preferably a compound having an effective absorption wavelength of about 270 to 350 nm. Representative examples include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl 2-cyano-3,3-diphenyl acrylate, isooctyl 2-cyano-3,3-diphenyl acrylate, hexadecyl 2-cyano-3 -(4-methylphenyl) acrylate, methyl 2-cyano-3-methyl-3- (4-methoxyphenyl) cinnamate, butyl 2-cyano-3-methyl-3- (4-methoxyphenyl) cinnamate, methyl 2- Carbomethoxy-3- (4-methoxyphenyl) cinnamate 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, N-(2-carbomethoxy-2-cyanovinyl) -2-methyl-indoline, and the like.

The oxalic acid diamide compound preferably has an effective absorption wavelength of about 250 to 350 nm. Representative examples include 4,4′-dioctyloxyoxanilide, 2,2′-dioctyloxy-5,5′-di-t-butyloxanilide, 2,2′-didodecyloxy-5,5 '-Di-t-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2' -Ethyl oxanilide, 2-ethoxy-2'-ethyl-5,4'-di-t-butyl oxanilide and the like.

The ultraviolet absorbing material of the present invention may further contain a light stabilizer and an antioxidant.
Preferable examples of the light stabilizer and the antioxidant include compounds represented by JP-A No. 2004-117997. Specifically, compounds described in JP-A No. 2004-117997, p29 middle stage, paragraph numbers [0071] to [0111] are preferable. The compounds represented by general formula (TS-I), general formula (TS-II), general formula (TS-IV) and general formula (TS-V) described in paragraph [0072] are particularly preferred.

Although the content of the compound represented by the general formula (1) in the ultraviolet absorbing material of the present invention differs depending on the purpose of use and the form of use, it cannot be uniquely determined, but those skilled in the art can perform some tests. Can be easily determined. Preferably, the content is 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass with respect to the total amount of the material. Moreover, content of ultraviolet absorbers other than the compound represented by the said General formula (1) can be suitably determined according to the objective of this invention.

In the present invention, although a sufficient ultraviolet shielding effect can be obtained practically with only an ultraviolet absorber, a white pigment having a strong hiding power, such as titanium oxide, may be used in combination when more strictness is required. 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 optical brightener include those commercially available and those described in JP-A-2002-53824.

Examples of the ultraviolet absorbing material of the present invention include packaging materials, containers, paints, coating films, inks, fibers, building materials, recording media, image display devices, solar cell covers, and glass coatings containing the ultraviolet absorbing material of the present invention. Can be used. Moreover, these manufacturing methods can be manufactured according to the cited reference in the example explained in full detail below.

The packaging material including the ultraviolet absorbing material of the present invention will be described. The packaging material containing the ultraviolet absorbing material of the present invention may be any packaging material. For example, thermoplastic resins described in JP-A-8-208765, polyvinyl alcohol described in JP-A-8-151455, polyvinyl chloride described in JP-A-8-245849, and JP-A-10-168292. Polyesters described in JP-A No. 2004-285189, heat-shrinkable polyesters described in JP-A No. 2001-323082, styrene resins described in JP-A No. 10-298397, JP-A No. 11-315175, Examples thereof include polyolefins described in JP-A Nos. 2001-26081 and 2005-305745, and ROMPs described in JP-T-2003-524019. For example, a resin having an inorganic vapor-deposited thin film layer described in JP-A-2004-50460 and JP-A-2004-243684 may be used. For example, paper coated with a resin containing an ultraviolet absorber described in Japanese Patent Application Laid-Open No. 2006-240734 may be used.

The packaging material including the ultraviolet absorbing material of the present invention may be any packaging material such as foods, beverages, drugs, cosmetics and personal care products. For example, for food packaging described in JP-A-11-34261, JP-A-2003-237825, colored liquid packaging described in JP-A-8-80928, and 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-2006-217781, and JP-A-7-287353 Photosensitive material packaging, photographic film packaging described in JP-A No. 2000-56433, UV-curable ink packaging described in JP-A No. 2005-178832, JP-A No. 2003-200966, JP-A No. 2006-323339 The shrink label etc. which are described in the gazette are mentioned.

The packaging material containing the ultraviolet absorbing material 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 including the ultraviolet absorbing material 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 other performances. May be. For example, those having gas barrier properties described in Japanese Patent Application Laid-Open No. 2002-160321, those containing an oxygen indicator described in, for example, Japanese Patent Application Laid-Open No. 2005-156220, and those described in, for example, Japanese Patent Application Laid-Open No. 2005-146278. And a combination of an ultraviolet absorber and an optical brightener.

The packaging material containing the ultraviolet absorbing material of the present invention may be manufactured 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 Examples thereof include a method of coating on a substrate film described in JP-A-9-142539, and a method of dispersing an ultraviolet absorber in an adhesive described in JP-A-9-157626.

The container containing the ultraviolet absorbing material of the present invention will be described. The container containing the ultraviolet absorbing material of the present invention may be a container made of any kind of polymer. 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 -238857, a polyethylene naphthalate container described in JP-A-2001-88815, a cyclic olefin-based resin composition container described in JP-A-7-216152, JP-A-2001-2001 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, a paper container containing a resin described in Japanese Patent Application Laid-Open Nos. 2001-114262 and 2001-213427 may be used. 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 use of the container containing the ultraviolet absorbing material of the present invention may contain any foods, beverages, drugs, cosmetics, personal care products, shampoos and the like. For example, liquid fuel storage containers described in JP-A-5-139434, golf ball containers described in JP-A-7-289665, foods 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-8-155007, beverage container described in JP-A-8-324572, JP-A-2006-298456 JP-A-9-86570, oil-based food containers, JP-A-9-113494, analytical reagent solution containers, JP-A-9-239910, instant noodle containers, JP-A-11- No. 180474, JP-A-2002-68322, JP-A-2005-278678, JP-A-11-2765 No. 0 pharmaceutical container, high purity chemical liquid container described in JP-A-11-290420, JP-A-2001-106218 liquid agent container, JP-A-2005-178832 UV curable ink containers, plastic ampules described in WO 04/93775 pamphlet, and the like can be mentioned.

The container containing the ultraviolet absorbing material 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. Also good. For example, an antibacterial container described in JP-A-10-237312, a flexible container described in JP-A-2000-152974, a dispenser container described in JP-A-2002-264979, such as JP-A-2005-255736, for example. Examples include biodegradable containers described in the publication.

The container containing the ultraviolet absorbing material of the present invention may be manufactured using any method. For example, a two-layer stretch blow molding method described in JP-A No. 2002-370723, a multilayer coextrusion blow molding method described in JP-A No. 2001-88815, and a container described in JP-A No. 9-241407 are provided outside the container. A method for forming an ultraviolet absorbing layer, JP-A-8-91385, JP-A-9-48935, JP-A-11-514387, JP-A-2000-66603, JP-A-2001-323082, 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 absorbing material of the present invention will be described. The paint containing the ultraviolet absorbing material of the present invention may be a paint comprising any component. 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 absorbing material of the present invention may be any application. For example, UV shielding paints described in JP-A-7-26177, JP-A-9-169950, JP-A-9-221163, JP-A-2002-80788, and UV-rays described in JP-A-10-88039. Near-infrared shielding coating, electromagnetic wave shielding coating described in JP-A-2001-55541, clear coating described in JP-A-8-81643, metallic coating 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 No. 2002-294165, JP-A No. 2000-273362, JP-A No. 2001-279189, Powder coating described in JP-A No. 2002-271227, and aqueous coating described in JP-A No. 2001-9357 Paint, water-based metallic paint, water-based clear paint, paint for top coating used in automobiles, buildings and civil engineering products described in JP-A-2001-316630, curable paint described in JP-A-2002-356655, Coating film forming composition used for plastic materials such as automobile bumpers described in JP-A No. 2004-937, metal plate paint described in JP-A No. 2004-2700, and JP-A No. 2004-169182 Cured gradient coating film, coating material for electric wires described in JP-A-2004-107700, automotive repair coating described in JP-A-6-49368, JP-A-2002-38084, JP-A-2005-307161 Anionic electrodeposition coatings described in JP-A-5-78606, JP-A-5-185031, JP-A-10-140089 No. 2000-509082, JP-T 2004-520284, pamphlet of WO 2006/097201, pamphlet for coated steel sheet described in JP-A-6-1945, JP-A-6-313148 Stainless steel paints described in Japanese Patent Publication No. 7-3189, lamp insect-proof paints disclosed in Japanese Patent Laid-Open No. 7-3189, ultraviolet curable paints described in Japanese Patent Laid-Open No. 7-82454, and antibacterials described in Japanese Patent Laid-Open No. 7-118576 Anti-fatigue paint described in JP-A No. 2004-217727, anti-fog paint described in JP-A No. 2005-314495, super-weather resistant paint described in JP-A No. 10-298493, Gradient paint described in Japanese Laid-Open Patent Application No. 9-241534, photocatalyst paint described in Japanese Patent Application Laid-Open No. 2002-235028, 109, paint for peeling concrete described in JP-A-6-346022, anticorrosion paint described in JP-A 2002-167545, protective paint described in JP-A-8-324576 A water-repellent protective coating described in JP-A-9-12924, a sheet glass scattering-preventing coating described in JP-A-9-157581, an alkali-soluble protective coating described in JP-A-9-59539, Aqueous temporary protective coating composition described in JP-A-2001-181558, floor coating described in JP-A-10-183057, emulsion coating described in JP-A-2001-115080, JP-A-2001-262856 Two-component water-based paint described in JP-A-9-263729, one-component paint described in JP-A-9-263729, and JP-A-2001-288410. UV curable coatings, electron beam curable coating compositions described in JP-A-2002-69331, thermosetting coating compositions described in JP-A-2002-80781, and JP-T-2003-525325 Water-based paint for baking lacquer, powder paint and slurry paint described in JP-A No. 2004-162021, repair paint described in JP-A No. 2006-233010, powder described in JP-T-11-51489 Examples thereof include paint water dispersions, plastic coatings described in JP-A Nos. 2001-59068 and 2006-160847, and electron beam curable coatings described in JP-A No. 2002-69331.

The coating material containing the ultraviolet absorbing material of the present invention is generally composed of a coating material (including a transparent resin component as a main component) and an ultraviolet absorber, but preferably a composition of 0 to 20% by mass of the ultraviolet absorber 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. Drying after application varies depending on the paint components, but it is preferably performed at room temperature to 120 ° C. for about 10 to 90 minutes.

The coating film containing the ultraviolet absorbing material of the present invention is a coating film formed using the above-described coating material containing the ultraviolet absorbing material of the present invention.

The ink containing the ultraviolet absorbing material of the present invention will be described. The ink containing the ultraviolet absorbing material of the present invention may be any form of ink. Examples thereof include dye ink, pigment ink, water-based ink, and oil-based ink. Moreover, you may use for any use. For example, the screen printing ink described in JP-A-8-3502, the flexographic printing ink described in JP-T-2006-521941, the gravure printing ink described in JP-T-2005-533915, and JP-T-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 Unexamined Patent Publication 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, and 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, and 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 absorbing material 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 can be mentioned. .

The fiber containing the ultraviolet absorbing material of the present invention will be described. The fiber containing the ultraviolet absorbing material of the present invention may be a fiber made of any kind of polymer. For example, JP-A-5-117508, JP-A-7-119036, JP-A-7-196661, JP-A-8-188921, JP-A-10-237760, JP-A-2000-54287, Polyester fibers described in JP-A-2006-299428 and JP-A-2006-299438, polyphenylene sulfide fibers described in JP-A-2002-322360 and JP-A-2006-265770, JP-A-7-76580 Polyamide fibers described in JP 2001-348785 A, JP 2003-41434 A, JP 2003-239136 A, epoxy fibers described in WO 03/2661 pamphlet, and JP 10-251981 A. Aramid fiber, JP-A-6-22881 Polyurethane fiber according to JP-like cellulose fibers described in JP-T-2005-517822.

The fiber containing the ultraviolet absorbing material of the present invention may be produced by any method. For example, as described in JP-A-6-228818, a polymer containing an ultraviolet absorber in advance may be processed into a fiber, for example, JP-A-5-9870, JP-A-8-188921, As described in JP-A-10-1587, a fiber processed may be treated with a solution containing an ultraviolet absorber. The treatment may be performed using a supercritical fluid as described in JP-A-2002-212884 and JP-A-2006-16710.

The fiber containing the ultraviolet absorbing material 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 No. 2004-11062, artificial leather described in JP-A No. 11-302982, insect-proof mesh sheet described in JP-A No. 7-289097, construction described in JP-A No. 10-1868 Mesh sheet, carpet described in JP-A-5-256464, moisture-permeable and waterproof sheet described in JP-A-5-193037, nonwoven fabric described in JP-A-6-114991, and JP-A-11-247028 No. 2000, No. 2000-144583, and a sheet-like material made of the fiber described in JP-A No. 2000-144583. Refreshing garments described in Japanese Patent Laid-Open No. 703, moisture-permeable waterproof sheets described in Japanese Patent Laid-Open No. 5-193037, flame retardant artificial suede-like structures described in Japanese Patent Laid-Open No. 7-18484, and Japanese Patent Laid-Open No. 8-41785 Resin tarpaulins described in Japanese Laid-Open Patent Publication No. 8-193136, film agents, exterior wall materials, agricultural houses, nets for building materials described in Japanese Patent Laid-Open No. 8-269850, meshes, Japanese Patent Laid-Open No. 8-280633 Filter substrate described in Japanese Patent No. 9-57889, an antifouling film agent described in Japanese Patent Application Laid-Open No. 9-57889, a mesh fabric described in Japanese Patent Application Laid-Open No. 9-137335, a land net, and Underwater net, extra fine fibers described in JP-A-11-247027 and JP-A-11-247028, JP-A-7-310283, special table 2003-528 74, the fabric for airbags described in JP-A-2001-30861, JP-A-7-324283, JP-A-8-20579, and JP-A-2003-147617. And the ultraviolet ray absorbing fiber product described.

The building material containing the ultraviolet absorbing material of the present invention will be described. The building material containing the ultraviolet absorbing material of the present invention may be a building material made of any kind of polymer. For example, the vinyl chloride type described in JP-A-10-6451, the olefin type described in JP-A-10-16152, the polyester type described in JP-A-2002-161158, and JP-A-2003-49065. Examples thereof include polyphenylene ethers described above and polycarbonates described in JP-A No. 2003-160724.

The building material containing the ultraviolet absorbing material of the present invention may be manufactured by any method. For example, it may be formed into a desired shape using a material containing an ultraviolet absorber as described in JP-A-8-269850, or an ultraviolet absorber as described in JP-A-10-205056, for example. For example, a coating layer using an ultraviolet absorber may be formed as described in JP-A-8-151457, for example, JP-A-2001-172531. And may be formed by painting a paint containing an ultraviolet absorber.

The building material containing the ultraviolet absorbing material 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-8-197511, The roofing material for building materials described in JP-A-9-183159, the antibacterial building material described in JP-A-11-236734, the base material for building material described in JP-A-10-205056, and JP-A-11-300880 Antifouling building materials described in JP-A-2001-9811, flame-retardant materials described in JP-A-2001-98231, ceramic-based building materials described in JP-A-2001-172531, and decorative building materials described in JP-A-2003-328523 Painted articles for building materials described in JP-A-2002-226774, JP-A-10-6451, JP-A-10-16152, JP-A-2006-306020 Cosmetic material described in Japanese Patent Publication No. 8-269850, a building material net described in Japanese Patent Laid-Open No. 8-277850, a moisture-permeable waterproof sheet for building material described in Japanese Patent Laid-Open No. 9-277414, and a building described in Japanese Patent Laid-Open No. 10-1868. Mesh sheet for construction, film for building material described in JP-A-7-269016, film for covering described in JP-A-2003-211538, JP-A-9-239921, JP-A-9-254345, A covering material for building materials described in Kaihei 10-44352, an adhesive composition for building materials described in JP-A-8-73825, a civil engineering structure described in JP-A-8-207218, No. 82608, a coating material for walking paths, a sheet-like photocurable resin described in JP-A-2001-139700, and JP-A-5-253559. A protective coating for wood, a cover for a pushbutton switch described in JP-A-2005-2941780, a bonding sheet agent described in JP-A-9-183159, a base material for building material described in JP-A-10-44352, Wallpapers described in JP 2000-226778 A, polyester films for covering described in JP 2003-111538 A, polyester films for covering molded members described in JP 2003-111606 A, JP 2004-3191 A The flooring described in the gazette can be used.

The recording medium containing the ultraviolet absorbing material of the present invention will be described. The recording medium containing the ultraviolet absorbing material of the present invention may be any recording medium as long as it contains the compound represented by the general formula (1) (ultraviolet absorber). For example, in JP-A-9-309260, JP-A-2002-178625, JP-A-2002-212237, JP-A-2003-266926, JP-A-2003-266927, and JP-A-2004-181813 Inkjet recording media described in Japanese Patent Application Laid-Open No. 8-108650 Image-receiving medium for thermal transfer ink, Sublimation transfer image-receiving sheet described in Japanese Patent Application Laid-Open No. 10-203033, Image recording medium described in Japanese Patent Application Laid-Open No. 2001-249430, Thermal recording medium described in JP-A-8-258415, Reversible thermal 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 including the ultraviolet absorbing material of the present invention will be described. Any image display device including the ultraviolet absorbing material of the present invention may be used. For example, an image display device using an electrochromic element described in JP-A-2006-301268, an image display device 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 absorbing material of the present invention may be one in which an ultraviolet absorbing layer is formed in a laminated structure described in, for example, Japanese Patent Application Laid-Open No. 2000-223271, or a circular polarizing plate described in, for example, Japanese Patent Application Laid-Open No. 2005-189645 is necessary. A member containing an ultraviolet absorber may be used.

A solar cell cover including the ultraviolet absorbing material of the present invention will be described. 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. Further, in a dye-sensitized solar cell, as described in JP-A-2006-282970, a metal oxide semiconductor that is activated by light (particularly ultraviolet rays) and becomes active 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 including the ultraviolet absorbing material 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.

The solar cell cover including the ultraviolet absorbing material of the present invention may be manufactured by any method. For example, an ultraviolet absorbing layer described in JP-A-11-40833 may be formed, or layers each containing an ultraviolet absorber described in JP-A-2005-129926 may be laminated, or JP2000-2000A It 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 absorbing material of the present invention may have any shape. Films and sheets described in JP-A-2000-91610 and JP-A-11-261085, for example, a laminated film described in JP-A-11-40833, a 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.

The glass containing the ultraviolet absorbing material of the present invention and the glass film will be described. Any form may be sufficient as the glass and glass film containing the ultraviolet-absorbing material of this invention. Moreover, you may use for any use. For example, heat ray blocking glass described in JP-A-5-58670 and JP-A-9-52738, wind glass described in JP-A-7-48145, coloring described in JP-A-8-157232, JP-A-10-45425, and JP-A-11-217234. Glass, UV sharp-cut glass for high-intensity light sources such as mercury lamps and metal halide lamps described in JP-A-8-59289, frit glass described in JP-A-5-43266, UV-blocking glass for vehicles described in JP-A-5-163174, Colored heat ray absorbing glass described in 5-270855, fluorescent whitening ultraviolet absorbing heat insulating glass described in JP-A-6-316443, ultraviolet heat ray-shielding glass for automobiles described in JP-A-7-237936, exterior packaging described in JP-A-7-267682 Stained glass, water-repellent ultraviolet red described in JP-A-7-291667 Line-absorbing glass, glass for vehicle head-up display device described in JP-A-7-257227, light control and heat-insulating multi-layer window described in JP-A-7-232938, JP-A-5-78147, JP-A-7-61835, JP-A-8 -217486, UV-infrared cut glass described in JP-A-6-127974, UV-cut glass described in JP-A-7-53241, UV-infrared absorbing glass for windows described in JP-A-8-165146, UV-rays for windows described in JP-A-10-17336 Blocking antifouling film, translucent panel for cultivation room described in JP-A-9-67148, UV-infrared absorbing low-transmitting glass described in JP-A-10-114540, low-reflectance low-transmitting glass described in JP-A-11-302037, JP An edge light device described in 2000-16171, a rough surface-formed plate glass described in Japanese Patent Application Laid-Open No. 2000-44286, Laminated glass for display as described in 2000-103655, glass with a conductive film as described in JP-A-2000-133987, anti-glare glass as described in JP-A-2000-191346, UV-infrared absorbing medium transmission glass as described in JP-A-2000-7371, A window glass for privacy protection described in JP 2000-143288, a glass for anti-fogging vehicle described in JP 2000-239045, a glass for paving material described in JP 2001-287777 A, and a glass described in JP 2002-127310 A. Glass plate having water droplet adhesion preventing property and heat ray blocking property, ultraviolet / infrared absorbing bronze glass described in JP-A-2003-342040, laminated glass described in W001 / 0197748, glass with ID identification function described in JP-A-2004-43212, JP-A-2005 Optics for PDP described in -70724 Examples thereof include a filter and a skylight described in JP-A-2005-105751. The glass containing the ultraviolet absorbing material of the present invention may be made by any method.

Other examples of use include a light source cover for a lighting device described in JP-A-8-102296, JP-A-2000-67629, and JP-A-2005-353554, JP-A-5-272076, and 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 , And window outside pasting described in JP-A-2002-36441 Hard coating for window covering, window covering film described in JP-A-10-250004, high-definition anti-glare hard-coating film described in JP-A-2002-36452, antistatic described in JP-A-2003-39607 Hard coat film, transparent hard coat film described in JP-A No. 2004-114355, anti-counterfeit book described in JP-A No. 2002-113937, and purpuration of turf described in JP-A No. 2002-293706 Agent, sealing agent for resin film sheet bonding described in JP-A-2006-274179, light guide described in JP-A-2005-326661, rubber coating agent described in JP-A-2006-335855, Agricultural covering materials and special tables described in Kaihei 10-34841 and JP-A 2002-114879 Dyeing candles described in JP-A-2004-532306 and JP-T-2004-530024, fabric rinsing compositions described in JP-T-2004-525273, prism sheet described in JP-A-10-287804, JP Protective layer transfer sheet described in JP-A-2000-71626, photocurable resin product described in JP-A-2001-139700, floor sheet described in JP-A-2001-159228, JP-A-2002-189415 A light-shielding printed label described in JP-A No. 2002-130591, an oil supply cup described in JP-A No. 2002-130591, an article coated with a hard coating film described in JP-A No. 2002-307619, and an intermediate transfer described in JP-A No. 2002-307845 Recording medium, artificial hair described in JP-A-2006-316395, pamphlet of WO99 / 29490 Lett, low-temperature heat-shrinkable film for labels described in JP-A No. 2004-352847, fishing equipment described in JP-A No. 2000-224942, microbeads described in JP-A No. 8-208976, JP-A No. 8- No. 318592, a precoated metal plate described in JP 2005-504735 A, a thin film described in JP 2005-504735 A, a heat shrinkable film described in JP 2005-105032 A, an in-mold described in JP 2005-37642 A Labels for molding, projection screens described in JP-A-2005-55615, JP-A-9-300537, JP-A-2000-25180, JP-A-2003-19776, JP-A-2005-74735 Decorative sheet, hot-melt adhesive described in JP-A-2001-207144 Adhesives described in JP-T-2002-543265, JP-A-2002-543266, and US Pat. No. 6,225,384, electrodeposition coats and base coats described in JP-A No. 2004-35283, and JP-A-7-268253 Wood surface protection described in Japanese Patent Publication No. 2003-253265, Japanese Patent Publication No. 2005-105131, Japanese Patent Publication No. 2005-300962, and Japanese Patent No. 3915339. Optical glass, a flashlight described in JP-A-2005-304340, a touch panel described in JP-A-2005-44154, a sealing agent for resin film sheet bonding described in JP-A-2006-274197, and JP-A-2006 Polycarbonate film coating described in JP-A-89697, JP 2000-23 044 optical fiber tape described in Japanese, and the like solid wax described in JP-T-2002-527559.

The ultraviolet absorbing material of the present invention can also be used as a cosmetic preparation. Next, the use of the ultraviolet absorbing material of the present invention as a cosmetic preparation will be described in detail.
Cosmetic preparations containing the UV-absorbing material according to the invention can be used, for example, in the form of creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat compositions, stick formulations, powders or ointments. As auxiliary agent and additive, mild surfactant, super fat agent, pearl essence wax, consistency regulator, thickener, polymer, silicone compound, fat, wax, stabilizer, active ingredient of biological origin, Odor active ingredient, anti-dandruff agent, film forming agent, swelling agent, further UV light protection factor, antioxidant, hydrotropic agent, preservative, insect repellent, self-tanning agent, solubilizer, perfume oil, coloring agent, Additional antibacterial agents may be included.

Substances suitable for use as the overfat agent include, for example, lanolin and lecithin, polyoxyethylenated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the fatty acid alkanolamides simultaneously Can act as a bubble stabilizer.

Examples of said suitable mild surfactants, in other words surfactants which are particularly well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono and / or di-alkyl sulfos. Succinate, fatty acid isethionate, fatty acid sarcosinate, fatty acid tauride, fatty acid glutamate, α-olefin sulfonic acid, ether carboxylic acid, alkyl oligoglucoside, fatty acid glucamide, alkyl amide betaine and / or protein fatty acid condensation product, The fatty acid condensation product is preferably based on wheat protein.

Examples of the pearl essence wax include: alkylene glycol ester, especially ethylene glycol distearate; fatty acid alkanolamide, especially coco fatty acid diethanolamide; partial glyceride, especially stearic acid monoglyceride; unsubstituted or hydroxy-substituted polycarboxylic acid Of esters with fatty alcohols having 6 to 22 carbon atoms, in particular long-chain esters of tartaric acid; fatty substances such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers having a total number of at least 24 carbon atoms and Fatty carbonates, in particular laurone and distearyl ether; fatty acids such as stearic acid, hydroxystearic acid or behenic acid, 12-22 olefin epoxides having 12-22 carbon atoms Fatty alcohols or ring-opening products with polyols having from 2 to 15 carbon atoms and 2 to 10 hydroxy groups having a carbon atom, as well as mixtures thereof are preferred.

Examples of the consistency adjusting agent include fatty alcohols or hydroxy fatty alcohols having 12 to 22, preferably 16 to 18, carbon atoms, partial glycerides, fatty acids and hydroxy fatty acids. Mixtures of such materials with alkyl oligoglucosides of the same chain length and / or fatty acid N-methylglucamide or polyglycerol poly-12-hydroxystearate are preferred. Suitable said thickeners are, for example, Aerosil type (hydrophilic silicic acid), polysaccharides, in particular xanthan gum, guar gum, agar, alginate and tyroses, carboxymethylcellulose and hydroxymethylcellulose, and also relatively high molecular weight Polyethylene glycol fatty acid mono- and di-esters, polyacrylic acid (eg Carbopol® from Goodrich or Synthalen® from Sigma), polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone, surfactants E.g. polyoxyethylene fatty acid glycerides, fatty acid esters with polyol esters such as pentaerythritol or trimethylolpropane, restriction Polyoxyethylene fatty alcohol ethers having a homologue distributions, alkyl oligoglucosides, as well as sodium chloride or an electrolyte such as ammonium chloride.

As examples of such polymers, suitable cationic polymers are, for example, cationic cellulose derivatives, such as quaternized hydroxymethylcellulose, cationic starch, diallyl, available under the name polymer JR400® from Amerchol. Copolymers of ammonium salts and acrylamides, quaternized vinyl pyrrolidone / vinyl imidazole polymers such as Luvicat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides such as Lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat® L / Gruenau), quaternized wheat polypeptide, polyethyleneimine, cationic silicone polymers such as amide methicone, adipic acid and Copolymers with methylaminohydroxypropyldiethylenetriamine (Cartaretin® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), eg FR-A-2252840 Polyaminopolyamides and their crosslinked water-soluble polymers as described, optionally dispersed as microcrystals, for example, cationic chitin derivatives of quaternized chitosan; dihaloalkyls such as dibromobutane, bisdialkylamines such as bisdimethyl Condensation products with amino-1,3-propane, cationic guar gums such as Cagelane's Jaguar (R) C-17, Jaguar (R) C-16, quaternized ammonium salt poly Chromatography, for example Miranol of Mirapol (registered trademark) A-15, Mirapol (registered trademark) AD-1, Mirapol (registered trademark) is AZ-1.

Examples of anionic, zwitterionic, amphoteric and nonionic polymers include vinyl acetate / crotonic acid copolymer, vinyl pyrrolidone / vinyl acrylate copolymer, vinyl acetate / butyl maleate / isobornyl acrylate copolymer Polymers, methyl vinyl ether / maleic anhydride copolymers and their esters, polyacrylic acid crosslinked with uncrosslinked polyacrylic acid and polyols, acrylamidopropyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / methacrylic acid tert-Butylaminoethyl / 2-hydroxypropyl methacrylate copolymer, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, vinyl pyrrolidone / dimethylaminoethyl methacrylate / vinyl cap Terpolymer lactam, and cellulose ethers and silicones is preferably induced by case.

Suitable silicone compounds include, for example, dimethylpolysiloxane, methylphenylpolysiloxane, cyclic silicone, and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and / or alkyl-modified. The silicone compound may be in liquid or resin form at room temperature. Also suitable is simethicone, which is a mixture of dimethicone having an average chain length of 200 to 300 dimethylsiloxane units with silicate hydride. In addition, Cosm. Toil. The volatile silicone described in 91, 27 (1976) is also suitable.

Examples of said fats include glycerides, which include inter alia bead wax, carnauba wax, candelilla wax, montan wax, paraffin wax, hydrogenated castor oil and optionally hydrophilic waxes such as cetylstearyl alcohol or Fatty acid esters or microwaxes that are solid at room temperature mixed with partial glycerides are preferred. Metal salts of fatty acids such as stearic acid or magnesium ricinoleate, aluminum, or zinc may be used as the stabilizer.

Examples of the active ingredient of the biological origin include tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acid, amino acid, ceramide, pseudoceramide, Essential oils, plant extracts, and vitamin complexes are preferred.

As the deodorant active ingredient, for example, an antiperspirant such as aluminum chlorohydrate (see J. Soc. Cosm. Chem. 24, 281 (1973)) is preferable. For example, an aluminum chlorohydrate corresponding to the formula Al ₂ (OH) ₅ Cl.2.5H ₂ O is commercially available under the registered trademark Locron® of Hoechst AG, Frankfurt (FRG), and its use is particularly preferred. (See J. Pharm. Pharmacol. 26, 531 (1975)). In addition to the chlorohydrate, hydroxy aluminum acetate and acidic aluminum / zirconium salts can also be used. An esterase inhibitor may be added as a further deodorant active ingredient. Such inhibitors are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate, in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Dusseldorf / FRG), which inhibits enzyme activity and thereby suppresses odor formation. Further substances considered as esterase inhibitors are sulfuric acid or phosphate sterols such as sulfuric acid or lanosterol phosphate, cholesterol, campesterol, stigmasterol and sitosterol, dicarboxylic acids and their esters such as glutaric acid, glutaric acid monoethyl ester Glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester, and hydroxycarboxylic acid and its esters, such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester . Antibacterial active ingredients that affect the flora, kill sweat-degrading bacteria or inhibit their growth can likewise be present in the formulation (especially stick formulations). Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-Chloro-2- (2,4-dichlorophenoxy) phenol (Irgasan®, Ciba Specialty Chemicals) has also proven to be particularly effective.

As the antiperspirant, for example, climazole, octopirox and zinc pyrithione can be used. Conventional film formers include, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, quaternary cellulose derivative polymer containing a high proportion of acrylic acid. , Collagen, hyaluronic acid and its salts, and similar compounds. As swelling agents for the aqueous phase, montmorillonite, clay minerals, pemulene and alkyl-modified type Carbopol (Goodrich) may be used. Further suitable polymers and swelling agents are described in R.A. Cosm. By Lochhead. Toil. 108, 95 (1993).

In cosmetic preparations containing the UV-absorbing material of the present invention, in addition to the primary photoprotective substance, secondary photoprotection of antioxidants that interfere with the photochemical reaction chain induced when UV rays penetrate the skin or hair Substances can also be used. Representative examples of such antioxidants are amino acids (eg glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (eg urocanic acid) and derivatives thereof, D, L-carnosine, D-carnosine, L- Peptides such as carnosine and derivatives thereof (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (eg dihydrolipoic acid), gold thiols Glucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and its glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, Oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) And sulphoximine compounds (eg, buthionine sulphoximine, homocysteine sulphoximine, butionine sulphones, penta-, hexa-, hepta-thionine sulphoximine) with very low tolerance (eg, pmol to μmol / kg) , As well as (metal) chelating agents (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acids, bile extracts, bili Bottles, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives thereof (eg Ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherol and its derivatives (eg, vitamin E acetate), vitamin A and derivatives (eg, vitamin A palmitate), and benzoin coniferyl benzoate, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, resinous nordihydroguaiaretic acid, nor Hydroguayretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, N- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] sulfanilic acid ( And salts thereof (eg disodium salt), zinc and derivatives thereof (eg ZnO, ZnSO ₄ ), selenium and derivatives thereof (eg selenium methionine), stilbene and derivatives thereof (eg stilbene oxide, trans-stilbene oxide) and Suitable derivatives of the active ingredient according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids). Mention may also be made of HALS (= “hindered amine light stabilizers”) compounds. The amount of antioxidant present is 0.001 to 30% by weight, preferably 0.01 to 3% by weight, based on the weight of the UV absorber.

In order to improve fluidity, hydrotropic agents such as ethanol, isopropyl alcohol or polyols can also be used. The polyols considered for that purpose preferably have 2 to 15 carbon atoms and at least 2 hydroxy groups.

Said polyols may contain further functional groups, in particular amino groups, and / or may be modified with nitrogen. Representative examples are: glycerin; alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycol having an average molecular weight of 100-1000 Da; 1.5-10 Technical oligoglycerin mixtures having a degree of intrinsic condensation, for example industrial diglycerin mixtures having a diglycerin content of 40-50% by weight;
-Methylol compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
Lower alkyl glucosides, especially those having 1 to 8 carbon atoms in the alkyl group, such as methyl and butyl glucoside; sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol; 5 to 12 carbons A sugar having an atom, such as glucose or saccharose; an amino sugar, such as glucamine; and a dialcohol amine, such as diethanolamine or 2-amino-1,3-propanediol.

Examples of suitable preservatives include phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid, and preservatives listed in Schedule 6, Part A and B of the Cosmetics Regulations.

As the perfume oil, mention may be made of a mixture of natural and / or synthetic aromatic substances. Natural fragrances are for example from flowers (lily, lavender, rose, jasmine, neroli, ylang ylang), from stems and leaves (geranium, patchouli, petitgren), from fruits (anis fruit, coriander, fennel, nezu), From fruit peel (bergamot, lemon, orange), from roots (Mace, Angelica, Celery, Cardamom, Costas, Iris, Shabu), from trees (Pine Tree, Sandalwood, Guayak Tree, Cedar Tree, Rosewood), From herbs and grasses (tarragon, lemongrass, sage, thyme), needles and twigs (spruce, pine, red pine, red pine), resin and balsam (galvanum, elemi, benzoin, myrrh, frankincense, opopanax) It is an extract. Mention may also be made of animal raw materials such as civet and castrium. Typical synthetic aromatic substances include, for example, products of esters, ethers, aldehydes, ketones, alcohols or hydrocarbons.

Aromatic compounds of esters include, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl glycinate Methyl phenyl, allyl cyclohexyl propionate, styryl propionate and benzyl salicylate. Examples of ethers include benzyl ethyl ether; examples of aldehydes include linear alkanals having 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronone Examples include ketones such as ionones, α-isomethylionone, and methyl cedryl ketone; examples of alcohols include anethole, citronellol, eugenol, isoeugenol, and geraniol. , Linalool, phenylethyl alcohol and terpinol; carbohydrates mainly include terpenes and balsams. It is preferred to use a mixture of various fragrances that together produce an attractive scent. Mainly used as an aromatic component, relatively low volatility ether oils such as sage oil, chamomile oil, clove oil, melissa oil, cinnamon leaf oil, lime flower oil, juniper oil, vetiver oil, Milky perfume oil, galvanum oil, labolanum oil and lavandin oil are also suitable as perfume oils. Bergamot oil, dihydromyrcenol, lyrial, rilal, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hezion, Sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandine oil, mascatel sage oil, β-damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur , Iso-E-super, fixolide NP, evanil, i It is preferable to use raldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotil and floramat alone or mixed with each other.

For example, the publication “Kosmetiche Farbemittel” of Farbstoffkomision der Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, p. Substances that are recognized and suitable for cosmetic purposes, such as edited in 81-106, may be used as colorants. The colorant is usually used at a concentration of 0.001 to 0.1% by weight based on the total mixture.

Examples of the antibacterial agent include 2,4,4′-trichloro-2′-hydroxydiphenyl ether, chlorohexidine (1,6-di (4-chlorophenylbiguanide) hexane) or TCC (3,4,4′-trichloro And a preservative having a specific action against Gram-positive bacteria such as carbanilide). Many aromatic substances and ether oils also have antibacterial properties.

Typical examples are eugenol, menthol and thymol which are active ingredients in clove oil, mint oil and thyme oil. A relevant natural deodorant is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-todecatrien-1-ol) present in lime flower oil. Glycerol monolaurate has also been proven to be a bacteriostatic agent. The amount of additional antibacterial agent present is usually 0.1-2% by weight, based on the solid content of the formulation.

Cosmetic preparations containing the UV-absorbing material of the present invention include an antifoaming agent such as silicone, a structural substance such as maleic acid, a solubilizing agent such as ethylene glycol, propylene glycol, glycerin or diethylene glycol, a latex, Opacifying agents such as styrene / PVP or styrene / acrylamide copolymers, complexing agents such as EDTA, NTA, β-alanine diacetic acid or phosphonic acid, propane / butane mixtures, N ₂ O, dimethyl ether, CO ₂ , N ₂ Or propellants such as air, so-called couplers such as oxidative dye precursors, and developer components, thioglycolic acid and derivatives thereof, reducing agents such as thiolactic acid, cysteamine, thiomalic acid or α-mercaptoethanesulfonic acid, or excess Hydrogen oxide, potassium bromide or sodium bromide It can include the oxidizing agent.

As said insect repellent, for example, N, N-diethyl-m-toluamide, 1,2-pentanediol or repellent 3535 are considered; suitable self-tanning agents are for example dihydroxyacetone, erythrulose or dihydroxyacetone and erythrulose And a mixture.

The cosmetic composition containing the ultraviolet absorbing material of the present invention can be contained in various cosmetic preparations. For example, the following preparations are particularly preferred: skin care preparations, for example skin-cleansing and cleansing preparations in the form of tablets or liquid soaps, synthetic detergents or washing pastes; bath preparations such as liquids (foam baths, milk, Shower preparations) or solid bath preparations such as bath cubes and bath salts; skin care preparations such as skin emulsions, multiemulsions or skin oils; cosmetic personal care preparations such as facial makeup in the form of day cream or powder cream Up, funny (powder or solid), blusher or cream make-up, eye care preparation, eg eye shadow preparation, mascara, eyeliner, eye cream or eye fix cream; lipstick, lip gloss, lip contour Lip care preparations such as nils, nail care preparations such as nail lacquers, nail lacquer removers, nail hardeners or cuticle removers; foot care preparations such as foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or Preparations for removing octopus; sun protection products such as sun milk, lotions, creams or oils, sunblocks or tropicals, pretanning preparations or aftersun preparations; skin tanning preparations such as self-tanning creams; Color products, eg skin bleaching products, or whitening products; insect repellents, eg insect repellent oils, lotions, sprays or sticks; deodorizing sprays, pump sprays Deodorant gels, deodorants such as sticks or roll-ons; antiperspirants, eg antiperspirant sticks, creams or roll-on; preparations for cleansing and caring for damaged skin, eg synthetic detergents (solid or liquid), peeling or scrubbing Products or peeling masks; hair removal products as chemicals (hair removal), eg hair removal powders, liquid hair removal products, hair removal products in cream or paste form, gel form or aerosol foam hair removal preparations; shaving Preparations such as shaving soap, foam shaving cream, non-foamed shaving cream, foams and gels, pre-shave preparations for dry shaving, aftershave or aftershave lotion; aromatic preparations such as fragrance Ron, Eau de Tore, Eau de Parfum, Parfant Allet, Parfum), perfume oil or perfume cream; and cosmetic hair treatment preparations such as shampoos and conditioners in the form of shampoos and conditioners, hair care preparations such as pre-treatment preparations, Hair tonic, styling cream, styling gel, pomade, hair rinse, treatment pack, strong hair treatment, hair structuring preparation, eg hair wave preparation for permanent wave (hot wave, mild wave, cold wave), hair straightening Preparations, liquid preparations, hair foams, hair sprays, bleach preparations, eg hydrogen peroxide solution, lightning shampoo, bleach cream, bleach powder, bleach Paste or oil, a temporary, semi-permanent hair color or permanent hair color, natural hair color, such as preparations or henna or camomile, including auto-oxidation dye.

Each of the preparations listed above can be in various forms, for example: W / O, O / W, O / W / O, W / O / W or liquids such as PIT emulsions and all types of microemulsions. In the form of a physical product, in the form of a gel, in the form of an oil, cream, milk or lotion, in the form of a powder, lacquer, tablet or make-up, in the form of a stick (spray containing propellant gas or a pump spray) Or in the form of an aerosol, in the form of a foam, or in the form of a paste.

The cosmetic preparation containing the ultraviolet absorbing material of the present invention is preferably an agent formulated in cosmetics in the form of encapsulating the ultraviolet absorbing material of the present invention in microcapsules. In some cases, a method of reducing the influence on the human body by encapsulating the functional component or increasing the stability of the compound is used. In particular, it is used as a method for stably using a light-sensitive component such as an ultraviolet absorber, and a commercially available product can be used as “Shirasoma (trade name of Seiwa Kasei Co., Ltd.)”. In the commercially available material, a silicone-resinized polypeptide comprising a silicone part and a polypeptide part obtained by hydrolyzing collagen, silk protein or the like is used as a microencapsulation material (membrane material). No. 2001-106612). The material to be encapsulated may be any material such as a natural polymer or a synthetic polymer, and it is preferable to use a naturally derived polymer such as collagen, gelatin, dextrin, or DNA. Moreover, it is also possible to discharge | release the ultraviolet absorber used for this invention from the part which exposed to light by providing photoresponsiveness to a capsule raw material (film | membrane material). In this case, since the absorbent contacts the skin only when necessary, it is preferable as a method for reducing the irritation to the skin as much as possible and maintaining the absorbent stably.

In the cosmetic preparation containing the UV-absorbing material of the present invention, a particularly preferred embodiment of the cosmetic preparation for the skin is a light protection preparation such as milk, lotion, cream, oil, sun block or tropical, Tanning preparations or after-sun preparations, and skin tanning preparations such as self-tanning creams. Of particular interest are sun protect creams, sun protect lotions, sun protect oils, sun protect milks, and sun protect preparations in the form of sprays.

In the cosmetic preparation containing the UV-absorbing material of the present invention, the above-mentioned preparation for hair treatment, particularly a shampoo, a hair-washing preparation in the form of a hair conditioner, is particularly preferred as an embodiment of a cosmetic preparation for hair. Hair care preparations such as pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, strong hair treatments, straightening preparations, liquid hair setting preparations, hair foams and hair sprays. Particularly preferred are hair shampoo preparations in the form of shampoos.

The shampoo preferably has the following composition, for example.
The ultraviolet ray absorbing material of the present invention was added in an amount of 0.01 to 5% by mass, laureth-2-sodium sulfate 12.0% by mass, cocamidopropyl betaine 4.0% by mass, sodium chloride 3.0% by mass, and water. 100%.

In the cosmetic preparation containing the ultraviolet-absorbing material of the present invention, for example, the following hair cosmetic formulations may be particularly used in the embodiment of the cosmetic preparation for hair.
a1) The ultraviolet-absorbing material of the present invention, PEG-6-C10 oxo alcohol, and sorbitan sesquioleate, water, and any desired quaternary ammonium compound, such as 4% mincamidopropyldimethyl-2 A self-emulsifying raw material formulation to which hydroxyethylammonium chloride or Quaternium 80 is added,
a2) consisting of the ultraviolet absorbing material of the present invention, tributyl citrate and PEG-20-sorbitan monooleate, water, and any desired quaternary ammonium compound such as 4% mincamidepropyldimethyl-2 A self-emulsifying raw material formulation to which hydroxyethylammonium chloride or Quaternium 80 is added,
b) quad-doped solutions of the UV-absorbing material of the present invention in butyl triglycol and tributyl citrate;
c) A mixture or solution of the UV-absorbing material of the present invention with n-alkylpyrrolidone.

When the UV-absorbing material of the present invention is used as a cosmetic preparation, for example, cream, gel, lotion, alcoholic and aqueous / alcoholic solution, water-containing emulsion, oil-containing emulsion, wax / fat composition, stick preparation, powder or ointment It can be used by containing.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.
The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Synthesis example 1
<Preparation of exemplary compound (50)>
1- (4,7-dihydroxybenzo [1,3] dithiol-2-ylidene) piperidinium acetate 1.64 g (0.005 mol) in 5 mL of N-methylpyrrolidone, 1,2-diphenyl-3,5- 1.26 g (0.005 mol) of pyrazolidinedione was added, and this was stirred at 100 ° C. for 30 minutes under nitrogen flow conditions, then cooled, added to 50 mL of dilute hydrochloric acid, and the precipitated solid was filtered off. 0.435 g (0.001 mol) of the obtained compound was dissolved in 5 mL of dimethylacetamide, 0.304 g (0.003 mol) of triethylamine was added, and the mixture was cooled to 0 ° C. Thereafter, 0.390 g (0.0024 mol) of 2-ethylhexanoyl chloride was added, and the mixture was returned to room temperature and stirred for 2 hours. After treatment with ethyl acetate and dilute hydrochloric acid, the target product was obtained by isolation on a silica gel column (hexane / ethyl acetate = 9/1). Yield 0.45 g, 66% yield. The maximum absorption wavelength of Example Compound (50) in an ethyl acetate solution was 382 nm.
¹ H NMR (deuterated chloroform) δ 0.95 (6H), 1.06 (6H), 1.4 to 1.9 (16H), 2.62 (2H), 7.15 (2H), 7.35 ( 6H), 7.45 ppm (4H).
FAB MS (matrix: 3-nitrobenzyl alcohol) m / z 687 ([M + H] ⁺ ), 686 ([M] ⁺ , 100%).
Anal. calcd. for C ₃₈ H ₄₂ N ₂ O ₆ S ₂ : C66.45, H6.16, N4.08%. Found: C66.21, H6.40, N4.01%.

Synthesis example 2
<Preparation of Exemplified Compound (34)>
1- (4,7-dihydroxybenzo [1,3] dithiol-2-ylidene) piperidinium acetate 1.64 g (0.005 mol) to 5 mL of N-methylpyrrolidone, 1,2-dimethyl-3,5- 0.64 g (0.005 mol) of pyrazolidinedione was added, and this was stirred at 100 ° C. for 30 minutes under a nitrogen flow condition, then cooled, added to 50 mL of dilute hydrochloric acid, and 1.63 g of the precipitated solid was filtered off. After 0.310 g (0.001 mol) of the obtained compound was dissolved in 5 mL of dimethylacetamide, 0.304 g (0.003 mol) of triethylamine was added and cooled to 0 ° C. Thereafter, 0.390 g (0.0024 mol) of 2-ethylhexanoyl chloride was added, and the mixture was returned to room temperature and stirred for 2 hours. After treatment with ethyl acetate and dilute hydrochloric acid, the target product was obtained by isolation on a silica gel column (hexane / ethyl acetate = 9/1). Yield 0.30 g, 53% yield. The maximum absorption wavelength of the exemplified compound (34) in the ethyl acetate solution was 371 nm, and it was found to have a long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.95 (6H), 1.06 (6H), 1.4 to 1.9 (16H), 2.6 (2H), 3.25 (6H), 7.3 ppm ( 2H).
FAB MS (matrix: 3-nitrobenzyl alcohol) m / z 563 ([M + H] ⁺ ), 562 ([M] ⁺ , 100%).
Anal. calcd. _{_{_{for C 28 H 38 N 2 O}}} 6 S 2: C59.76, H6.81, N4.98%. Found: C59.55, H7.10, N4.90%.

Synthesis example 3
<Preparation of exemplary compound (52)>
Exemplified compound (52) was prepared according to the following scheme.

After adding 185 mL (1.15 mol) of diethyl malonate to 50.0 g (0.23 mol) of N, N-dibutylhydrazine dihydrochloride, the reaction system was purged with nitrogen, and then the ethanol produced in the reaction was distilled off. The mixture was stirred at an external temperature of 170 ° C for 4 hours. The reaction solution was cooled to room temperature, decompressed to distill off unreacted diethyl malonate, and then purified by silica gel column purification to obtain 43.5 g (yield 88.9%) of synthetic intermediate A.
To 14.0 g (0.066 mol) of the obtained synthetic intermediate A, 19.7 g (0.06 mol) of 1- (4,7-dihydroxybenzo [1,3] dithiol-2-ylidene) piperidinium acetate, 60 mL of N-methylpyrrolidone was added, and the mixture was stirred at 80 ° C. for 1 hour under nitrogen flow condition, and then cooled. Added to 600 mL of dilute hydrochloric acid, the precipitated solid was collected by filtration and dried to obtain 24.89 g of synthetic intermediate B. 100%).
After 1.97 g (0.005 mol) of the obtained synthetic intermediate B was dissolved in 15 mL of dimethylacetamide, 1.52 g (0.012 mol) of triethylamine was added and cooled to 0 ° C. Thereafter, 2.08 mL (0.0024 mol) of 2-ethylhexanoyl chloride was added, and the mixture was stirred for 1 hour under ice cooling. After treatment with ethyl acetate and dilute hydrochloric acid, the target product was obtained by isolation on a silica gel column (hexane / ethyl acetate = 7/1). Yield 2.91 g, 90% yield. The maximum absorption wavelength of Exemplified Compound (19) in an ethyl acetate solution was 373 nm, and it was found to have long-wave ultraviolet absorption ability (melting point: 49-50 ° C.)
¹ H NMR (deuterated chloroform) δ 0.95 (12H), 1.06 (6H), 1.3 to 1.9 (24H), 2.61 (2H), 3.68 (4H), 7.25 ppm ( 2H).

Synthesis example 4
<Preparation of exemplary compound (51)>
Exemplified compound (51) was obtained in the same manner as in Synthesis Example 3, except that acetyl chloride was used in place of 2-ethylhexanoyl chloride. The maximum absorption wavelength of Exemplified Compound (51) in the ethyl acetate solution was 371 nm, and it was found to have a long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.92 (6H), 1.29 (4H), 1.52 (4H), 2.35 (6H), 3.66 (4H), 7.27 ppm (2H).

Synthesis example 5
<Preparation of exemplary compound (54)>
After 20.0 g (0.0507 mol) of the synthetic intermediate B was dissolved in 200 mL of dimethylacetamide, 15.4 g (0.111 mol) of potassium carbonate and 15.3 mL (0.142 mol) of n-butyl bromide were added at room temperature. Added at. Then, it stirred at 90 degreeC for 3 hours under nitrogen flow conditions. The reaction solution was cooled, added to 600 mL of dilute hydrochloric acid, and the precipitated solid was collected by filtration, dried, and then isolated with a silica gel column (hexane / ethyl acetate = 4/1) to obtain the desired product. Yield 21.1 g, 82% yield. The maximum absorption wavelength of Exemplified Compound (21) in an ethyl acetate solution was 380 nm, and it was found to have long-wave ultraviolet absorption ability (melting point: 141 to 142 ° C.).
¹ H NMR (deuterated chloroform) δ 0.95 (12H), 1.31 (4H), 1.55 (8H), 1.79 (4H), 3.64 (4H), 4.06 (4H), 6 72 ppm (2H).

Synthesis Example 6
<Preparation of exemplary compound (53)>
Exemplified compound (53) was obtained in the same manner as in Synthesis Example 5, except that methyl bromoacetate was used instead of n-butyl bromide. The maximum absorption wavelength of the exemplified compound (53) in the ethyl acetate solution was 379 nm, and it was found to have a long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.92 (6H), 1.31 (4H), 1.58 (4H), 3.68 (4H), 3.80 (6H), 4.74 (4H), 6 71 ppm (2H).

Synthesis example 7
<Preparation of exemplary compound (55)>
Exemplified compound (55) was obtained in the same manner as in Synthesis Example 3, except that benzoyl chloride was used in place of 2-ethylhexanoyl chloride. The maximum absorption wavelength of the exemplified compound (55) in the ethyl acetate solution was 374 nm, and it was found that the compound has long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.89 (6H), 1.27 (4H), 1.51 (4H), 3.51 (4H), 7.49 (2H), 7.56 (4H), 7 .69 (2H), 8.21 ppm (4H).

Synthesis example 8
<Preparation of exemplary compound (56)>
Exemplified compound (56) was obtained in the same manner as in Synthesis Example 5, except that N, N-dimethylcarbamoyl chloride was used in place of n-butyl bromide. The maximum absorption wavelength of the exemplified compound (56) in the ethyl acetate solution was 375 nm, and it was found to have a long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.91 (6H), 1.25 (10H), 1.52 (4H), 3.42 (8H), 3.65 (4H), 7.31 ppm (2H).

Synthesis Example 9
<Preparation of exemplary compound (57)>
Exemplified compound (57) was obtained in the same manner as in Synthesis Example 3, except that pivaloyl chloride was used in place of 2-ethylhexanoyl chloride. The maximum absorption wavelength of the exemplified compound (57) in an ethyl acetate solution was 373 nm, and it was found that the compound (57) has long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.94 (6H), 1.34 (4H), 1.41 (18H), 1.58 (4H), 3.66 (4H), 7.25 ppm (2H).

Synthesis Example 10
<Preparation of Exemplified Compound (58)>
Exemplified compound (58) was obtained in the same manner as in Synthesis Example 5, except that methyl 2-bromopropionate was used instead of n-butyl bromide. The maximum absorption wavelength of Exemplified Compound (58) in an ethyl acetate solution was 377 nm, and it was found that the compound has long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.92 (6H), 1.31 (4H), 1.58 (4H), 1.69 (6H), 3.68 (4H), 3.77 (6H), 4 .82 (2H), 6.78 ppm (2H).

Synthesis Example 11
<Preparation of exemplary compound (59)>
Exemplified compound (59) was obtained in the same manner as in Synthesis Example 3, except that p-toluenesulfonyl chloride was used in place of 2-ethylhexanoyl chloride. The maximum absorption wavelength of Exemplified Compound (59) in an ethyl acetate solution was 371 nm, and it was found to have a long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.95 (6H), 1.22-1.39 (4H), 1.49-1.61 (4H), 1.69 (6H), 2.47 (6H), 3.65 (4H), 7.30-7.41 (6H), 7.81 ppm (4H).

Synthesis Example 12
<Preparation of exemplary compound (61)>
Exemplified Compound 61 was prepared in the same manner as in Synthesis Example 1 except that 1-acyl-2-phenyl-3,5-pyrazolidinedione was used instead of 1,2-diphenyl-3,5-pyrazolidinedione. Got. The maximum absorption wavelength of the exemplified compound (61) in the ethyl acetate solution was 383 nm, and it was found that the compound has long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.91-1.12 (12H), 1.35-1.49 (8H), 1.61-1.89 (8H), 2.59 (2H), 2.68 (3H), 7.36 ppm (6H).

Synthesis Example 13
<Preparation of exemplary compound (62)>
In the same manner as in Synthesis Example 1 except that 1-p-methoxyphenyl-2-phenyl-3,5-pyrazolidinedione was used instead of 1,2-diphenyl-3,5-pyrazolidinedione, Exemplified compound (62) was obtained. The maximum absorption wavelength of the exemplified compound (62) in the ethyl acetate solution was 381 nm, and it was found that the compound has long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.95 (6H), 1.07 (6H), 1.31-1.49 (8H), 1.59-1.90 (8H), 2.60 (2H), 3.72 (3H), 6.82 (2H), 7.12 (1H), 7.32 (6H), 7.41 ppm (2H).

Synthesis Example 13-1
<Preparation of exemplary compound (63)>
Exemplified compound (63) in the same manner as in Synthesis Example 1, except that 1,2-dibenzyl-3,5-pyrazolidinedione was used instead of 1,2-diphenyl-3,5-pyrazolidinedione. Got. The maximum absorption wavelength of Exemplified Compound (63) in an ethyl acetate solution was 376 nm, and it was found to have a long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.91 (6H), 1.02 (6H), 1.31-1.45 (8H), 1.59-1.89 (8H), 2.60 (2H), 4.71 (4H), 7.09 (4H), 7.27 (6H), 7.31 ppm (2H).

Synthesis Example 14
<Preparation of Exemplified Compound (64)>
Exemplified compound (64) was obtained in the same manner as in Synthetic Example 1, except that synthetic intermediate C was used instead of 1,2-diphenyl-3,5-pyrazolidinedione. The maximum absorption wavelength of Exemplified Compound (64) in the ethyl acetate solution was 376 nm, and it was found to have a long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.85-1.18 (18H), 1.31-1.51 (8H), 1.55-1.89 (8H), 1.95 (4H), 2.62 (2H), 7.38 ppm (2H).

Synthesis Example 15
<Preparation of exemplary compound (65)>
Exemplified compound (64) was obtained in the same manner as in Synthesis Example 1, except that 1-H-2-phenylpyrazolidinedione was used instead of 1,2-diphenyl-3,5-pyrazolidinedione. . The maximum absorption wavelength of Exemplified Compound (64) in the ethyl acetate solution was 372 nm, and it was found to have a long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.81-1.05 (12H), 1.20-1.58 (8H), 1.59-1.90 (8H), 2.62 (2H), 7.19 (1H), 7.31 (2H), 7.41 (2H), 7.69 (2H), 7.81 ppm (1H).

Synthesis Example 16
<Preparation of Exemplified Compound (66)>
Exemplified compound (66) was obtained in the same manner as in Synthetic Example 3, except that N, N-dihexylhydrazine was used instead of N, N-dibutylhydrazine. The maximum absorption wavelength of Exemplified Compound (66) in an ethyl acetate solution was 373 nm, and it was found that the compound has long-wave ultraviolet absorption ability.
¹ H NMR (deuterated chloroform) δ 0.81-0.99 (12H), 1.02-1.11 (6H), 1.35-1.44 (4H), 1.50-1.1.61 ( 4H), 1.64-1.90 (8H), 2.61 (2H), 3.62 (4H), 7.27 ppm (2H).

Example 1
<Preparation of sample solutions 201-208>
A sample solution was prepared by dissolving 5 mg of the exemplified compound (50) in 100 mL of ethyl acetate and further diluting with ethyl acetate so that the absorbance was in the range of 0.95 to 1.05. Similarly, sample solutions 201 to 208 were prepared for the exemplary compounds (29) and (34) and the comparative compounds (C1) to (C5).

<Evaluation of UV absorbing ability and photostability>
The absorbance of each of the sample solutions 201 to 208 was measured in a 1 cm quartz cell using a spectrophotometer UV-3100 (trade name) manufactured by Shimadzu Corporation. FIG. 1 shows an absorption spectrum of a sample solution 202 (Example of the present invention) using the exemplified compound (29).

The maximum absorption wavelength (λ _max ) is measured from the spectrum chart obtained for each sample solution, A having a maximum absorption wavelength in the long wavelength ultraviolet region of 370 nm or more, A having a wavelength of 360 nm or more and less than 370 nm, B being less than 360 nm Some were rated as C in three grades.
Further, the degree of coloration of the solution was visually confirmed, and evaluation was made in three stages, with A indicating no coloration, B indicating slight coloration, and C indicating apparent coloration.

In addition, the cell in which the sample solution was sealed was irradiated with a xenon lamp from which the UV filter was removed so that the illuminance was 170,000 lux, and the remaining amount of the UV absorber after one week of irradiation was measured. The rate was evaluated in three stages, with A being 90% or more, A being 80% or more but less than 90%, and C being less than 80%. 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 4 below.

As is apparent from the results in Table 4, each of the solutions 201 to 203 of the ultraviolet absorbing material of the present invention has an absorptivity in a longer wavelength ultraviolet region closer to the visible region as compared with the solutions 204 to 208 of the comparative compound. It has been found that it has high stability against light. Among the solutions of the ultraviolet absorbing material of the present invention, in particular, the solution containing the exemplified compounds (29) and (34) which are compounds represented by the general formula (2) is less colored and used as a long wavelength ultraviolet absorber. It was found to have excellent performance (Samples 202 and 203).
From this, it was found that the ultraviolet absorbing material of the present invention is excellent in long wave ultraviolet absorbing ability, and this absorbing ability is maintained for a long period of time and is excellent in light resistance.

Example 2
<Preparation and evaluation of coating film 301>
2.0 mg of the exemplified compound (34) was dissolved in 2 mL of 1,1,2,2-tetrafluoropropanol and filtered using a 0.2 μm Millipore filter. Using this solution, on a glass substrate having a thickness of 1.1 mm, a spin coater 1H-D7 (trade name) manufactured by Mikasa Co., Ltd. was used to change the rotational speed between 500 and 2000 rpm, and at room temperature. A coating film 301 was produced under a nitrogen atmosphere. The absorbance of the prepared coating film 301 was measured using a spectrophotometer UV-3100 (trade name) manufactured by Shimadzu Corporation. FIG. 2 shows an absorption spectrum of the coating film 301 using the exemplary compound (34). As is apparent from FIG. 2, it has an absorptivity in a long wavelength ultraviolet region close to the visible region, and can be usefully used as an ultraviolet absorbing material such as a coating film.

The ultraviolet absorbing material of the present invention is suitably used for packaging materials, containers, paints, coating films, inks, fibers, building materials, recording media, image display devices, solar cell covers, glass coatings, cosmetic preparations, and the like. be able to.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application claims priority based on Japanese Patent Application No. 2008-090289 filed in Japan on March 31, 2008 and Japanese Patent Application No. 2008-248082 filed on September 26, 2008 in Japan. The contents of which are hereby incorporated by reference.

Claims

An ultraviolet-absorbing material comprising a compound represented by the following general formula (1):

(In the general formula (1), X 1 and X 2 each independently represents an oxygen atom, a sulfur atom or —NR 17 —, and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 Each independently represents a hydrogen atom or a monovalent substituent.)
The ultraviolet-absorbing material according to claim 1, wherein X 1 and X 2 in the general formula (1) are both sulfur atoms.
A compound represented by the following general formula (2).

(In the general formula (2), R 21 and R 22 each independently represents a substituted or unsubstituted alkyl group, and R 23 , R 24 , R 25 and R 26 each independently represent a hydrogen atom or a monovalent substituent. Represents.)
The R 23 , R 24 , R 25 and R 26 in the general formula (2) are atomic groups necessary for the sum of the Hammett's substituent constant σ p values to be 0 or more. Compound.
A compound represented by the following general formula (3).

(In the general formula (3), R 31 and R 32 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted or unsubstituted. Acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted Or an unsubstituted sulfamoyl group, wherein R 33 and R 36 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted or Unsubstituted acyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted alkoxy It represents a carbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted sulfamoyl group.)
R 31 and R 32 in the compound represented by the general formula (3) are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted acyl group, and R 33 and R 36 are each independently The compound according to claim 5, which is a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted carbamoyl group.