JP2010180288A - Ultraviolet absorber composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet absorber composition which is excellent in the long-wave ultraviolet absorbing ability, is excellent in the stability at a long-period preservation, and has such heat resistance (heat fastness) as is melt-kneadable. <P>SOLUTION: The ultraviolet absorber composition comprises such a specific ultraviolet absorber as is exemplified at the left side between the formulae, and such a specific compound as is exemplified at the right side between the formulae. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an ultraviolet absorber composition. More specifically, the present invention is excellent in long-wave ultraviolet absorbing ability without causing precipitation of the ultraviolet absorber and bleeding out due to long-term use, and this absorbing ability is prolonged. It is related with the ultraviolet absorber composition which is maintained for a period and is excellent in heat resistance and light resistance.

Conventionally, ultraviolet absorbers have been imparted by sharing ultraviolet absorbers with various resins. An inorganic ultraviolet absorbent and an organic ultraviolet absorbent may be used in combination as the ultraviolet absorbent. 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 is little degree of freedom, and there is nothing that can absorb up to 320 to 400 nm long wave ultraviolet (UV-A) region, and those that absorb long wave ultraviolet rays have absorption up to the visible region and are therefore colored.
On the other hand, since the organic ultraviolet absorber has a high degree of freedom in the structural design of the absorbent, it is possible to obtain various absorption wavelengths by devising the structure of the absorbent.

  In the past, systems using various organic ultraviolet absorbers have been studied. When absorbing up to the long wave ultraviolet region, use one with a maximum absorption wavelength in the long wave ultraviolet region or increase the concentration. There are two possible ways. However, those having the maximum absorption wavelength described in Patent Documents 4 and 5 in the long wave ultraviolet region have poor light resistance, and the absorption ability decreases with time.

  In contrast, benzophenone and benzotriazole UV absorbers have relatively good light resistance, and can be cut relatively clearly up to a long wavelength region by increasing the concentration and film thickness (see, for example, Patent Documents 6 and 7). .) Usually, when these ultraviolet absorbers are mixed and applied in a resin or the like, the film thickness is limited to about several tens of μm. When cutting to a long wavelength region with this film thickness, it is necessary to add an ultraviolet absorber at a considerably high concentration. However, there is a problem that coloring occurs simply by adding to a high concentration. In addition, some benzophenone and benzotriazole ultraviolet absorbers have skin irritation properties and accumulation properties in the living body, and careful attention is required for use. Patent Documents 8 and 9 describe a 5-membered ring compound containing two sulfur atoms. However, there is no description of ultraviolet absorbers that can absorb in the long wavelength region with a sharp waveform and the danger of coloring.

  By the way, polymer materials and resins prevent deterioration by adding many additives. The essence of degradation of polymer materials is auto-oxidation, and many polymer materials to suppress this are UV absorbers, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, This was addressed by adding several types of additives selected from acid capture agents and the like (Patent Documents 10 and 11). However, it is generally known that when a UV absorber and other additives are simply added to a polymer material, a phenomenon that the particles float on the polymer surface (bleed out) due to the deterioration of the compatibility with the polymer.

  On the other hand, when an organic ultraviolet absorber is mixed with a resin or the like, there are mainly a method in which the ultraviolet absorber is dissolved in a solvent together with the polymer resin, and a method in which the ultraviolet absorber is melt kneaded into the polymer resin. When a polymer resin having poor solubility in a solvent is used, the latter method is often employed, but melt kneading requires high-temperature treatment. For example, when polyethylene terephthalate, which is a general-purpose resin, is used, it is exposed to high temperature conditions of 200 ° C. or higher, and many organic ultraviolet absorbers volatilize or decompose under such conditions.

  UV absorbers that can be applied to melt kneading are limited, and those thermally robust UV absorbers have at least one of high light fastness and absorption characteristics that can effectively shield up to long waves. Not done. Therefore, there has been a demand for an ultraviolet absorber that satisfies all of high heat fastness, high light fastness, and effective long wave ultraviolet shielding ability.

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 60-170842 A Japanese Patent Publication No.49-11155 JP 2008-52041 A JP 2004-117997 A

  An object of the present invention is to satisfy the above-described requirements, and to provide an ultraviolet absorbent composition having excellent long-wave ultraviolet absorption ability, excellent stability in long-term storage, and heat resistance (heat fastness) that can be melt-kneaded. It is to provide.

As a result of intensive studies, the inventors of the present invention have the general formula (TS-I) or (TS-II) in at least one of the ultraviolet absorbers represented by the general formula (1) having excellent long-wave ultraviolet absorption ability. It has been found that a composition using at least one of the compounds represented by (2) is excellent in heat resistance and light resistance while maintaining long-wave ultraviolet absorption ability. Furthermore, the ultraviolet absorber composition obtained by using at least one of the compounds represented by the general formula (TS-I) or (TS-II) in combination with the ultraviolet absorber represented by the general formula (1) It has been found that the heat resistance and the light resistance are dramatically improved, and that this composition does not cause precipitation of constituent components or bleed out due to long-term use even when mixed in a resin. It is surprising that no bleed out, which is a concern when using an ultraviolet absorber as a composition, was observed.
The present invention has been made based on such findings.

The object of the present invention has been achieved by the following method.
<1> comprising at least one ultraviolet absorber represented by the following general formula (1) and at least one compound represented by the following general formula (TS-I) or (TS-II): UV absorber composition.

(In the general formula (1), ^{X 1} and ^{X 2} each independently represent an oxygen atom, a sulfur atom or ^{-NR 17} - ^{represents, 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.)

[In the general formula (TS-I), R ₉₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted group. Or an unsubstituted acyl group, a substituted or unsubstituted alkyl or alkenyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or -Si (R ₉₇ ) (R ₉₈ ) (R ₉₉ ) is represented. Here, R ₉₇ , R ₉₈ and R ₉₉ may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group or an aryloxy group. —X ₉₁ — represents —O—, —S— or —N (—R ₁₀₀ ) —. Here, R ₁₀₀ is synonymous with R ₉₁ . R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ and R ₉₆ may be the same as or different from each other, and each represents a hydrogen atom or a substituent. However, R ₉₁ , R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ , R ₉₆ and R ₁₀₀ are not all hydrogen atoms, and the total number of carbon atoms is 10 or more.
In general formula (TS-II), R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, and R ₁₀₁ and R ₁₀₂ , R ₁₀₃ and R ₁₀₄ may combine to form a 5- to 7-membered ring. X ₁₀₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted alkyl or alkenyloxycarbonyl Group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkyloxycarbonyloxy group, substituted or unsubstituted alkenyloxycarbonyloxy group, Substituted or unsubstituted aryloxycarbonyloxy group, substituted or unsubstituted alkyl or alkenylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkyl or alkenylsulfinyl group Represents a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted carbamoyl group, a hydroxy group, or an oxy radical group. X ₁₀₂ represents a hetero atomic group necessary for forming a 5- to 7-membered ring. ]
<2> The ultraviolet absorbent composition according to <1>, wherein the ultraviolet absorbent represented by the general formula (1) is an ultraviolet absorbent 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.)
<3> The total content of the ultraviolet absorber represented by the general formula (1) or (2) is greater than 0% by mass and equal to or less than 90% by mass with respect to the entire composition, <1> or <2 > UV absorber composition as described in>.
<4> The total content of the compound represented by the general formula (TS-I) or (TS-II) is greater than 0% by mass and equal to or less than 80% by mass with respect to the entire composition, <1> to The ultraviolet absorber composition according to any one of <3>.
<5> The mixing ratio of the ultraviolet absorber represented by the general formula (1) or (2) and the compound represented by the general formula (TS-I) or (TS-II) is 10: The ultraviolet absorber composition according to any one of <1> to <4>, which is 1-1: 1.
<6> The ultraviolet absorbent composition according to any one of <1> to <5>, comprising at least one compound represented by the general formula (TS-I).
<7> The ultraviolet absorption according to any one of <1> to <6>, wherein the compound represented by the general formula (TS-I) is a compound represented by the following general formula (TS-Ia): Agent composition.

(In the general formula (TS-Ia), R ₉₂ , R ₉₃ , R ₉₅ , R ₉₆ , R ₈₂ , R ₈₃ , R ₈₅ , R ₈₆ may be the same as or different from each other, and each represents a hydrogen atom or a substituent. Provided that R ₉₂ , R ₉₃ , R ₉₅ , R ₉₆ , R ₈₂ , R ₈₃ , R ₈₅ , and R ₈₆ are not all hydrogen atoms, L _p represents a linking group, and n is 0 or Represents an integer of 1)
<8> An ultraviolet absorbent dispersion containing the ultraviolet absorbent composition according to any one of <1> to <7>.
<9> An ultraviolet absorbent solution comprising the ultraviolet absorbent composition according to any one of <1> to <7>.
<10> A polymer material comprising the ultraviolet absorbent composition according to any one of <1> to <7>.

  The ultraviolet absorbent composition of the present invention has excellent long-wave ultraviolet absorbing ability over a long period of time, has heat resistance that can be melt kneaded into a polymer resin, and is further mixed with a polymer resin. Even in this case, there is an excellent effect of preventing precipitation of constituent components of the ultraviolet absorber composition and bleeding out due to long-term use.

Hereinafter, the present invention will be described in detail.
The ultraviolet absorber composition of the present invention includes at least one of the ultraviolet absorber represented by the general formula (1) and at least one of the compounds represented by the general formula (TS-I) or (TS-II). It is characterized by including one. The compound represented by the general formula (TS-I) or (TS-II) suppresses thermal decomposition of the ultraviolet absorbent represented by the general formula (1) in the ultraviolet absorbent composition, and variously. It also functions as a light stabilizer that prevents decomposition of the resin by sharing it with other resins.
Hereinafter, the ultraviolet absorber represented by the following 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, the James edition, “The Theory of the Photographic Process ”, 4th edition, Macmillan Publishers, 1977, page 197. The merocyanine pigments here are, for example, Shin Okawara, Ken Matsuoka, Hirashima Tsuneaki, Kojiro Kitao, “Functional dyes”, Kodansha Scientific Co., 1992, p. 52)).

In 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 both X ¹ and X ² are sulfur atoms.

R ¹⁷ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, more preferably a substituted or unsubstituted C 1 to 20 carbon group. 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, a sulfur atom or a nitrogen atom, and may be condensed with an alicyclic ring, an aromatic ring or a 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.
R ¹¹ and R ¹² may combine with each other to form a ring.

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 1-30. 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 a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group 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. As the alkenyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms is preferable. 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 a 2-cyclopenten-1-yl group and a 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 in which one hydrogen atom of a bicycloalkene having one double bond is removed. 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 thereof include a methoxy group, an ethoxy group, an isopropoxy group, an n-octyloxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 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, or 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 a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, and a pn-hexadecyloxyphenoxycarbonyloxy group. 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, or 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 phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group, and the like. 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 is 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 at 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. Examples thereof include methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl group and the like.

  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, a phenoxysulfonyl, 2-naphthoxyphenyl group, etc. 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 each independently 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, 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. A 6-30 aryloxy group, a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, a hydroxyl group, or a halogen atom, more preferably hydrogen. Atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms, substituted or unsubstituted acyloxy groups having 2 to 20 carbon atoms, or 1 to carbon atoms 20 substituted or unsubstituted carbamoyloxy group, particularly preferably a substituted or unsubstituted acyloxy group having 2 to 18 carbon atoms or 1 to 18 carbon atoms. A conversion or unsubstituted carbamoyloxy group.

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 or 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. Whether 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 or a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, wherein R ¹⁴ is a hydrogen atom, or a substituted or unsubstituted carbon number 1 to 1 an 30 alkyl group, a R ¹⁵ is a hydrogen atom, or R ¹⁶ is a substituted or unsubstituted substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms Or a substituted or unsubstituted carbamoyloxy group having prime 1-30.
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, and R ¹³ is a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acyloxy group having 2 to 20 carbon atoms, or 1 to 20 carbon atoms. A substituted or unsubstituted carbamoyloxy group, R ¹⁴ is a hydrogen atom, 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 group Or a substituted or unsubstituted carbamoyloxy group having 1 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. a 1 to 18 alkyl ^{group, R 13} is a substituted or unsubstituted substituted or unsubstituted carbamoyloxy group having 1 to 18 carbon atoms or an acyloxy group having 2 to 18 carbon ^{atoms, R 14} is a hydrogen atom Whether R ¹⁵ is a hydrogen atom, and R ¹⁶ is a substituted or unsubstituted acyloxy group having 2 to 18 carbon atoms or a substituted or unsubstituted carbamoyloxy group having 1 to 18 carbon atoms And a compound represented by the general formula (2).

Hereinafter, the ultraviolet absorber represented by the following general formula (2) will be described in detail.

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 meaning and the same preferable ranges as R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ in the general formula (1), respectively.

  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. A C1-30 alkoxy group, a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, and R ²⁴ is a hydrogen atom. 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 group. The combination is an acyloxy group having 2 to 30 carbon atoms or a substituted or unsubstituted carbamoyloxy group having 1 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, a substituted or unsubstituted acyloxy group having 2 to 20 carbon atoms, or a substituted or unsubstituted carbamoyloxy group having 1 to 20 carbon atoms, and R ²⁴ is a hydrogen atom R ²⁵ is a hydrogen atom, and R ²⁶ is a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acyloxy group having 2 to 20 carbon atoms, or 1 to carbon atoms. A combination of 20 substituted or unsubstituted carbamoyloxy groups.
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. Or a substituted or unsubstituted carbamoyloxy group having 1 to 18 carbon atoms, R ²⁴ is a hydrogen atom, R ²⁵ is a hydrogen atom, and R ²⁶ is substituted or The combination is an unsubstituted acyloxy group having 2 to 18 carbon atoms or a substituted or unsubstituted carbamoyloxy group having 1 to 18 carbon atoms.

  The ultraviolet absorber represented by the general formula (1) or (2) in the present invention can be synthesized according to a conventionally known method for synthesizing similar compounds (for example, Journal of Chemical Crystallography (Journal of Chemical Crystallography)). Crystallography) 27, 997, 516 pages, right line 3 to 520, right line 15 lines, Liebigs Analen der Chemie 726, 106 pages 15 lines to 109 pages 37 lines, JP No. 49-1115, page 3, left line 7 to page 5, left line 8, line 8, Bioorganic & Medicinal Chemistry Letters 7 1997, page 652, lines 9 to 19, Journal of Organic Chemistry 43, 1978, page 2153, 2nd line to 12th line, JP 4-338759, page 4 left line 2nd line to 5th page, left 2nd line, JP-A-3-54566, 7th page, left line 6th to 8th page, left line 10th line, Synthesis 1986, 968 page, 1st line, 1st line to 22nd line. It can be synthesized by the description, citation or synthesis method based on these described in the line.

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

  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. 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 exemplary compounds 1 to 68 are also specific examples of the compound represented by the general formula (2).

  The molecular weight of the compound represented by the general formula (1) or (2) used in the present invention is preferably 300 or more and 1500 or less, and 350 or more and 1000 or less, from the viewpoints of volatilization suppression and bleed resistance. More preferably, it is 400 or more and 900 or less.

  Then, the compound represented by the following general formula (TS-I) or (TS-II) used for this invention is demonstrated.

In general formula (TS-I), R ₉₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group (including cyclic alkyl groups such as a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), a substituted or unsubstituted group. An alkenyl group (including cyclic alkenyl groups such as a cycloalkenyl group, a bicycloalkenyl group, and a tricycloalkenyl group), a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, A substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group (a cyclic alkylsulfonyl group such as a cycloalkylsulfonyl group, a bicycloalkylsulfonyl group, or a tricycloalkylsulfonyl group; Included), substituted or unsubstituted a Rusuruhoniru represents group, or -Si a _{(R 97) (R 98)} (R 99). Here, R ₉₇ , R ₉₈ and R ₉₉ may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group or an aryloxy group. —X ₉₁ — represents —O—, —S— or —N (—R ₁₀₀ ) —. Here, R ₁₀₀ is synonymous with R ₉₁ . R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ and R ₉₆ may be the same as or different from each other, and each represents a hydrogen atom or a substituent. However, R ₉₁ , R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ , R ₉₆ and R ₁₀₀ are not all hydrogen atoms, and the total number of carbon atoms is 10 or more.

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

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

The general formula (TS-I) will be described in more detail.
R ₉₁ includes a hydrogen atom, an alkyl group (including a cyclic alkyl group such as a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group, such as a methyl group, an i-propyl group, an s-butyl group, a dodecyl group). Group, methoxyethoxy group, benzyl group), alkenyl group (including cycloalkenyl group, bicycloalkenyl group, for example, allyl group), aryl group (for example, phenyl group, p-methoxyphenyl group) heterocyclic group (for example, 2- Tetrahydrfuryl group, pyranyl group), acyl group (for example, acetyl group, pivaloyl group, benzoyl group, acryloyl group), alkyl or alkenyloxycarbonyl group (for example, mexycarbonyl group, hexadecyloxycarbonyl group), aryloxycarbonyl group ( For example, phenoxycarbonyl group, p-methoxy Phenoxycarbonyl group), an alkylsulfonyl group (e.g., methanesulfonyl group, butanesulfonyl group), an arylsulfonyl group (e.g., benzenesulfonyl group, p- toluenesulfonyl group), or _{-Si (R 97) (R 98} ) (R 99) Represents. Here, R ₉₇ , R ₉₈ and R ₉₉ may be the same or different, and are each an alkyl group (for example, methyl group, ethyl group, t-butyl group, benzyl group), alkenyl group (for example, allyl group), aryl A group (for example, phenyl group), an alkoxy group (for example, methoxy group, butoxy group), an alkenyloxy group (for example, allyloxy group), or an aryloxy group (for example, phenoxy group) is represented. Since it is inferior in the solubility with respect to a solvent and the compatibility with a polymer, it is preferable that it is not a phosphinotolyl group and a phosphinyl group.

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

Among them, preferred substituents are alkyl groups (for example, methyl group, t-butyl group, t-hexyl group, benzyl group), alkenyl groups (aryl group), aryl groups (for example, phenyl group), alkoxycarbonyl groups (for example, methoxy group). Carbonyl group, dodecyloxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkyl or alkenylsulfonyl group (for example, methanesulfonyl group, butanesulfonyl group), arylsulfonyl group (for example, benzenesulfonyl group, p-hydroxybenzene) Sulfonyl group) or -X ₉₁ -R ₉₁ .
R ₉₁ and R ₉₂ , R ₁₀₀ and R ₉₆ , R ₉₁ and R ₁₀₀ are bonded to each other to form a 5- to 7-membered ring (for example, chroman ring, morpholine ring) because of poor solubility in a solvent and compatibility with a polymer. Preferably it is not formed. Furthermore, R ₉₂ and R ₉₃ , R ₉₃ and R ₉₄ are also bonded to each other so as not to form a 5- to 7-membered ring (for example, chroman ring, indane ring), spiro ring, or bicyclo ring. It is preferable from the viewpoint of compatibility. However, R ₉₁ , R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ , R ₉₆ , and R ₁₀₀ are not all hydrogen atoms, and the total number of carbons is 10 or more, preferably 16 or more. is there.

More preferred as the substituent of the general formula (TS-I) are X ₉₁ is an oxygen atom, R ₉₁ is a hydrogen atom, and R ₉₂ and R ₉₆ are branched alkyl groups having 4 or more carbon atoms.

  The compound represented by the general formula (TS-I) used in the present invention is a general formula (IIIa) of JP-B-2-37575, a general formula of JP-A-2-50457, or JP-A-2-66541. General formula (I) (II) of the publication, general formula (III) of the publication 2-139544, general formula (III) of the publication 3-200758, general formula (II) of the publication 3-48845, The compounds represented by the general formula (B) of JP-A-3-266636 and the general formula (I) of JP-A-3-96944 are included.

  The molecular weight of the compound represented by the general formula (TS-I) is preferably 500 or more, and particularly preferably 600 or more. When the molecular weight is large, scattering of the compound is suppressed under heating conditions.

  The general formula (TS-I) is particularly preferably a compound represented by the following general formula (TS-Ia).

_{Wherein, R 92, R 93, R} 95, R 96 has the same meaning as _{R 92, R 93, R 95} , R 96 in the formula (TS-I), and preferred ranges are also the same. R ₈₂ , R ₈₃ , R ₈₅ and R ₈₆ have the same meanings as R ₉₂ , R ₉₃ , R ₉₅ and R ₉₆ in formula (TS-I), and preferred ranges are also the same. R ₉₂ , R ₉₆ , R ₈₂ , and R ₈₆ are particularly preferably a branched alkyl group having 4 or more carbon atoms. More preferably, R ₈₂ and R ₉₂ , R ₈₃ and R ₉₃ , R ₈₅ and R ₉₅ , and R ₈₆ and R ₉₆ are equal substituents.

  In the general formula (TS-Ia), n represents an integer of 0 or 1. Here, when n is 0, two benzene rings are directly connected, that is, the general formula (TS-Ia) is represented by the following general formula (TS-Ib).

In the formula, R ₉₂ , R ₉₃ , R ₉₅ , R ₉₆ , R ₈₂ , R ₈₃ , R ₈₅ , and R ₈₆ have the same meanings as in the general formula (TS-Ia).
From the viewpoint of solubility, n is preferably 1 in the general formula (TS-Ia).

In the general formula (TS-Ia), when n is 1, the linking group L _p is a divalent substituent represented by the following general formula (d).

In general formula (d), ma1-ma10 represents the integer of 0-2.
La _{1 to} La ₁₀ are each independently —CO—, —O—, —SO ₂ —, —SO—, —S—, —NRa _L —, a divalent substituted or unsubstituted alkyl group, divalent Represents a substituted or unsubstituted alkenyl group, or a divalent substituted or unsubstituted aryl group. Ra _L represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

Specific examples of Ra _L include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a phenyl group, and a naphthyl group. A monovalent substituent may be present at any position on the alkyl group and the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Ra _L is preferably a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. More preferably, it is a substituted or unsubstituted alkyl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

In view of the function as thermal and photolysis inhibition, at least one of La _{1 to} La ₁₀ is preferably —S—, and particularly preferably one is —S—. Further, in view of solubility, the La ₁ ~La ₁₀ is, - (Lb) -CO- (Lc ) -, - (Lb) -O- (Lc) -, or - (Lb) -CO-O- It is preferable that at least one combination of (Lc)-is included, and it is particularly preferable that two or more combinations of-(Lb) -CO-O- (Lc)-are included. Here, Lb and Lc are synonymous with La _{1 to} La _10, and are particularly preferably a divalent unsubstituted alkyl group having 2 or more carbon atoms.

  Specific examples of the compound represented by formula (TS-I) are shown below, but the present invention is not limited thereto.

  Among the above specific examples, TI-30, TI-48, TI-51, TI-52, TI-54, TI-55, and TI-57 to 62 are compounds included in the general formula (TS-Ia). is there.

In the general formula (TS-II), R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group (a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, etc. And a substituted or unsubstituted alkenyl group (including a cyclic alkenyl group such as a cycloalkenyl group, a bicycloalkenyl group, and a tricycloalkenyl group), and R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ may be bonded to form a 5- to 7-membered ring.
X ₁₀₁ is a hydrogen atom, a substituted or unsubstituted alkyl group (including cyclic alkyl groups such as a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), a substituted or unsubstituted alkenyl group (a cycloalkenyl group, a bicycloalkenyl group). Group, cyclic alkenyl group such as tricycloalkenyl group, etc.) group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkyl or alkenyloxycarbonyl group, substituted or unsubstituted Substituted aryloxycarbonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkyloxycarbonyloxy group, substituted or unsubstituted alkenyloxycarbonyloxy group, substituted or unsubstituted Aryloxycarbonyloxy group Substituted or unsubstituted alkyl or alkenylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkyl or alkenylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted sulfamoyl group, substituted Or an unsubstituted carbamoyl group, a hydroxy group, or an oxy radical group is represented.
X ₁₀₂ represents a hetero atomic group necessary for forming a 5- to 7-membered ring.

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

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

In the formula, X ₁₀₁ has the same meaning as X ₁₀₁ in formula (TS-II), and the preferred range is also the same. R ₂₀₀ represents a monovalent substituent. Examples of the monovalent substituent include the examples of the monovalent substituent described above.

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

  Specific examples of the compound represented by the general formula (TS-II) are shown below, but the present invention is not limited thereto.

  When two or more compounds represented by the general formula (TS-I) or (TS-II) are contained, two or more compounds from the same group may be used in combination (for example, the general formula (TS-I) ), Two or more compounds may be used in combination over a plurality of groups (for example, the compound represented by the general formula (TS-I) and the general formula (TS -When the compound represented by II) is used one by one). Preferably, two or more types are used in combination over a plurality of groups.

In the present invention, two or more kinds of ultraviolet absorbers represented by the general formula (1) having different structures may be used in combination, or the ultraviolet absorber represented by the general formula (1) and the others. One or more ultraviolet absorbers having a structure (ultraviolet absorber) may be used in combination. When two types (preferably three types) of ultraviolet absorbers are used in combination, ultraviolet rays in a wide wavelength region can be absorbed. In addition, when two or more kinds of ultraviolet absorbers are used in combination, the dispersion state of the ultraviolet absorber is also stabilized. Any ultraviolet absorber having a structure other than 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, benzoic acid ester oxalic acid diamide, etc., known as UV absorber structures Compounds. For example, Fine Chemical, May 2004 issue, pages 28-38, published by Toray Research Center, Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999), pages 96-140, Junichi Okachi Supervised “Development of Polymer Additives and Environmental Measures” (CM Publishing, 2003), pages 54-64, etc.
A benzotriazole-based, benzophenone-based, salicylic acid-based, acrylate-based, or triazine-based compound is preferable because of its large molar extinction coefficient. More preferred are benzotriazole-based, benzophenone-based, and triazine-based compounds having excellent light fastness. Particularly preferred are benzotriazole and triazine compounds.

  The benzotriazole-based compound is preferably a compound having an effective absorption wavelength of about 270 to 380 nm and represented by any of the following general formulas (IIa) or (IIb). General formulas (IIa) and (IIb) will be described in detail.

[In the general formula (IIa),
R ₃₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group.
R ₃₂ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
R ₃₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a —COOR ₃₄ group (where R ₃₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, Or a substituted or unsubstituted aryl group. ]

[In the general formula (IIb),
T represents a hydrogen atom or a substituted or unsubstituted alkyl group.
T ₁ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group.
L represents a divalent linking group or a single bond, and m represents 0 or 1.
n represents an integer of 1 to 4. When n is 1, T ₂ represents a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. When n is 2, T ₂ represents a divalent substituent, when n is 3, T ₂ represents a trivalent substituent, and when n is 4, T ₂ represents a tetravalent substituent. ]

(General formula (IIa))
R ₃₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group.
R ₃₁ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms. R ₃₁ is particularly preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms.

  A substituted alkyl group, a substituted cycloalkyl group, and a substituted aryl group represent an alkyl group, a cycloalkyl group, or an aryl group having a monovalent substituent at any position. Examples of monovalent substituents include halogen Atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methyl, ethyl), 6 to 20 carbon atoms (preferably Are 6-10) aryl groups (eg phenyl, naphthyl), cyano groups, carboxyl groups, C1-C20 (preferably 1-10) alkoxycarbonyl groups (eg methoxycarbonyl), C6-C20 (preferably Is an aryloxycarbonyl group (for example, phenoxycarbonyl) having 6 to 10), a substituted or unsubstituted carbon having 0 to 20 carbon atoms (preferably 0 to 10). Moyl group (for example, carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), C1-C20 (preferably 1-10) alkylcarbonyl group (for example, acetyl), C6-C20 (preferably 6- 10) an arylcarbonyl group (for example, benzoyl), a nitro group, a substituted or unsubstituted amino group having a carbon number of 0 to 20 (preferably 0 to 10) (for example, amino, dimethylamino, anilino), a carbon number of 1 to 20 ( Preferably an acylamino group of 1 to 10) (eg acetamide, ethoxycarbonylamino),

C0-20 (preferably 0-10) sulfonamide group (for example, methanesulfonamide), C2-20 (preferably 2-10) imide group (for example, succinimide, phthalimide), C1-20 (Preferably 1-10) imino group (for example, benzylideneamino), hydroxy group, C1-C20 (preferably 1-10) alkoxy group (for example, methoxy), C6-C20 (preferably 6-10) ), An aryloxy group (for example, phenoxy), an acyloxy group having 1 to 20 carbon atoms (preferably 1 to 10), for example, acetoxy, and an alkylsulfonyloxy group having 1 to 20 carbon atoms (preferably 1 to 10) (for example, methane). Sulfonyloxy), arylsulfonyloxy groups having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) such as benzenesulfo Ruoxy), a sulfo group, a substituted or unsubstituted sulfamoyl group having 0 to 20 carbon atoms (preferably 0 to 10) (for example, sulfamoyl, N-phenylsulfamoyl), 1 to 20 carbon atoms (preferably 1 to 10). An alkylthio group (for example, methylthio), an arylthio group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), an alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methanesulfonyl), C6-C20 (preferably 6-10) arylsulfonyl group (for example, benzenesulfonyl), 4- to 7-membered ring (preferably 5-6-membered ring) heterocyclic group (for example, pyridyl, morpholino), etc. Can do.

R ₃₂ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ₃₂ is preferably a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 18 carbon atoms, or a substituted or unsubstituted group having 6 to 24 carbon atoms. An aryl group. R ₃₂ is particularly preferably a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.

R ₃₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a —COOR ₃₄ group (where R ₃₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, Or a substituted or unsubstituted aryl group. R ₃₃ is preferably a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, or a —COOR ₃₄ group (where R ₃₄ represents A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.

R ₃₁ and R ₃₂ may be in any position as long as they are substituted on the benzene ring, but are preferably substituted on the 2-position and 4-position of the hydroxyl group.

(General formula (IIb))
T represents a hydrogen atom or a substituted or unsubstituted alkyl group. T is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms.
T ₁ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. T ₁ is preferably a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.

-L- represents a divalent linking group or a single bond, and m represents 0 or 1.
When m is 0, it represents a case where T ₂ is directly bonded to a benzene ring without L being interposed, that is, a case where -L- represents a simple bond.
The divalent linking group -L- will be described. -L- is a divalent substituent represented by the following general formula (a).
Formula (a)
_{- (L 1) m1 - (} L 2) m2 - (L 3) m3 - (L 4) m4 - (L 5) m5 -

In general formula (a), m1-m5 represent the integer of 0-2.
L _{1 to} L ₅ are each independently —CO—, —O—, —SO ₂ —, —SO—, —NR _L —, a substituted or unsubstituted divalent alkyl group, substituted or unsubstituted 2 Represents a valent alkenyl group or a substituted or unsubstituted divalent aryl group. R _L represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

Specific examples of _RL include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a phenyl group, and a naphthyl group. A monovalent substituent may be present at any position on the alkyl group and the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. R _L is preferably a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. More preferably, it is a substituted or unsubstituted alkyl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

That The-L-2 monovalent _{substituent, -O-CO-C 2 H} 4 -CO-O -, - O-CO-C 3 H 6 -, - NH-CO-C 3 H 6 -CO- NH -, - NH-CO- C 4 H 8 -, - CH 2 -, - C 2 H 4 -, - C 3 H 6 -, - C 4 H 8 -, - C 5 H 10 -, - C 8 H ₁₆ —, —C ₄ H ₈ —CO—O—, —C ₆ H ₄ —C ₆ H ₄ —, —NH—SO ₂ —C ₃ H ₆ — and the like are preferable.

In the general formula (IIb), n represents an integer of 1 to 4.
When n is 1, T ₂ represents a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. When n is 1, T ₂ is preferably a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.

When n is 2, T ₂ represents a divalent substituent. Specific examples of T ₂ when n is 2 include the above divalent substituents -L-. When n is 2, T ₂ is preferably —CH ₂ —, —O—CO—C ₂ H ₄ —CO—O—, —NH—CO—C ₃ H ₆ —CO—NH—.

When n is 3, T ₂ represents a trivalent substituent. The trivalent substituent will be described. The trivalent substituent is a trivalent alkyl group, a trivalent aryl group, or the following general formula

It is a substituent represented by these.
Among the trivalent substituents, preferably a trivalent alkyl group having 1 to 8 carbon atoms, a trivalent aryl group having 6 to 14 carbon atoms, or the following general formula:

It is a substituent represented by these.
When n is 4, T ₂ represents a tetravalent substituent. The tetravalent substituent will be described. The tetravalent substituent is a substituent represented by a tetravalent alkyl group or a tetravalent aryl group. Of the tetravalent substituents, a tetravalent alkyl group having 1 to 8 carbon atoms and a tetravalent aryl group having 6 to 14 carbon atoms are preferable.

In general formula (IIb), it is particularly preferred that n is 1 or 2.
That is, as a preferable combination of the general formula (IIb),
when n is 1, T is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, T ₁ is a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, An aryl group having 6 to 24 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, wherein L is —O—CO—C ₃ H ₆ —, —CH ₂ —, —C ₃ H ₆ —, —C ₅ H; ₁₀ −, —C ₈ H ₁₆ —, —NH—CO—C ₄ H ₈ — or a simple bond, and T ₂ is a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or 6 carbon atoms It is a combination of 24 to 24 substituted or unsubstituted aryl groups.
When n is 2, T is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and T ₁ is a hydrogen atom, a chlorine atom, or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms. Group, an aryl group having 6 to 24 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, L is —CH ₂ — or a simple bond, and T ₂ is —CH ₂ —, —O—CO—C. ₂ H ₄ —CO—O— or —NH—CO—C ₃ H ₆ —CO—NH—.
When n is 2, m is 0, T is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and T ₁ is a hydrogen atom, a chlorine atom, or a carbon atom having 1 to 18 carbon atoms. A substituted or unsubstituted alkyl group, an aryl group having 6 to 24 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and T ₂ is —CH ₂ —, —O—CO—C ₂ H ₄ —CO—. A combination that is O— or —NH—CO—C ₃ H ₆ —CO—NH— is also preferable.

  Representative examples of the compound represented by the general formula (IIa) or (IIb) include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 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) benzotriazole, 2- (2'-hydroxy-3'-(3,4,5,6-tetrahydrophthalimidylmethyl) -5'-methylbenzyl) phenyl) benzo Triazole, 2- (3′-sec-butyl-5′-t-butyl-2′-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-bis- (α, α-dimethylbenzyl) -2 ′ -Hydroxyphenyl) benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-t -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) phenylben Triazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol], 2- [3'-t-butyl-5 ' A transesterification product of-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300;

(Wherein R = 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl),
2- [2′-hydroxy-3 ′-(α, α-dimethylbenzyl) -5 ′-(1,1,3,3-tetramethylbutyl) -phenyl] benzotriazole; 2- [2′-hydroxy- And 3 ′-(1,1,3,3-tetramethylbutyl) -5 ′-(α, α-dimethylbenzyl) -phenyl] benzotriazole.

  The triazine compound is preferably a compound having an effective absorption wavelength of about 270 to 380 nm and represented by the following general formula (III).

[In the general formula (III),
The substituent Y ₁ is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. Lf represents a divalent linking group or a single bond.
u is 1 or 2, v is 0 or 1, and r is an integer from 1 to 3,
When u is 1, Y ₂ is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. When u is 2, Y ₂ represents a divalent substituent. ]

Y ₁ represents, independently of each other, a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. Y ₁ is preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, or a substituted or unsubstituted group having 1 to 18 carbon atoms. It is a substituted alkoxy group.

Lf represents a divalent linking group or a simple bond. u represents 1 or 2; r represents an integer of 1 to 3. v is 0 or 1, and when v is 0, Lf represents a simple bond.
The divalent linking group -Lf- will be described. The divalent substituent Lf is a divalent substituent represented by the following general formula (b).
General formula (b)
− (Lf ₁ ) _{mf 1} − (Lf ₂ ) _{mf 2} − (Lf ₃ ) _{mf 3} − (Lf ₄ ) _{mf 4} − (Lf ₅ ) _{mf 5} −

In general formula (b), mf1-mf5 represents the integer of 0-2.
Lf _{1 to} Lf ₅ are each independently —CO—, —O—, —SO ₂ —, —SO—, —NRf _L —, a divalent substituted or unsubstituted alkyl group, divalent substituted or unsubstituted. It represents a substituted alkenyl group or a divalent substituted or unsubstituted aryl group. Rf _L represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

Specific examples of Rf _L include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a phenyl group, and a naphthyl group. A monovalent substituent may be present at any position on the alkyl group and the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Rf _L is preferably a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. More preferably, it is a substituted or unsubstituted alkyl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

That is, as the divalent substituent _{-Lf-, -O-CO-C 2} H 4 -CO-O -, - O-CO-C 3 H 6 -, - NH-CO-C 3 H 6 -CO- NH -, - NH-CO- C 4 H 8 -, - CH 2 -, - C 2 H 4 -, - C 3 H 6 -, - C 4 H 8 -, - C 5 H 10 -, - C 8 H ₁₆ —, —C ₄ H ₈ —CO—O—, —C ₆ H ₄ —C ₆ H ₄ —, —NH—SO ₂ —C ₃ H ₆ — and the like are preferable.

When u is 1, Y ₂ is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. When u is 1, Y ₂ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.

When u is 2, Y ² represents a divalent substituent. Examples of the divalent substituent include the examples of the above divalent substituent -L-. Y ₂ is preferably a substituted or unsubstituted divalent alkyl group, a substituted or unsubstituted divalent alkenyl group, a substituted or unsubstituted divalent aryl group, —CH ₂ CH (OH) CH ₂ —O. _{-Y 11 -OCH 2 CH (OH)} CH 2 -, - CO-Y 12 -CO -, - CO-NH-Y 13 -NH-CO-, or _{- (CH 2) t -CO 2} -Y 14 - OCO— (CH ₂ ) _t —.
Where t is 1, 2 or 3;
Y ₁₁ represents a substituted or unsubstituted alkylene, phenylene, or -phenylene-M-phenylene- (where M is —O—, —S—, —SO ₂ —, —CH ₂ — or —C (CH ₃ ) ₂ −))
Y ₁₂ is a substituted or unsubstituted divalent alkyl group, a substituted or unsubstituted divalent alkenyl group, or a substituted or unsubstituted divalent aryl group,
Y ₁₃ is a substituted or unsubstituted divalent alkyl group, or a substituted or unsubstituted divalent aryl group, and Y ₁₄ is a substituted or unsubstituted divalent alkyl group, or substituted or unsubstituted Of the divalent aryl group.

That is, when u is 2, Y ₂ is preferably a substituted or unsubstituted divalent alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 24 carbon atoms, —CH _{2. CH (OH) CH 2 -O-} CH 2 -OCH 2 CH (OH) CH 2 -, - CH 2 CH (OH) CH 2 -O-C (CH 3) 2 -OC 8 H 16 -, or - ( _{CH 2) 2 -CO 2 -C 2} H 4 -OCO- (CH 2) 2 - is.

  Representative examples of the compound represented by the general formula (III) 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- (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) -Butyloxypropo Si) 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-) Meto Xylphenyl) -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-hydroxyphenyl) -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) And (oxy) phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine.

  As the benzophenone compound, a compound having an effective absorption wavelength of about 270 to 380 nm is preferable, and a compound represented by the following general formula (IVa) or (IVb) is preferable.

[In the general formula (IVa), X ₁₁ and X ₁₂ are each independently a hydrogen atom, halogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted. Alkoxy group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, sulfonic acid group, substituted or unsubstituted alkyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, or substituted or unsubstituted Represents a substituted amino group. s1 and s2 each independently represent an integer of 1 to 3. ]

[In the general formula (IVb), X ₁₁ represents a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. An alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a sulfonic acid group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted amino group, Represents an integer of 1 to 3.
Lg represents a divalent substituent or a simple bond, and w represents 0 or 1.
tb represents 1 or 2, and when tb is 1, X ₁₃ represents a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group, Substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, sulfonic acid group, substituted or unsubstituted alkyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, or substituted or unsubstituted amino group Represents. When tb is 2, X ₁₃ represents a divalent substituent. ]

(General formula (IVa))
X ₁₁ and X ₁₂ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted It represents an alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a sulfonic acid group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted amino group. X ₁₁ and X ₁₂ are preferably a hydrogen atom, a chlorine atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, or 1 to 1 carbon atoms. 18 substituted or unsubstituted alkoxy groups, alkyloxycarbonyl groups having 2 to 18 carbon atoms, aryloxycarbonyl groups having 7 to 24 carbon atoms, sulfonic acid groups, or substituted or unsubstituted amino groups having 1 to 16 carbon atoms It is. X ₁₁ and X ₁₂ are particularly preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms.

(General formula (IVb))
tb is 1 or 2, w is 0 or 1, and s1 is an integer of 1 to 3.
Substituent X ₁₁ represents a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylsulfonyl group, a substituted or It represents an unsubstituted arylsulfonyl group, a sulfonic acid group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted amino group.

X ₁₁ is preferably a hydrogen atom, a chlorine atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, or a substituted group having 1 to 18 carbon atoms. Alternatively, it is an unsubstituted alkoxy group, an alkyloxycarbonyl group having 2 to 18 carbon atoms, an aryloxycarbonyl group having 7 to 24 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms. X ₁₁ is particularly preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms.

-Lg- represents a divalent linking group or a simple bond, and w represents an integer of 0 to 1. When w is 0, X ₃ is directly bonded to the benzene ring without Lg, that is, -Lg- represents a simple bond.
The divalent linking group -Lg- will be described. The divalent substituent Lg is a divalent substituent represented by the following general formula (c).
Formula (c)
− (Lg ₁ ) _{mg 1} − (Lg ₂ ) _{mg 2} − (Lg ₃ ) _{mg 3} − (Lg ₄ ) _{mg 4} − (Lg ₅ ) _{mg 5} −

In general formula (c), mg1 to mg5 represent an integer of 0 to 2.
Lg _{1 to} Lg ₅ are each independently —CO—, —O—, —SO ₂ —, —SO—, —NRg _L —, a substituted or unsubstituted divalent alkyl group, substituted or unsubstituted 2 Represents a valent alkenyl group or a substituted or unsubstituted divalent aryl group. Rg _L represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

Specific examples of Rg _L include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a phenyl group, and a naphthyl group. A monovalent substituent may be present at any position on the alkyl group and the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Rg _L is preferably a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. More preferably, it is a substituted or unsubstituted alkyl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

That is, as the divalent substituent -Lg-, -O -, - O- CO-C 2 H 4 -CO-O -, - O-C 4 H 8 -O -, - O-CO-C 3 H _{6 -, - NH-CO-} C 3 H 6 -CO-NH -, - NH-CO-C 4 H 8 -, - CH 2 -, - C 2 H 4 -, - C 3 H 6 -, - C _{4 H 8 -, - C 5} H 10 -, - C 8 H 16 -, - C 4 H 8 -CO-O -, - C 6 H 4 -C 6 H 4 -, - NH-SO 2 -C 3 H _6- and the like are preferable.

When tb is 1, X ₁₃ is a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylsulfonyl group A substituted or unsubstituted arylsulfonyl group, a sulfonic acid group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted amino group.
When tb is 1, X ₁₃ is preferably a hydrogen atom, a hydroxyl group, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, carbon A substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, an alkyloxycarbonyl group having 2 to 18 carbon atoms, an aryloxycarbonyl group having 7 to 24 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted group having 1 to 16 carbon atoms Of the amino group.
X ₁₃ is particularly preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms.

When tb is 2, X ₁₃ represents a divalent substituent.
When tb is 2, specific examples of X ₁₃ include the above divalent substituent -L-. When tb is 2, X ₃ is preferably —CH ₂ —, —C ₄ H ₈ —, —O—C ₄ H ₈ —O—, —O—CO—C ₂ H ₄ —CO—O—, or -NH-CO-C ₃ H ₆ is -CO-NH-.

In the general formula (IVb), it is particularly preferable that tb is 1.
That is, preferred combinations of the general formula (IVb) are as follows.
Specifically, when tb is 1,
X ₁₁ is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms,
Lg is —O—, —O—CO—C ₂ H ₄ —CO—O—, —O—C ₄ H ₈ —O—, —O—CO—C ₃ H ₆ —, —NH—CO—C _3. H ₆ —CO—NH—, —NH—CO—C ₄ H ₈ —, —CH ₂ —, —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ —, —C ₈ H ₁₆ —, —C ₄ H ₈ —CO—O—, —C ₆ H ₄ —C ₆ H ₄ —, or —NH—SO ₂ —C ₃ H ₆ —, or a simple bond. ,
X ₁₃ is a hydrogen atom, a hydroxyl group, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted group having 1 to 18 carbon atoms The combination which is a C2-C18 alkyloxycarbonyl group, a C7-24 aryloxycarbonyl group, a sulfonic acid group, or a C1-C16 substituted or unsubstituted amino group is preferable.

When tb is 2,
X ₁₁ is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms,
Lg is —O—, —O—CO—C ₂ H ₄ —CO—O—, —O—C ₄ H ₈ —O—, —O—CO—C ₃ H ₆ —, —NH—CO—C _3. H ₆ —CO—NH—, —NH—CO—C ₄ H ₈ —, —CH ₂ —, —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ —, —C ₈ H ₁₆ —, —C ₄ H ₈ —CO—O—, —C ₆ H ₄ —C ₆ H ₄ —, or —NH—SO ₂ —C ₃ H ₆ —, or a simple bond. ,
X ₁₃ is —CH ₂ —, —C ₄ H ₈ —, —O—C ₄ H ₈ —O—, —O—CO—C ₂ H ₄ —CO—O—, or —NH—CO—C ₃ H. A combination that is _6- CO-NH- is preferred.

  Representative examples of the benzophenone compounds 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'-hexyloxycarbonylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 1,4-bis (4-benzyloxy-3-hydroxyphenoxy) butane and the like.

  The salicylic acid-based compound is preferably a compound having an effective absorption wavelength of about 290 to 330 nm, and typical examples thereof include phenyl salicylate, 4-t-butylphenyl salicylate, 4-octylphenyl salicylate, dibenzoylresorcinol, bis ( 4-t-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxysalicylate, hexadecyl 3,5-di-t-butyl-4- Hydroxy salicylate and the like can be mentioned.

  The acrylate compound is preferably a compound having an effective absorption wavelength of about 270 to 350 nm, and typical examples thereof 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'-diphenyl Acryloyl) oxy) -2,2-bis (((2′-cyano-3,3′-diphenylacryloyl) oxy) methyl) propane, N- (2-carbomethoxy-2-cyanovinyl) -2-methylindoline, etc. Can be mentioned.

  The oxalic acid diamide compound preferably has an effective absorption wavelength of about 250 to 350 nm. Typical examples thereof include 4,4′-dioctyloxyoxanilide and 2,2′-dioctyloxy-5. 5′-di-t-butyl oxanilide, 2,2′-didodecyloxy-5,5′-di-t-butyl oxanilide, 2-ethoxy-2′-ethyl oxanilide, N, N '-Bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide, 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxa Nilide etc. can be mentioned.

  In addition to the ultraviolet absorber represented by the general formula (1) and the compound represented by the above (TS-I) or (TS-II), the ultraviolet absorber composition of the present invention can be used depending on the purpose. In addition, any other compound can be appropriately contained as the other component.

The total content of the ultraviolet absorber represented by the general formula (1) is preferably greater than 0% by mass and 90% by mass or less, more preferably 5% by mass with respect to the entire ultraviolet absorber composition. % Or more and 90% by mass or less, particularly preferably 10% by mass or more and 90% by mass or less.
Moreover, the total content of the compound represented by the general formula (TS-I) or (TS-II) is preferably greater than 0% by mass and 80% by mass or less with respect to the entire ultraviolet absorbent composition. More preferably, it is the case of 1 mass% or more and 60 mass% or less, Most preferably, it is the case of 1 mass% or more and 50 mass% or less.

  In the ultraviolet absorbent composition of the present invention, the mixing ratio of the ultraviolet absorbent represented by the general formula (1) and the compound represented by the general formula (TS-I) or (TS-II) is a molar ratio. The ratio is preferably 20: 1 to 1:20, more preferably 10: 1 to 1:10, particularly preferably 10: 1 to 1: 1. In the description of the above-mentioned ratio of A: B, A is the ratio of the ultraviolet absorber represented by the general formula (1), and B is the general formula (TS-I) or (TS-II). Represents the proportion of the compound represented. When the compound represented by the general formula (TS-I) or (TS-II) is a polymer, the molar ratio is calculated using the formula amount of the repeating unit constituting the polymer. .

  The combination of the compound represented by the general formula (1) and the compound represented by the general formula (TS-I) or (TS-II) is represented by the compound represented by the general formula (2) and the general formula (TS-I). The combination of the compound represented and the combination of the compound represented by the general formula (2) and the compound represented by the general formula (TS-II) are preferable, and the compound represented by the general formula (2) and the general formula (TS-Ia) The combination of compounds represented is particularly preferred.

  In the ultraviolet absorbent composition of the present invention, the ultraviolet absorbent represented by the general formula (1) and the compound represented by the general formula (TS-I) or (TS-II) are each present alone. However, they may be linked to each other in advance or by forming a bond in the composition. In addition, a monomer is obtained by bonding a polymerizable group, and the ultraviolet absorber represented by the general formula (1) and the general formula (TS-I) or (TS-II) are represented by polymerizing the monomer. It may be a copolymer containing a compound to be formed in a unit structure. Another monomer not bonded to these may be used in combination to form a copolymer. Preferably, the composition as a monomer is a case where polymerization is performed at a desired time to form a copolymer.

  The ultraviolet absorbent composition of the present invention may be in any form. For example, in the form of a homogeneous mixture of the ultraviolet absorber represented by the general formula (1) and the compound represented by the general formula (TS-I) or (TS-II), or using a medium, a polymer, or the like. , Liquid dispersions, solutions, polymer materials and the like. The ultraviolet absorbent composition of the present invention exhibits ultraviolet absorption with a maximum absorption wavelength of 330 to 410 nm as a dispersion, solution or the like.

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

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

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

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

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

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

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

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

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

  The solution of the ultraviolet absorbent composition of the present invention may contain any other compound in addition. Examples thereof include dyes, pigments, infrared absorbers, fragrances, polymerizable compounds, polymers, inorganic substances, metals, and the like. Other than the ultraviolet absorbent composition of the present invention, it does not necessarily have to be dissolved.

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

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

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

  The total content of the ultraviolet absorbent composition of the present invention with respect to the polymer material is preferably greater than 0% by mass and 50% by mass or less, more preferably 0% by mass or more and 40% by mass with respect to the entire polymer material. It is a case of mass% or less, and particularly preferably 0 mass% or more and 30 mass% or less. The ultraviolet absorber composition of the present invention has an excellent feature that no bleed-out is observed when used at a low concentration of 0 to 10% by mass, and no bleed-out is observed even when used at a high concentration of 10% by mass or more. Have.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<19> Polycarbonate and polyester carbonate.

<20> Polyketone.

<21> Polysulfone, polyethersulfone and polyetherketone.

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

<23> Dry and non-dry alkyd resins.

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

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

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

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

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

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

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

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

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

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

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

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

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

The polymer material of the present invention comprises the above polymer substance. The polymer material of the present invention may be formed only from the polymer substance, or may be formed by dissolving the polymer substance in an arbitrary solvent.
The polymer material of the present invention can be used for all applications in which a synthetic resin is used, but can be particularly preferably used for applications that may be exposed to sunlight or light including ultraviolet rays. Specific examples include, for example, glass substitutes and surface coating materials thereof, window glass for houses, facilities, and transportation equipment, coating materials for daylighting glass and light source protection glass, interior and exterior materials and interior and exterior materials for housing, facilities, and transportation equipment. Materials for light sources that emit ultraviolet rays such as clothing paints, fluorescent lamps, mercury lamps, precision machinery, components for electronic and electrical equipment, shielding materials for electromagnetic waves generated from various displays, containers or packaging materials for food, chemicals, chemicals, etc. Industrial sheet or film material, anti-fading agent such as printed matter, dyed matter and dyeing pigment, sunscreen cream, shampoo, rinse, hairdressing cosmetics, sportswear, stockings, hats and other textile products for textiles and textiles, curtains , Carpets, wallpaper and other home interior items, plastic lenses, contact lenses, artificial eyes, and other medical instruments, optical filters, prisms, mirrors, photos Optical articles such as the material, a tape, such as ink stationery, sign plate, and a marking device such as a surface coating material or the like.

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

  Since the polymer material of the present invention contains the ultraviolet absorbent composition of the present invention, it has excellent light resistance (fastness to ultraviolet light), and bleeding out due to precipitation of the ultraviolet absorbent or long-term use. Will not occur. In addition, since the polymer material of the present invention has an excellent long-wave ultraviolet absorbing ability, it can be used as an ultraviolet absorbing filter or a container, and can protect compounds that are sensitive to ultraviolet rays. For example, a molded product (such as a container) made of the polymer material of the present invention can be obtained by molding the polymer substance by any method such as extrusion molding or injection molding. In addition, a molded article coated with the ultraviolet absorbing film made of the polymer material of the present invention can be obtained by applying and drying the polymer substance solution to a separately produced molded article.

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

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

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

  The packaging material containing the ultraviolet absorbent composition 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. It may be.

  The packaging material containing the ultraviolet absorbent composition 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 combines other performances. You may have it. For example, those having gas barrier properties described in JP-A-2002-160321, those containing an oxygen indicator described in JP-A-2005-156220, for example, described in JP-A-2005-146278 And a combination of an ultraviolet absorber and an optical brightener.

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

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

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

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

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

  The coating material and coating film containing the ultraviolet absorber composition of the present invention will be described. The paint containing the ultraviolet absorbent composition of the present invention includes the ultraviolet absorbent represented by the general formula (1) and the compound represented by the general formula (TS-I) or (TS-II). Any paint may be used. 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 absorbent composition of the present invention may be any use. For example, the ultraviolet shielding paint described in JP-A-7-26177, JP-A-9699950, JP-A-9-221631, JP2002-80788, UV described in JP-A-10-88039 Near-infrared shielding paint, electromagnetic wave shielding paint described in JP-A-2001-55541, clear paint described in JP-A-8-81643, metallic paint composition described in JP-A-2000-186234, Cationic electrodeposition paint described in Kaihei 7-166112, antibacterial and lead-free cationic electrodeposition paint described in JP-A-2002-294165, JP-A 2000-273362, JP-A-2001-279189, Powder paint described in JP-A-2002-271227, water-borne intermediate coating, water-based metallic paint described in JP-A-2001-9357, water-based clear paint, automobile and architecture described in JP-A-2001-316630 Paints for top coating used in products and civil engineering products, curable paints described in JP-A No. 2002-356655, JP-A No. 2004-937 Coating film-forming composition used for plastic materials such as automobile bumpers described in the report, paint for metal plates described in JP-A-2004-2700, cured gradient coating film described in JP-A-2004-169182, The coating material for electric wires described in JP-A-2004-107700, the automobile repair paint described in JP-A-6-49368, the anion electrodeposition described in JP-A-2002-38084 and JP-A-2005-307161 Paint, JP-A-5-78606, JP-A-5-85031, JP-A-10-140089, JP2000-509082, JP2004-520284, WO2006 / 097201 pamphlet Paints for automobiles, paints for coated steel sheets described in JP-A-6-945, stainless steel paints described in JP-A-6-313148, insect repellent paints for lamps described in JP-A-7-3189, UV-curable coatings described in JP-A-7-82454, antibacterial coatings described in JP-A-7-118576, and eyestrain described in JP-A-2004-217727 Work prevention paint, anti-fogging paint described in JP-A-2005-314495, super-weather resistant paint described in JP-A-10-298493, gradient paint described in JP-A-9-241534, JP-A 2002 -235028 photocatalyst paint, JP-A 2000-345109 peelable paint, JP-A 6-346022 concrete peeling paint, JP-A 2002-167545 anti-corrosion Paint, protective paint described in JP-A-8-324576, water-repellent protective paint described in JP-A-9-12924, paint for preventing sheet glass scattering described in JP-A-9-57581, JP-A-9- No. 59539, alkali-soluble protective coating, JP-A-2001-181558, water-based temporary protective coating composition, JP-A-10-183057, floor coating, JP-A-2001-115080 Emulsion paint described in Japanese Patent Laid-Open No. 2001-262056, two-component water-based paint described in Japanese Patent Laid-Open No. 2001-262056, one-component paint described in Japanese Patent Laid-Open No. 9-263729, UV curable paint described in JP 2001-288410 A, electron beam curable coating composition described in JP 2002-69331 A, thermosetting paint composition described in JP 2002-80781 A, special table Water-based paint for baking lacquer described in 2003-525325, powder paint and slurry paint described in Japanese Patent Application Laid-Open No. 2004-162021, paint for repair described in Japanese Patent Application Laid-Open No. 2006-233010, 11- An aqueous dispersion of powder coating material described in Japanese Patent No. 514689, a coating material for plastics described in Japanese Patent Application Laid-Open No. 2001-59068, Japanese Patent Application Laid-Open No. 2006-160847, and an electron beam curable coating material described in Japanese Patent Application Laid-Open No. 2002-69331 Etc.

  The paint containing the ultraviolet absorbent composition of the present invention is generally composed of a paint (including a transparent resin component as a main component) and an ultraviolet absorbent composition. Preferably, the ultraviolet ray of the general formula (1) is applied to the resin. The total content of the absorbent and the compound represented by the general formula (TS-I) or (TS-II) is more than 0 and 20% by mass or less. The thickness at the time of application is preferably 2 to 1000 μm, more preferably 5 to 200 μm. The method of applying these paints is arbitrary, but there are a spray method, a dipping method, a roller coat method, a flow coater method, a flow coating method and the like. Although drying after application varies depending on the paint components, it is preferably performed at room temperature to 120 ° C. for about 10 to 90 minutes.

  The coating film coated with the paint containing the ultraviolet absorbent composition of the present invention comprises the ultraviolet absorbent represented by the general formula (1) and the compound represented by the general formula (TS-I) or (TS-II). It is a coating film formed using the coating material containing said ultraviolet absorber composition of this invention.

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

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

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

  You may manufacture the fiber containing the ultraviolet absorber composition of this invention by any method. For example, as described in JP-A-62-281818, an ultraviolet absorber represented by the general formula (1) and a compound containing the compound represented by the general formula (TS-I) or (TS-II) in advance are included. The molecule may be processed into a fiber shape, for example, for those processed into a fiber shape as described in JP-A-5-9870, JP-A-8-188921, JP-A-10-1587 You may process using the solution etc. which contain the compound represented by the said General formula (1). As described in JP 2002-212884 A and JP 2006-16710 A, treatment may be performed using a supercritical fluid.

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

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

  The building material containing the ultraviolet absorbent composition of the present invention may be produced by any method. For example, as described in JP-A-8-269850, a material containing an ultraviolet absorber represented by the general formula (1) and a compound represented by the general formula (TS-I) or (TS-II) And may be formed into a desired shape. For example, as described in JP-A-10-205056, the ultraviolet absorber represented by the general formula (1) and the general formula (TS-I) or ( A material containing a compound represented by TS-II) may be formed by laminating, and for example, as described in JP-A-8-151457, an ultraviolet absorber represented by the general formula (1) and You may form the coating layer using the compound represented by the said general formula (TS-I) or (TS-II), for example, as described in Unexamined-Japanese-Patent No. 2001-172531, the said general formula ( 1) and the general formula (TS-I) or (TS-I) The compound represented by) coating may be formed by coating the containing.

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

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

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

  The cover for solar cells containing the ultraviolet absorbent composition 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. Also, in dye-sensitized solar cells, as described in JP-A-2006-282970, a metal oxide semiconductor that becomes active when excited by light (particularly ultraviolet rays) is used as an electrode material, so that it is adsorbed as a photosensitizer. There is a problem that the dyes that have been deteriorated and the photovoltaic power generation efficiency gradually decreases, and it has been proposed to provide an ultraviolet absorbing layer.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Example 1
(Evaluation of thermal stability)
A predetermined amount of the ultraviolet absorber A represented by the general formula (1) and the compound represented by the general formula (TS-I) (additive B) are mixed, the mixed powder is placed on a slide glass, and hot The plate was heat-treated at 280 ° C. for 30 minutes. The sample after heat treatment was dissolved in ethyl acetate, the absorption spectrum was measured, and the sample was compared with the spectrum of the sample before heat treatment. From the obtained spectrum chart, the absorbance at a wavelength of 400 nm relative to the absorbance at the maximum absorption wavelength and the maximum absorption wavelength was calculated.
As a comparative example, the same comparison was made for a sample in which additive B was not mixed and only ultraviolet absorber A was heat-treated under the same conditions as described above. The results are shown in Table 4 below.

As shown in Table 4, with the ultraviolet absorber alone, the absorbance at 400 nm increased after the heat treatment, and coloring was observed accordingly. This is not preferable when used as an ultraviolet absorber. On the other hand, those containing the ultraviolet absorber represented by the general formula (1) and the compound represented by the general formula (TS-I) remarkably suppress the increase in absorbance at 400 nm as seen in the comparative example. It was done. This effect was similarly seen even when the addition amount was reduced to 1/10.
The above heat treatment conditions are almost the same as those used when kneading PET, which is a general-purpose polymer, and it is clear that the UV-absorbing composition of the present invention is also suitably used for kneading polymers that require high-temperature processes. It is.

Example 2
(Preparation of UV-absorbing PET film)
With respect to 5 g of polyethylene terephthalate, Example Compound (52) was added so that the absorbance at the maximum absorption wavelength was 1.0 when a 50 μm film was produced. Further, Example Compound (TI-57) was equimolar with Example Compound (52). After adding the amount, melt kneading at 265 ° C. for 30 minutes and then cooling, a bulk UV agent-containing polyethylene terephthalate was obtained. The UV agent-containing polyethylene terephthalate was stretched at 280 ° C. to prepare an ultraviolet absorbing composition-containing polymer film sample 101. Moreover, the film samples 102-104 were produced by the same method except having changed exemplary compound (52).
As a comparative example, Exemplified Compound (34) or Exemplified Compound (52) was used as an ultraviolet absorber, and film samples 105 and 106 were produced in the same manner as described above except that Exemplified Compound (TI-57) was not added.

(Evaluation)
The prepared film sample was visually observed, and x was marked when the color derived from the thermal decomposition of the UV absorber was marked, △ was marked when slightly colored, and ○ was marked when no color was seen. did.

  As shown in Table 5, the films (105, 106) not using the compound represented by the general formula (TS-I) (additive B) are apparently derived from the thermal decomposition of the ultraviolet absorber. A brown color was observed. On the other hand, in the film samples 101 to 104 produced using the ultraviolet absorber as a composition comprising the ultraviolet absorber represented by the general formula (1) and the compound represented by the general formula (TS-I), No significant coloring was seen. In addition, the bleed-out phenomenon, which was a concern when an additive was added to the ultraviolet absorber, was not observed at all in the composition according to the present invention.

Example 3
(Preparation of UV-absorbing polymer film)
As a polyester resin, 2.58 g of Byron 200 (trade name, manufactured by Toyobo Co., Ltd., Tg = 67 ° C.) 29.1% solution (toluene-methyl ethyl ketone 1: 1 mixed solvent), 2.58 g of Exemplified Compound (56), 0.018 g and Exemplified Compound (TI-57) 0.002 g was dissolved, applied on a slide glass with a wire bar so that the dry film thickness was about 5 μm, and the absorbance at the maximum absorption wavelength of the polymer film was about 1, and this was dried. Thus, a polymer film sample 201 having ultraviolet absorbing ability was produced. In addition, the example compound (56) was replaced with the example compound (34), and the polymer film sample 202 was similarly prepared except that the addition amount of the example compound was adjusted so that the absorbance at the maximum absorption wavelength of the polymer film was about 1. Was made. Furthermore, a polymer film sample 203 was produced in the same manner as the polymer film sample 201 except that the exemplified compound (TI-57) was replaced with (TII-17).
As a comparative example, a polymer film sample 204 was produced in the same manner except that the exemplified compound (TI-57) was not added.

  The produced polymer film sample was visually observed, but no bleed out was observed.

(Evaluation)
<Forced evaluation of light fastness>
The absorbance of each polymer film was measured using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation using a polymer film not containing an ultraviolet absorber as a reference. The polymer film was irradiated with xenon light (170000 lux) for 165 hours, and the residual ratio of the ultraviolet absorber after irradiation was measured. The residual rate was calculated according to the following formula.
Residual rate (%) = 100 × (absorbance after irradiation) / (absorbance before irradiation)
The absorbance is a value measured at the maximum absorption wavelength of the polymer film.

  As shown in Table 6, it was prepared from a composition in which the compound represented by the general formulas (TS-I) and (TS-II) (additive B) was added to the ultraviolet absorber represented by the general formula (1). The film (201, 202, 203) was more stable to light than the film (204) not using additive B.

  As described above, the ultraviolet absorbing composition according to the present invention has excellent long wave ultraviolet absorbing ability, can be mixed with a polymer resin by a high temperature process, has excellent light stability, and does not cause bleed out. Met.

Claims (10)

UV absorption characterized by comprising at least one UV absorber represented by the following general formula (1) and at least one compound represented by the following general formula (TS-I) or (TS-II) Agent composition.

(In the general formula (1), ^{X 1} and ^{X 2} each independently represent an oxygen atom, a sulfur atom or ^{-NR 17} - ^{represents, 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.)

[In the general formula (TS-I), R ₉₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted group. Or an unsubstituted acyl group, a substituted or unsubstituted alkyl or alkenyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or -Si (R ₉₇ ) (R ₉₈ ) (R ₉₉ ) is represented. Here, R ₉₇ , R ₉₈ and R ₉₉ may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group or an aryloxy group. —X ₉₁ — represents —O—, —S— or —N (—R ₁₀₀ ) —. Here, R ₁₀₀ is synonymous with R ₉₁ . R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ and R ₉₆ may be the same as or different from each other, and each represents a hydrogen atom or a substituent. However, R ₉₁ , R ₉₂ , R ₉₃ , R ₉₄ , R ₉₅ , R ₉₆ and R ₁₀₀ are not all hydrogen atoms, and the total number of carbon atoms is 10 or more.
In general formula (TS-II), R ₁₀₁ , R ₁₀₂ , R ₁₀₃ , and R ₁₀₄ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, and R ₁₀₁ and R ₁₀₂ , R ₁₀₃ and R ₁₀₄ may combine to form a 5- to 7-membered ring. X ₁₀₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted alkyl or alkenyloxycarbonyl Group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkyloxycarbonyloxy group, substituted or unsubstituted alkenyloxycarbonyloxy group, Substituted or unsubstituted aryloxycarbonyloxy group, substituted or unsubstituted alkyl or alkenylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkyl or alkenylsulfinyl group Represents a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted carbamoyl group, a hydroxy group, or an oxy radical group. X ₁₀₂ represents a hetero atomic group necessary for forming a 5- to 7-membered ring. ] The ultraviolet absorber composition according to claim 1, wherein the ultraviolet absorber represented by the general formula (1) is an ultraviolet absorber 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 ultraviolet ray according to claim 1 or 2, wherein the total content of the ultraviolet absorber represented by the general formula (1) or (2) is greater than 0% by mass and equal to or less than 90% by mass with respect to the entire composition. Absorbent composition.   Any of Claims 1-3 whose total content of the compound represented by the said general formula (TS-I) or (TS-II) is more than 0 mass% and 80 mass% or less with respect to this whole composition. The ultraviolet absorber composition according to claim 1.   The mixing ratio of the ultraviolet absorber represented by the general formula (1) or (2) and the compound represented by the general formula (TS-I) or (TS-II) is 10: 1 to 1 in terms of molar ratio. The ultraviolet absorber composition according to any one of claims 1 to 4, which is 1.   The ultraviolet absorber composition according to any one of claims 1 to 5, comprising at least one compound represented by the general formula (TS-I). The ultraviolet absorber composition according to any one of claims 1 to 6, wherein the compound represented by the general formula (TS-I) is a compound represented by the following general formula (TS-Ia).

(In the general formula (TS-Ia), R ₉₂ , R ₉₃ , R ₉₅ , R ₉₆ , R ₈₂ , R ₈₃ , R ₈₅ , R ₈₆ may be the same as or different from each other, and each represents a hydrogen atom or a substituent. Provided that R ₉₂ , R ₉₃ , R ₉₅ , R ₉₆ , R ₈₂ , R ₈₃ , R ₈₅ , and R ₈₆ are not all hydrogen atoms, L _p represents a linking group, and n is 0 or Represents an integer of 1)   The ultraviolet absorber dispersion containing the ultraviolet absorber composition of any one of Claims 1-7.   The ultraviolet absorber solution containing the ultraviolet absorber composition of any one of Claims 1-7.   The polymeric material containing the ultraviolet absorber composition of any one of Claims 1-7.